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ISSN 0369-0369 VOLUME 61,2004 MEMOIRS OF THE nstitute of I cientific and S ndustrial I esearch R OSAKA UNIVERSITY
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Page 1: MEMOIRS VOLUME61

ISSN 0369-0369

VOLUME 61,2004

MEMOIRS OF THE

nstitute ofIcientific andSndustrialIesearchR

OSAKA UNIVERSITY

Page 2: MEMOIRS VOLUME61

Contents

Foreword 111 ・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・

Outline of ISIR 1. Research Activities 112 2. Education 113 3. International Exchange 114 4. Concluding Remarks 115

Activities of Divisions Quantum Engineering 119 Advanced Materials Science & Technology 153 Organic Molecular Science 109 Intelligent Systems Science 141 Biological Sciences 172 Quantum Beam Science & Technology 193

Activities of Facilities Nanoscience Nanotechnology Center 207 Materials Analysis Center 295 Service Facilities 298

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Foreword The Institute of Scientific and Industrial Research was started as a part of Osaka University in 1939. Since then, the Institute had developed into one of the leading research organization for science and engineering in our country. We are hoping that our research on materials/devices, information/intelligence, biology/biotechnology, and their interdisciplinary areas will contribute to the industries, and ultimately to the next generations. "Memoirs of the Institute of Scientific and Industrial Research (ISIR)" has witnessed the sixty-three years’ history of the Institute, since it was published in 1940, one year after the foundation of ISIR. The roles of Memoirs had been changed with time. During the first decade, its main role was to publish original research papers. However, staff of the Institute started to publish their original work in international journals, and Memoirs became a vehicle for reviews of joint researches and abstracts of papers published by the members of the Institute. Since 1997, Memoirs has become our annual publication summarizing the scientific activities of ISIR.

We report here information such as current research programs and recent findings of each laboratory, list of publications, financial supports from granting agencies, and all other scientific activities. We hope that this publication will be useful and stimulating for researchers in universities, research institutes and industries, and young scientists outside as well as inside our Institute. Masamitsu Futai Former Director,

Tomoji Kawai Present Director,

The Institute of Scientific and Industrial Research

- 1 -

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Outline of ISIR

1. Research Activities

1) History and Organization

The Institute of Scientific and Industrial Research (ISIR) was founded in 1939 as a part of Osaka University, in response to the strong requests from the industrial community of the Kansai area in Japan. The original buildings were constructed in Sakai supported financially by an association of leading private enterprises in Osaka. ISIR moved to the present place in Suita Campus in 1968. For more than half a century, ISIR has been very active as a University-associated research Institute, and dedicated to the advance of basic and applied sciences, especially in the fields of electronics, computer science, metallurgy, inorganic chemistry, organic chemistry, biochemistry, and radiation science. The Institute also has been developing industrial applications of the results obtained by staff members. We celebrated the fiftieth anniversary in 1989. In April 1995, ISIR was reorganized in order to respond effectively to the highly developed science and technology in this country. It has modified its structure to expand basic original research, and to promote interdisciplinary programs based on the three major fields: material sciences, information sciences, and biological sciences. ISIR has at present six research divisions and two institute-associated research centers. The organization of ISIR is shown on the next page. A new building was constructed in 2001 in response to the increased number of scientists. The Nanotechnology and Nanoscience Center started in April 2002. The number of staff scientists is 108 in total, including full professors, associate professors, and assistant professors. Ages and Alma Maters of professors and research staff are shown below. In almost all the large national universities in this country, most of the faculties are graduates of their own university. However, more than half of the staff scientists in ISIR were graduated from other universities. This is an exceptional case in this country, and contributes to promoting scientific activities of the Institute.

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Divisions Departments

Quantum Engineering Quantum Molecular Devices

Photonic and Electronic Materials Semiconductor Electronics Condensed Matter Physics Advanced Materials Structural Characterization and Design Science & Technology Metallic Materials Process

Atom Scale Science Functional Ceramic Materials Structure Ceramic Materials Advanced-Energy Materials Organic Molecular Science Organometallic Compounds

Organic Fine Chemicals Organic Molecular Materials Molecular Excitation Chemistry Synthetic Organic Chemistry Intelligent Systems Science Knowledge Systems

Intelligent Media Architecture for Intelligence Advanced Reasoning Biological Science Structural Molecular Biology

Molecular Cell Biology Cell Membrane Biology Quantum Beam Accelerator Science Science & Technology Beam Materials Science Research Centers (Two Centers)

Nanoscience and Division of Nanomaterials and Nanodevices Nanotechnology Center Department of Artificial Nanomaterials for

Bio-Information Systems Department of Single-Molecular Integrated Devices Department of Supramolecular Chemistry Department of Nanobiology Department of Nanodevice Characterization Department of Nanosystem Design

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Division of Beam Science for Nanotechnology Department of Beam Science for Nanofabrication Department of Quantum Beams for Nanotechnology Department of Beam Processing for Nanotechnology Department of Advanced Nanofabrication Department of Ultrafast Spectroscopy of Nanostuctures

Division of Nanoscience and Nanotechnology for Industrial Applications Department of Nanomaterials and Environmentally Conscious Technology Department of Computational Nanomaterials Design Department of Nano-Bio-Intelligent Systems Science Department of Propatent Strategy for Nanotechnology Department of Nanotechnology Transfer

Radiation Laboratory

Materials Analysis Center Service Facilities Workshop Electronic Processing Laboratory Electron Microscope Laboratory Laboratory for Radio-Isotope Experiments Library

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- 5-

Staffs, Age (years old) - As of 3. 30. 2004

ProfessorAssociateProfessor

AssistantProfessor

ResearchAssociate

Staffs, Alma Mater (As of 3. 30. 2004 )

ProfessorAssociateProfessor

AssistantProfessor

No.

60~63

35~44

50~5455~59

2

7

4

9

No. 10

7

6

1

3

60~63

50~59

45~49

40~44

35~39

No.

83

4

4

2

2

16

14

25~2960~63

55~59

50~54

45~49

40~44

35~39

30~34No.

0

No. No.

No. No.

2

10

15

Private Univ.

OtherNationalUniv.

Osaka Univ.7

20

Osaka Univ.

OtherNationalUniv.

0

16

17

6

11

ForeignUniv.

PrivateUniv.

PublicUniv.

OtherNationalUniv.

Osaka Univ.

45~495

30~34

1

ResearchAssociate

1

Private Univ.

3

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2) Administration

Administration and management of ISIR are conducted by the Director elected from the full professors of ISIR. The Director's term of office is for two years. Reappointment is possible, but the Director cannot be in the position for more than four years. The Director as of March 31, 2004 is Professor Masamitsu Futai. Two professors represent ISIR as members of the University Council, the Director and one elected from the full professors of ISIR. The other University Council Member as of March 31, 2004 is Professor Koichi Niihara. Important matters of ISIR are discussed and determined by the Faculty Council, which consists of the Director and all the full professors of ISIR. Various committees such as International Exchange, Self-Review, Circumstances and so on are working for each purpose. Future Plan Committee started in 1998. Administration of the Institute-associated Centers is conducted by Director of each Center and its Executive Committee. Office of Information Network was started in 1998. Evaluation Committee composed of outside experts of academic societies was established in 1998. The committee evaluated several items such as management, budget, facilities and research activities. Evaluation Report was published in March 1999.

3) Research Budget

The budget of ISIR is mainly composed of Institute budget, Grants-in-Aid for Scientific Research of Ministry of Education, Sports, Culture, Science and Technology, Donations for Research, and Budget of Joint Research. The recent trend in the expenditure of ISIR is shown in the next page. Institute budget is composed of various items including Project Research. Project Research was planned in the Research Plan Committee of ISIR and the plan was proposed to Ministry. After the judgment of Ministry, the budget was granted to the Institute. In 1997, research group "Atom Scale Processing for the Creation of Highly Harmonized Functional Materials" (Project leader: Professor T. Kawai) was designated as a Center of Excellence by Ministry of Education, Culture, Sports, Science and Technology.

In 2002, the following project has been selected as a 21st Century Center of Excellence (COE) program from the Ministry of Education, Culture, Sports, Science and Technology.

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Field: Interdisciplinary, Multi and New Fields Program Title: Towards Creating New Industries Based on Inter-Nanoscience Program Leader: Professor Tomoji Kawai (Division of Advanced Materials Science and Technology, ISIR)

Grants-in Aid for Scientific Research of Ministry of Education, Culture, Sports, Science and Technology are delivered to researchers and the total budget in 2003 is 686,997,000 yen. Donation for Research Donation for Research is accepted after the Judgement of Committee and the amount in these two years are as follows.

(Unit : kilo yen , ( ) Number) Division

Year

Quantum Engineering

Advanced Materials Science and Technology

Organic Molecular Science

Intelligent System Sciences

2002

3,581 ( 6)

33,913 (32)

9,486 (15)

7,920 ( 7)

2003

1,500 ( 2)

24,300 (20)

10,250 (13)

6,480 ( 5)

Division

Year

Biological Science

Quantum Beam

Sciences and Technology

Nanoscience and

nanotechnology center

Others Total

2002

13,899 ( 4)

1,111 ( 3)

6,850 ( 7)

76,760 (74)

2003

8,350 ( 9)

2,000 ( 3)

11,050 (14)

1,000 ( 1)

64,930 (67)

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4) Cooperative Research

Cooperative Researches and Contract Researches in 2002 and 2003 financial years are as follows: Cooperative Researches are carried out with 13 organizations. The budget in 2003 is 66,393,000 yen. Contract Researches are 36. The budget in 2003 is 473,471,000 yen.

5) International Research Projects

Koichi Niihara Core University Program between Japan and Korea “New Processing and Nanostructure/Property Relationship for Multi-Functionl Ceramic Materials”

6) Symposia, Seminars, Workshops and Lectures

A symposium on a special topic and a subsequent conference for presenting results of research activities made by the members of the Institute are held annually in November. They are open to the public. In 2003, the symposium was held on November 28. The topics were “Message for Creating New Industries”. The second 21st century COE Program / The seventh SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science, -Perspectives in Nanoscience- ” was held on January 13-14, 2004. The International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003) was held on 8-9 December, 2003 at the Lecture Hall, ISIR, Osaka University. This International Symposium was co-sponsored by the Nanoscience and Nanotechnology Center, The Institute of Scientific and Industrial Research (ISIR) and the Grant-in Aid for Specially Promoted Research “Function Harmonized Materials Research” from the Ministry of Education, Culture, Sports, Science and Technology, Japan. In this symposium, invited lectures by 18 outstanding researchers from the world and invited talks by 8 researchers from the ISIR as well as over 60 poster papers were presented. The number of participants was over 150. The first SANKEN International Workshop on Intelligent Systems was held by students in the division of Intelligent Systems Science on December 17, 2003.

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Other Lectures and Seminars

12 May 2003 Wolfgang Braun

(Paul Drude Institute, Germany, Researcher)

“In Situ Synchrotron X-Ray Diffraction Studies of MBE Growth”

22 May 2003 Michiyoshi Nukaga (University of Connecticut, U.S.A. )

“X-ray crystallographic analysis of β-lactamase in ultrahigh resolution”

26 May 2003 Kichisuke Nishimoto (Okayama University of Science, Guest Professor)

“The basic quantum chemistry and primary study for Gaussian98”

27 Jun 2003 Jin-Chun Kim (Korea Institute of Machinery and Materials(KIMM), Researcher)

“Preparation of WC and WC-Co Nanopowders by Chemical Vapor Condensation Proces”

15 Jul 2003 Thimaporn Phetkaew (Chulalongkorn University, Thailand)

“Reordering Adaptive Directed Acyclic Graphs: An Improved Algorithm for Multiclass Support Vector Machines”

16 Jul 2003 Kichisuke Nishimoto (Okayama University of Science, Guest Professor)

“The fundamental equation of quantum chemistry and the difference between MOPAC and DFT”

7 Aug 2003 Masashi Furukawa (RIKEN, Postdoctoral Researcher)

“Analyses of conduction mechanism in DNA using electron spectroscopies”

6 Oct 2003 Kiyonori Suzuki (Monash University, Senior Lecturer)

“Soft Magnetic Properties of Nano-Structured Magnetic Materials”

23 Oct 2003 Ljupco Todorovski (Jozef Stefan Institute, Slovenia, Researcher)

“Using Domain-Specific Knowledge for Automated Modeling”

23 Oct 2003 Tomoko Ohnishi (University of Pennsylvania, U.S.A. Professor)

“Insights into the reaction mechanism of proton-translocationg NADH-quinone oxidoreductase(Complex Ⅰ)”

5 Dec 2003 Hansjoerg Griese (Fraunhofer Institute)

“Microintegration and Reliability of Electronics for a sustainable development

5 Dec 2003 Tomas Pajdla (Czech Technical University in Prague, Associate Professor)

“Non-central cameras, their models, and stereo geometries”

13 Jan 2004 Sinn-wen Chen (National Tsing Hua University)

“Lead free solder/Ni Interfacial reactions in the electronic products”

15 Jan 2004 Jin-Hyeok Kim (Chonnam National University,

“Heteroepitaxial Growth of Oxide Thin Films On Si Substrates by

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Associate Professor) Physical Vapor Deposition Methods” 16 Jan 2004 Jin-Hyeok Kim

(Chonnam National University, Associate Professor)

“Structural Characterization of Oxide Thin Films Using High Resolution Transmission Electron Microscopy”

16 Jan 2004 Horst W. Hahn (Darmstadt University of Technology, Professor)

“Toward Creating New Industry Based on Nanosized Particle Systems”

16 Jan 2004 Teruhisa Ohno (Kyushu Inst. Tech. Professor)

“Visible light reactive TiO2 Photocatalyst”

16 Jan 2004 Ryuji Kato (Nat. Inst. Adv. Ind. Sci. Tech. )

“Observation of photoreactive species in a film of TiO2 nanoparticles with visible-nIR transient absorption measurement”

16 Jan 2004 Fumio Kokai (Mie University, Professor)

“Synthesis and modification of carbon nanotubes with laser irradiation”

19 Jan 2004 Kazuhiko Nakatani (Kyoto University, Associate Professor)

“Surface Plasmon Sensors for DNA mismatch detection”

19 Jan 2004 M. Joanne Lemieux (University of Alberta, Canada)

“Structure and Mechanism of GlpT, the glycerol-3-phosphate transporter from E. coli”

20 Jan 2004 Akira Murakami (Kyoto Inst. Tech., Professor)

“Transcriptome analysis using photo-functionalized nucleic acid derivatives”

20 Jan 2004 Kazunari Yamana (Himeji Inst. Tech., Associate Professor)

“Fluorescence and electrochemical detection of DNA mismatch”

31 Jan 2004 Akira Yamada (Kyushu University, Professor)

“Phototechnological application of gold nanoparticles-from catalyst to photonics”

31 Jan 2004 Teijiro Ichimura (Tokyo Inst. Tech., Professor)

“Molecular world developed by laser chemistry”

31 Jan 2004 Minoru Yamaji (Gunma University, Associate Professor)

“Recent photochemical reactions involving triplet energy transfer”

2 Feb 2004 King-Ning Tu (UCLA, Professor)

“Mechanism of spontaneous Sn whisker growth”

4 Feb 2004 Tomiki Ikeda (Tokyo Inst., Tech., Professor)

“Preparation of photofunctional materials applied by cooperative phenomena”

6 Feb 2004 Toyohiko J. Konno (Osaka Prefecture University, Professor)

“Roles of electron microscopy in nanotechnology”

6 Feb 2004 Shigeo Mori (Osaka Prefecture University, Associate Professor)

“Nanoscale ferromagnetism in CMR manganites”

13 Feb 2004 Hiroshi Onishi “Analysis of photocatalytic reaction

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(Kanagawa Academy of Sci. Tech.)

with probe microscopy and time-resolved spectroscopy”

14 Feb 2004 Yoshio Nosaka (Nagaoka Sci. Tech. University, Professor)

“Recent development of reaction mechanism of TiO2 photocatalyst”

19 Feb 2004 Yasumaru Hatanaka (Toyama Med. Pham. University, Professor)

“Photoaffinity analysis for drug design”

19 Feb 2004 Atsutaka Kunai (Hiroshima University, Professor)

“Synthesis and properties of organosilicone compounds towards functional materials”

21 Feb 2004 Yasunao Kuriyama (Yamagata University, Associate Professor)

“Photochemistry in zeolite pores”

21 Feb 2004 Nobuo Ikota (Radiation Medical Inst.)

“Oxidative stress and redox control by radiation”

23 Feb 2004 Takashi Karatsu (Chiba University, Associate Professor)

“Preparation of organosilicone compounds for materials”

23 Feb 2004 Kazuo Tsujimoto (Adv. Inst. Sci. Tech., Professor)

“Relationship between ant-oxidation and anti-photoaging of organonatural compounds”

23 Feb 2004 Hisafumi Ikeda (Tokyo Sci. University, Associate Professor)

“Artificial functionalized nucleic PNA”

24 Feb 2004 Hiroyuki Akinaga (National Institute of Advanced Industrial Science & Technology, Superior Nanostructure Group Leader)

“Advanced status of spin electronics and their related works”

24 Feb 2004 Masahiko Sisido (Okayama University, Professor)

“Preparation of non-natural aminoacids-modified protein”

24 Feb 2004 Shigeo Murata (Nat. Inst. Adv. Ind. Sci. Tech. )

“Ultrafast electron transfer and exciplex formation”

24 Feb 2004 Kenichi Sugiura (Tokyo Metropolitan University, Associate Professor)

“Chemistry of porphyrin oligomers”

25 Feb 2004 Chikashi Toyoshima (Institute of Molecular and Cellular Biosciences, University of Tokyo, Professor)

“Mechanism of ion transport by calcium pump”

28 Feb 2004 Takashi Hayashi (Kyushu University, Associate

“Functionalization of myoglobin proteins”

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Professor) 28 Feb 2004 Shuichi Hashimoto

(Gunma Int. Tech., Professor) “Diffusion of adsorbed molecules in zeolites”

28 Feb 2004 Nobuyuki Tamaki (Nat. Inst. Adv. Ind. Sci. Tech.)

“Photoresponsible molecular assemblies”

28 Feb 2004 Hirofumi Yajima (Tokyo Sci. University, Professor)

“Single-wall carbon nanotube-biopolymer conjugates”

28 Feb 2004 Hiroyuki Niino (Nat. Inst. Adv. Ind. Sci. Tech.)

“Fabrication of quartz surface by liquid laser ablation”

1 Mar 2004 Yoshio Sakaguchi (Inst. Phys. Chem. Res.)

“Reaction control by magnetic field and micro-wave”

1 Mar 2004 Mitsuru Ishikawa (Nat. Inst. Adv. Ind. Sci. Tech.)

“Preparation of SERS surface for single molecular detection”

1 Mar 2004 Hideo Higuchi (Tohoku University, Associate Professor)

“Control and systematic construction of protein motions”

1 Mar 2004 Kazunari Akiyoshi (Tokyo Med. Dent. University, Professor)

“Biomaterials by nanogel technology”

7) Public Information Activity

Public information activity of ISIR in 2003 is as follows: • Bulletin of ISIR (2003) (in both Japanese and English) • Memoirs of the Institute of Scientific and Industrial Research,

Osaka University (Vol.60, 2003) (in English) • Annual Report of ISIR (2003) (in Japanese) • SANKEN News Letters, 19-21(in Japanese) • Report on SANKEN TECHNO SALON (2003) (in Japanese) • WWW home-page (http://www.sanken.osaka-u.ac.jp/)

(English version is available.)

8) Research Reports

The number of scientific and technological papers published in 2003 is 490. The details are described in the part of activity of divisions and facilities.

9) Scientific Awards

T.Kawai Medal with Purple Ribbon (Cabinet Office)

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K.Tanizawa The Vitamin Society of Japan Award (The Vitamin Society of Japan)

M.Futai The Pharmaceutical Society of Japan Award’03 (The Pharmaceutical Society of Japan)

T.Kawano BCSJ Award (The Chemical Society of Japan)

T.Oku The 53rd Metallographic Award (The Japan Institute of Metals)

H.Motoda Encouragement Award of The Japanese Society for Artificial Intelligence

T.Washio Encouragement Award of The Japanese Society for Artificial Intelligence

K.Sato Award for Encouragement of Research in Material Science (The Materials Research Society of Japan)

S.Hyun Excellent Paper Award (Society for the Advancement of Materials Process Engineering)

H.Nakajima Excellent Paper Award (Society for the Advancement of Materials Process Engineering)

T.Ikeda Excellent Paper Award (Society for the Advancement of Materials Process Engineering)

Y.Yagi 10th ACM Symposium on Virtual Reality Software and Technology 2003 Honorable Mention Award

K.Nishino Kuroya’s Scholarship Award (Japanese Society for Microbiology)

2. Education ISIR accepts graduate students (about 190) from the Graduate Schools of Science, Engineering, Engineering Science, Pharmaceutical Science, and Frontier Biosciences, Information Science and Technology, and Frontier Bioscience, and also researchers for special training, including those from industry and from abroad. Staff members also belong to various Faculties: Faculty of Science, Faculty of Engineering, Faculty of Engineering Science, Faculty of Pharmaceutical Science, Faculty of Information Science and Technology, and Faculty of Frontier Bioscience. Some members belong to two Faculties. They give lectures for graduate and undergraduate students in each Faculty.

Number of graduate students as of March 1, 2004 is as follows.

G.S. Course

Science Engineering Engineering Science

Pharmaceutical Science

Information Science and Technology

Frontier Bioscience

Total

Master Course 38 48 16 8 6 1 117 Doctor Course 28 36 5 3 2 0 74 Total 66 84 21 11 8 1 191

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Number of students who had obtained Master's or Doctor's Degree in 2003 is as follows.

Field Degree

Science Engineering Engineering Science

Pharmaceutical Science

Information Science and Technology

Frontier Bioscience

Total

Master Degree 23 34 3 4 0 0 64 Doctor Degree 8 12 1 0 0 0 21 Total 31 46 4 4 0 0 85 SANKEN Open Seminar described previously also supplies a chance of education for members of society. 3. International Exchange 1) Exchange Agreement

The international exchange with universities and research institutions all over the world is promoted by International Exchange Committee of ISIR. “Japan-Korea Joint Research Project” starts for “Novel Processing and Synthesis of Ceramic/Metal Nanocomposits” by JSP and KOSEF, in 1999. Osaka university (Japan) and Handing University (Korea) are selected as core universities. Academic Exchange Agreements are now concluded with the following six organizations. ○Faculty of Natural Science, Otto-Von-Guericke University, Magdeburg (Germany) ○University of Maryland (U.S.A.) ○Basic Science Research Institute, Pukyong National University (Korea) ○Research Center Juelich (Germany) ○University College London (U.K.) ○Hanyang University (Korea) 2) Foreign Researchers and Students

Number of foreign researchers and students staying in ISIR as of March 31, 2004 is 28 in total. Details are: Research Associates (7),Visiting Researchers (1), Research Students (6), Graduate Students (Doctor Course) (13), (Master Course) (1). Their nationalities are : Korea (14), China (7), Thailand (2), India (2), Taiwan (1), Finland (1), Philippines (1) Foreign visitors in 2003 are as follows:

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U.S.A. (4), Germany (6), Korea (7), U.K. (1), China (1), Canada (3), Switzerland (1), Spain (1), Australia (1), Netherlands (2), Thailand (17), Taiwan (1), Malaysia (2), Belgium (1) Total (48). 3) International Conferences and Symposiums

Number of presentations (plenary, invited, oral and poster in various international conferences and symposia) by staff of ISIR is 665 in total. Number of ISIR staffs who have been working as committee members of International Conferences or Editorial Board of international academic journals are 171 in total. For more details, see the part of activity of divisions and facilities. 4. Concluding Remarks

Research activities of ISIR were evaluated in 1998 by an Evaluation Committee formed from outside experts of academic and industrial societies. Report of evaluation was published in March, 1999. Their opinion and proposal for our future are summarized from the report. (1) Management of Organization and Management System In the reorganization of the Institute in 1995, previous small research divisions were grouped to larger ones including several professors, associate professors and research associates in order to increase joint research and scientific communication among scientists. The new organization was highly evaluated, but the joint researches programs should be increased. Many committees are working for the administration of the Institute. However, simpler and more efficient organizations of faculty committees should be considered. 2) Budget and Facilities Outside experts reported that the sufficient research budget has been obtained compared with other research institutes. Necessary facilities and research equipments are installed to a considerable level. In 1997, Harmonized Materials Research Group was designated as one of the Centers of Excellence (COE) of Ministry of Education, indicating the high research activity of the Institute. The COE budget is an important source for the Institute. However, more support is still required for some Departments carrying out important research.

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A serious problem was the lack of space for research activity. We requested the construction of a new building to the Government, and completed the second building. (3) Graduate and Undergraduate Education About 190 graduate students from various Osaka University Graduate Schools such as Science and Engineering are working with us, and obtaining valuable experience in collaboration with our faculties. Staffs of our Institute partly take part in undergraduate education. A few members of the evaluation committee had opinions that we should be mainly engaged in research and not in such education. However, considering the situation of Osaka University, we should support the undergraduate education to some extent. It was pointed out that the Institute should make more efforts for science education for society members including industrial communities. Accepting the suggestion we started Sanken Techno-Salon providing a forum between our staff and people from industries specialized for electronics, organic chemicals, semiconductors, drugs, etc. We also started seminars for the seeds of new technologies to the industrial communities. (4) Contribution to Societies Presentation in scientific meetings and publications of research achievements by the Institute members are highly evaluated by the Committee. Contact to industries is being made through the efforts of individual professors and through Sanken Techno Salon started in 1998. Mutual understanding between the Institute and industries is obtained to considerable extents by the Salon. We started five workshops in 2001 for studying practical use of methods or materials invented and developed by the Institute. Through such workshops, we will be able to transfer our industrial seeds for new technology and ideas for new materials. (5) International Exchange Evaluation Committee pointed out that the more foreign researchers and students could be able to join the Institute. Responding to this comment, we are trying to invite more staffs and students from other countries. International Conferences sponsored by our Institute have been held twice a year since 1998. Taking into consideration of required expenses and efforts for the organization, two times is the appropriate number for one year.

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(6) Future Plan and Prospect In 1998, Future Planning Committee was established in the Institute by reorganization of Research Plan and Reorganization Committee. Future plan of the Institute was discussed in this Committee and summarized in annual report which can be seen in the Home Page of ISIR (http://www.sanken.osaka-u.ac.jp/). The Institute of Scientific and Industrial Research is making continued efforts toward higher levels contribution to science and industries.

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Activity of Divisions

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Division of Quantum Engineering Outline

New, advanced materials and fabrication techniques of nanostructures that allow the realization of the desired quantum effects of electrons, photons and spins are indispensable for the creation of novel electronic, photonic and spintronic devices. The Division of Quantum Engineering is engaged in experimental and theoretical research on these subjects aiming to establish the basis of future electronic/photonic/spintronic devices based on novel quantum effects. The Division of Quantum Engineering is composed of four departments: Quantum Molecular Devices, Photonic and Electronic Materials, Semiconductor Electronics and Condensed Matter Physics. Various approaches are being taken in the fields of electronic materials design and tailoring, surface physics, nanometer scale materials fabrication and characterization, semiconductor nanostructures for quantum devices, semiconductor-based new bio/chemical sensors and computational physics. Research areas studied and techniques employed by the Division of Quantum Engineering include atomic and electronic structures of semiconductor surfaces and interfaces, nanofabrication processes using scanning probe microscopy, arrangement of biomolecules on silicon substrates, epitaxial growth of compound semiconductors by molecular beam epitaxy, characterization of structural, electric, optical and magnetic properties of semiconductor materials, formation and characterization of low-dimensional semiconductor quantum structures, fabrication of new semiconductor and quantum structure devices, control of the physical properties of carbon nanotibes and the fabrication of single electron transistor, and prediction of new functional materials and fabrication processes design using first principles and electronic structure calculations. Interdisciplinary researches in cooperation with other divisions are also pursued. Achievements

• Thermodynamic study of atomic steps on Si surfaces and development of

bio/chemical imaging sensor • Crystal growth and characterization of new semiconductors including Tl-III-V, III-V

nitrides, magnetic III-V semiconductors and quantum nanostructures • Formation and characterization of low-dimensional semiconductor quantum

structures • Control of the physical properties of carbon nanotibes and the fabrication of single

electron transistor • Prediction of new functional materials and fabrication processes using first principles

and electronic structure calculations • Materials design for semiconductor spintronics from the first principles • Materials process design by electronic excitations from the first principles

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Department of Quantum Molecular Devices Professor: Hiroshi IWASAKI Associate Professor: Tatsuo YOSHINOBU Research Associates: Toshiyuki ADACHI, Koichi SUDOH Post Doctoral Fellow: Keisuke KAMETANI, Hongwen LIU Research Technical Expert: Morio INOUE Graduate Students: Hitoshi KURIBAYASHI, Yasuhito UI, Konobu

KIMURA, Yuzuru MIYATA, Hideaki FUJIMURA Support Staff: Fumi TOGAI Outlines

The Department of Quantum Molecular Devices is engaged in development of novel devices that integrate the quantum mechanical features of semiconductors and molecular functions of biomolecules including DNA and protein. We are also developing the Scanning Chemical Microscope for visualization of chemical and biological specimens. Current Research Programs 1. Layer Growth of CaF2 on Si(111) Surfaces In submonolayer growth of CaF2 on vicinal Si(111) surfaces, transition from step to island nucleation with increasing substrate terrace width has been investigated, using scanning tunneling microscopy. 2. Properties of Atomic Steps on SrTiO3(001) Surfaces Thermodynamic properties of unit-cell-high steps on SrTiO3(001) surfaces has been studied by STM. Analyzing the terrace width distributions on SrTiO3(001) vicinal surfaces with various misorientation angles, the interactions between neighboring steps have been quantitatively characterized. 3. Shape Transformation of Si Trenches by Hydrogen Annealing Mechanism of shape transformation of micron-sized trench structures fabricated on Si(001) by high temperature hydrogen annealing has been studied. By analyzing the time dependence of the trench corner curvature, it was shown that surface self diffusion is responsible for the shape transformation. Numerical simulation method of shape transformation of 3-D structures via surface diffusion was developed. 4. Patterning of Biomolecules on Si by AFM Anodic Oxidation Processes for micropatterning of protein and DNA molecules on Si weredeveloped based on the anodic oxidation technique of the Si surface by an AFM probe. 5. Observation of Protein by AFM, STM and Spectroscopic Ellipsometry AFM, STM and (scanning) spectroscopic ellipsometry were applied to observation and detection of protein molecules on solid surfaces.

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6. Application of the Chemical Imaging Sensor to Microfluidic Devices A flow channel was microfabricated on the surface of the chemicalimaging sensor, which allows visualization of ion distributions inside the channel. Publications Original Papers AFM Fabrication of Oxide Patterns and Immobilization of Biomolecules on Si Surface, T. Yoshinobu, J. Suzuki, H. Kurooka, W. C. Moon and H. Iwasaki: Electrochimica Acta, 48 (2003) 3131-3135. Shape Transformation of Silicon Trenches during Hydrogen Annealing, H. Kuribayashi, R. Hiruta, R. Shimizu, K. Sudoh and H. Iwasaki: J. Vac. Sci. Technol. A 21 (2003) 1279-1283. The Double K+/Ca2+ Sensor Based on Laser Scanned Silicon Transducer (LSST) for Multi-Component Analysis, Yu. Ermolenko, T. Yoshinobu, Yu. Mourzina, K. Furuichi, S. Levichev, M. J. Schöning, Yu. Vlasov and H. Iwasaki: Talanta., 59 (2003) 785-795. Anion-Selective Light-Addressable Potentiometric Sensors (LAPS) for the Determination of Nitrate and Sulphate Ions, Yu. G Mourzina, Yu. E Ermolenko, T. Yoshinobu, Yu. Vlasov, H. Iwasaki and M. J. Schöning: Sensors and Actuators B 91 (2003) 32-38. Detection of Protein-Protein Interactions on SiO2/Si Surfaces by Spectroscopic Ellipsometry, S. Kodera, T. Okajima, H. Iwabuki, D. Kitaguchi, S. Kuroda, T. Yoshinobu, K. Tanizawa, M. Futai and H. Iwasaki: Analytical Biochemistry 321 (2003) 65-70. K+-Selective Field-Effect Sensors as Transducers for Bioelectronic Alications, Yu. Mourzina, Th. Mai, A. Poghossian, Yu. Ermolenko, T. Yoshinobu, Yu. Vlasov, H. Iwasaki and M. J. Schöning: Electrochimica Acta. 48 (2003) 3333-3339. Portable Light-Addressable Potentiometric Sensor (LAPS) for Multisensor Alications, T. Yoshinobu, M. J. Schöning, R. Otto, K. Furuichi, Yu. Mourzina, Yu. Ermolenko and H. Iwasaki: Sensors and Actuators B 95 (2003) 352-356. Investigation on Light-Addressable Potentiometric Sensor as a Possible Cell-Semiconductor Hybrid, A. B. Md. Ismail, T. Yoshinobu, H. Iwasaki, H. Sugihara, T. Yukimasa, I. Hirata and H. Iwata: Biosensors and Bioelectronics 18 (2003) 1509-1514. Flow-Velocity Microsensors Based on Semiconductor Field-Effect Structures, A. Poghossian, T. Yoshinobu and M. J. Schöning: Sensors 3 (2003) 202-212.

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Ambient STM and in-situ AFM Study of Nitrite Reductase Proteins Adsorbed on Gold and Graphite, S. Antoranz Contera, H. Iwasaki and S. Suzuki: Ultramicroscopy 97 (2003) 65-72. Review Papers Nanolithography on SiO2/Si with a Scanning Tunnelling Microscope, H. Iwasaki, T. Yoshinobu and K. Sudoh: Nanotechnology 14 (2003) R55-R62. Step Dynamics in Faceting on Vicinal Si(113) Surfaces, K. Sudoh and H. Iwasaki: J. Phys.: Cond. Mat. 15 (2003) S3241-S3253. International Conferences Multi-Analyte LAPS Based on Photocurable Polymeric Membranes, T. Yoshinobu, Yu. Ermolenko, Yu. Mourzina, H. Iwasaki, Yu. Vlasov, *M. J. Schöning. BioSensorSymposium (BSS2003), Potsdam, Germany, 30 March - 2 April 2003. Multi-Component Analysis Based on the Light-Addressable Potentiometric Sensor (LAPS), *T. Yoshinobu, H. Iwasaki, Y. Ermolenko, Y. Mourzina, Y. Vlasov and M. J. Schöning, Sensor 2003, Nürnberg, Germany, 13 - 15 May 2003. Flow-Velocity Microsensors Based on Semiconductor Field-Effect Structures, *A.Poghossian, T. Yoshinobu and M. J. Schöning, International Symposium on Sensor Science (I3S), Paris, France, 16 - 20 June 2003. Amorphous Silicon as Semiconductor Material for High Resolution LAPS, *W. Moritz, T. Yoshinobu, F. Finger, S. Krause and M. J. Schöning, 17th European Conference on Solid-State Transducers (Eurosensors XVII), Guimaraes, Portugal, 21 - 24 September 2003. A Multisensor Based on Laser Scanned Silicon Transducer (LSST): Development and Properties, Yu. Ermolenko, *T. Yoshinobu, Yu. Mourzina, M.J. Schöning, Yu. Vlasov and H. Iwasaki, 17th European Conference on Solid-State Transducers (Eurosensors XVII), Guimaraes, Portugal, 21 - 24 September 2003. Thin-Film a-Si LAPS: Preparation and pH Sensitivity, *T. Yoshinobu, M. J. Schöning, F. Finger, W. Moritz and H. Iwasaki, 17th European Conference on Solid-State Transducers (Eurosensors XVII), Guimaraes, Portugal, 21 - 24 September 2003. Formation of Aligned SiC Dots on Vicinal Si(111) Using CaF2 Masks (Poster), *K. Kametani, K. Sudoh and H. Iwasaki, The 7th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-7), Nara, Japan, 16 - 20 November 2003. Effect of Hydrogen Ambient on Corner Rounding of Silicon Trench during High Temperature Annealing (Poster), *H. Kuribayashi, R. Hiruta, R. Shimizu, K. Sudoh and

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H. Iwasaki, The 7th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-7), Nara, Japan, 16 - 20 November 2003. In situ Observation and Analysis of Step Structures on Tetragonallysozyme (110) Surface during Crystal Growth (Poster), *K. Kimura, T. Yoshinobu, K. Sudoh and H. Iwasaki, The 7th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-7), Nara, Japan, 16 - 20 November 2003. In situ Observation and Analysis of Step Structures on Tetragonal Lysozyme (110) Surface during Crystal Growth (Poster), *K. Kimura, T. Yoshinobu, K. Sudoh and H. Iwasaki, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, 8 - 9 December 2003. Biomolecules Patterning on Si Surface by AFM Oxidation (Poster), *W. C. Moon, T. Yoshinobu, A. Nishikawa and H. Iwasaki, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, 8 - 9 December 2003. Light-Addressable Potentiometric Sensor for Detection of Ion Distribution in Microfluidic Channel (Poster), *Y. Ui, T. Yoshinobu and H. Iwasaki, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, 8 - 9 December 2003. Step Kinetics in Step-Flow Growth of CaF2 on Si(111) (Poster), *Y. Miyata, K. Sudoh, K. Kametani and H. Iwasaki, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, 8 - 9 December 2003. An STM Study of Step Distributions on SrTiO3(001) Surfaces (Poster), *K. Sudoh and H. Iwasaki, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, 8 - 9 December 2003. Patterned Surface as a Template for DNA-Based Nanotechnology, W.C. Moon, * A. Nishikawa, T. Yoshinobu and H. Iwasaki, 2003 Congress on Evolutionary Computation (CEC 2003), Canberra, Australia, 8 - 12 December 2003. Publications in Domestic Meetings The Japan Society of Applied Physics 9 papers The Physical Society of Japan 3 papers The Society of Instrument and Control Engineers 2 papers The Electrochemical Society of Japan 1 paper

Academic Degrees

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Master Degree of Engineering

Y. Ui Application of the Chemical Imaging Sensor to the Measurement of Ion Concentration in a Microfluidic Channel

K. Kimura Study on Crystal Growth of Hen-Egg Lysozyme Y. Miyata Study on Layer Growth of CaF2 on Si(111) Surfaces

Sponsorship Grant-in-Aid for Scientific Research (C) (2) T. YOSHINOBU Development of Multiple Ion Imaging Sensor and

its Application to Biological Specimens ¥900,000

Grant-in-Aid for Young Scientists (B) K. SUDOH Thermodynamic and Kinetic Properties of Steps on

Metal Oxide Surfaces ¥600,000

Other Research Fund H. IWASAKI Foundation for Biomedical Research and

Innovation 2,3-D Display of Cells and Its Application to Next Generation Analysis System

¥4,437,500

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Department of Photonic and Electronic Materials Professor: Hajime ASAHI Associate Professor: Shigehiko HASEGAWA Research Associates: Shuichi EMURA, Yi-Kai ZHOU Post Doctor Fellow: Xi-Jun LI, Shanthi SUBASHCHANDRAN Graduate Students: Jun MORI, Masahiko HASHIMOTO, Hwe-Jae LEE

Atsushi FUJIWARA, Moo-Seong KIM Akinori, IMADA, Yusuke OSUMI, Hiroyuki TANAKA Sosuke NISHIDA, Shigeya KIMURA, Takashi SHIMADA Wataru DOI, Toshikazu MUKAI, Hironori MUNAKATA Takashi YAMASHITA

Research Student: Sung-Woo CHOI Support Staff: Noriko KIKUMOTO Outlines

The department of Photonic and Electronic Materials makes research on materials, mainly semiconductors and related materials, and their processing. Four steps are required in materials research, that is, materials design, materials synthesis (crystal growth) and processing, materials characterization, and device application. In materials design, study on finding required characteristics by changing the combination and ratio of atoms is conducted. In materials synthesis, study on molecular beam epitaxy growth is mainly carried out, in which crystal growth is done by supplying molecules and atoms onto the substrate surface. In materials characterization, structure investigation by X-ray diffraction, STM, EXAFS and so on, optical characterization by photoluminescence, Raman scattering and so on, electrical characterization by Hall measurement, and magnetic characterization by SQUID are carried out. In device application, basic researches on photonic devices such as lasers, electronic devices such as field emission devices, and spintronic devices are conducted. Current Research Programs 1. Crystal Growth and Properties of Diluted Magnetic Semiconductors Diluted magnetic semiconductors, which have two characters of semiconductors and magnetic materials, are gathering interest as a candidate for new functional materials. In 2001, we succeeded in the growth of GaCrN and observed the room temperature ferromagnetism. In 2002, we observed the PL emission at room temperature. We also observed the room temperature ferromagnetism together with sharp PL emission for the rare-earth doped GaN, GaGdN and GaEuN. In 2003, we have conducted the EXAFS studies on GaCrN, GaGdN, GaEuN and confirmed that Cr, Gd and Eu atoms occupy the Ga site. Studies on the time resolved PL and the excitation power dependence of PL revealed that the PL from GaCrN is due to the band-to-band transition and that those from GaGdN and GaEuN is the f-f atomic level transition. We also demonstrated the spin tunnel characteristics in DyN/GaN superlattice structures.

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2. Growth, Characterization and Device Application of Semiconductor-Semimetal Mixed Crystals; New Semiconductors Including Tl In 1995, we proposed new semiconductors TlInGaAs in which the bandgap energy is independent of temperature. We have succeeded in the growth of TlInGaAs by MBE, though small composition of Tl. We confirmed the very small temperature variations of PL and electroluminescence (EL) peak energies. In 2001, pulsed-current injection laser operation was achieved in TlInGaAs/InP DH laser diodes (LDs) at room temperature. In 2002, we confirmed the small temperature variation of lasing peak wavelength as small as 0.06 nm/K. In 2003, we have measured the temperature dependence of refractive index and confirmed the small temperature variation, which agrees with the small temperature variation of the lasing peak wavelength. Further, we proposed TlInGaAsN/AlGaAs for both temperature-stable wavelength and threshold current LDs. We succeeded in the growth of TlInGaAs/GaAs heterostructures and observed the small temperature variation of the PL peak wavelengths. 3. Crystal Growth and Characteristics of Nitride Semiconductor Mixed Crystals III-V nitride semiconductors gather much interest from the viewpoint of application to light emitting devices as well as devices used in harsh environment. We tried the growth of GaN on quartz glass substrate and observed the strong PL emission from the grown polycrystalline GaN. We proposed the wide variety of device applications. In 2001, we obtained the good electric field emission characteristics of electrons from GaN/metal samples, which is promising to fabricate the field emission electron source devices. In 2002, we confirmed the improvement in field emission threshold voltage by the growth of thin AlN layer because of small electron affinity of AlN. In 2003, We have formed the GaN nano-rod structures on Si substrate and obtained the very small threshold voltage of 1.1 V/µm for the electron emission. 4. Self-Formation and Properties of Semiconductor Quantum Structures

In 1997, we found that the QDs were self-formed by growing GaP/InP short-period superlattices (SPSLs) on GaAs (N11) substrates and that they are aligned along two perpendicular directions with high density. We realized the laser operation in QD laser diodes. By growing GaAs/InAs SPSLs on InP (411)A substrates, we succeeded in the fabrication of QDs showing the controlled PL emission at wavelengths of 1.3-1.6 µm, which is very important wavelength region in the optical information communication systems. In 2003, by using these QDs we have realized the 1.3-1.5 µm LEDs.

5. Nano-observation and characterization of short-channel MOSFET

The cross sections of the short-channel MOSFETs, which were fabricated by the ion implantation with various implantation angles, were studied. We have succeeded in the visualization of the device nano-structures, such as the sizes and structures of the extension as well as the overlap lengths between the extension and the gate. We also demonstrated that the relation between the fabrication conditions and the fabricated device structures can be analyzed in nano-scale by this technique. Publications

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Original Papers New III-V-based Magnetic Semiconductors and Quantum Nano-structures, H. Asahi: J. Korean Phys. Soc.42 (2003) S499-S503. Magnetic and Optical Properties of GaMnN Grown by Ammonia Source Molecular Beam Epitaxy, M. Hashimoto, Y.K. Zhou, H. Tampo, M. Kanamura and H. Asahi: J. Cryst. Growth, 252 (2003) 499-504. MBE Growth and Properties of GaCrN, M. Hashimoto, Y.K. Xhou, M. Kanamura, H. Katayama-Yoshida and H. Asahi: J. Cryst. Growth, 251 (2003) 327-330. Gas Source MBE Growth of TlInGaAs/InP Laser Diodes and Their Room Temperature Operation, H.J. Lee, A. Fujiwara, A. Imada and H. Asahi: J. Cryst. Growth 251 (2003) 800-803. Room Temperature Ferromagnetism in III–V-Based Diluted Magnetic Semiconductor GaCrN Grown by ECR Molecular-Beam Epitaxy, Y.K. Zhou, M. Hashimoto, M. Kanamura, H. Asah: Journal of Superconductivity: Incorporating Novel Magnetism 16(1) (2003) 37-40. New III-V-based Magnetic Semiconductors and Their Optical and Magnetic Properties, H. Asahi, Y.K. Zhou, M. Hashimoto, R. Asano and H. Tanaka: Proc. of SPIE 4999 (2003) 221-228. Tunable Synchrotron Radiation Used to Induce Emission from the 31 Year Isomer of 178Hf, C. B. Collins, N.C. Zoita, A.C. Rusu, M.C. Iosif, D.T. Camase, F. Davanloo, S. Emura, T. Uruga, R. Dussart, J.M. Pouvesle, C.A. Ur, I.I. Popescu, V.I. Kirischuk, N.V. Strichuk, and F.J. Agee: Europhys. Lett., 57 (2002) 677-682. Formation of Ce1-xPdxO2 - Solid Solution in Combustion Synthesized Pd/CeO2 Catalyst: XRD, XPS and EXAFS Investigation, K.R. Priolkar, P. Bera, P.R. Sarode,, M.S. Hegde, S. Emura, R. Kumashiro, and N.P.Lalla: Chem. Mater 14 (2002) 2120-2128. Structural Investigation of Combustion Synthesized Cu/CeO2 Catalyst by EXAFS and Other Physical Techniques: Formation of a Ce1-xCuxO2-Delta Solid Solusion, P. Bera, K.R. Priolkar, P.R. Sarode, M.S. Hegde, S. Emura, R. Kumashiro, and N.P. Lalla: Chem. Mater. 14 (2002) 3591-3601. Structure Analysis of Ag-In-Sb-Te Phase-change Material, H. Tashiro, M. Harigaya, Y. Kageyama, K. Ito, M. Sinotsuka, K. Tani, A. Watada, N. Yiwata, Y. Nakata and S. Emura: Jpn. J. Appl. Phys., 41 (2002) 3758-3759. Study of Local Environment of Ag in Ag/CeO2 Catalyst by EXAFS, P.R. Sarode, K. R.

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Priolkar, P. Bera, M.S. Hegde, S. Emura, and R. Kumashiro: Material Research Bulletin, 37 (2002) 1679-1690. Structural Change of Li1-xMn0.5Ni0.5O2 Cathode Materials for Lithium-Ion Batteries by Synchrotron Radiation, Y. Arachi, H. Kobayashi, S. Emura, Y. Nakata, M. Tanaka, and T. Asai: Chemistry Letters. 32 (2003) 60-61. Crystal Structure and Electronic Transport of Dy@C82, Y. Kubozono, Y. Takabayashi, K. Shibata, T. Kanbara, S. Fujiki, T. Hosokawa, S. Kashino, A. Fujiwara, S. Emura, and T. Uritsu: Phys. Rev. B, 67 (2003) 11510-1-8. Ionic Dispersion of Pt over CeO2 by the Combustion Method: Structural Investigation by XRD, TEM, XPS, and EXAFS, P. Bera, K.R. Priolkar, A. Gayen, P.R. Sarode, M.S. Hegde, S. Emura, R. Kumashiro, V. Jayaram, and G.N. Subbanna: Chem. Mater. 15 (2003) 2049-2060. Scanning Tunneling Microscopy Study on Stacking Processes of InAs Dots on GaAs (001), S. Hasegawa, O. Suekane, and H. Nakashima: Phys. Stat. Sol. (c) 0, No.4 (2003) 1125-1128. Scanning Tunneling Microscopy Study of GaAs Overgrowth on InAs Islands Formed on GaAs (001), S. Hasegawa, O. Suekane, M. Takata, and H. Nakashima: J. Crystal Growth 251 (2003) 161-165. Electric Field Emission from Nitride Semiconductor Grown on Mo Substrate, S. Nishida , T. Yamanaka , S. Hasegawa and H. Asahi: Phys. Stat. Sol. (c) 0(7) (2003) 2416-2419. Local Structure of Rare-earth-doped Diluted Magnetic Semiconductor GaGdN, M. Hashimoto, S. Emura, R. Asano, H. Tanaka, Y.K. Zhou, N. Teraguchi, A. Suzuki, Y. Nanishi, T. Honma, N. Umesaki and H. Asahi: Phys. Stat. Sol. (c) 0(7) (2003) 2650-2653. Optical and Magnetic Properties of DyN/GaN Superlattice, Y.K. Zhou, N. Teraguchi, M. Hashimoto, H. Tanaka, A. Suzuki, Y. Nanishi, and H. Asahi: Phys. Stat. Sol.(b) 240(2) (2003) 440-442. Magnetic Properties of Rare-earth-doped Semiconductor GaEuN, H. Tanaka, M. Hashimoto, R. Asano, Y. K. Zhou, H. Bang, K. Akimoto, H. Asahi: Phys. Stat. Sol. (c)0(7) (2003) 2864-2868. Magnetic Properties of Eu-doped GaN Grown by Plasma-assisted Molecular Beam Epitaxy, M. Hashimoto, A. Yanase, R. Asano, H. Tanaka, H. Bang, K. Akimoto and H.

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Asahi: Jpn. J. Appl. Phys. 42 (10A) (2003) L1112-L1115. Reduced Temperature-dependence of Refractive-index in TlInGaAs Quaternary Alloys Grown on InP Substrates, A. Imada, H.-J. Lee, A. Fujiwara, S. Emura, S. Hasegawa and H. Asahi: J. Appl. Phys. 94(10) (2003) 6976-6978. Observation of Small Temperature Variation of Longitudinal-mode Peak Wavelength in TlInGaAs/InP Laser Diodes, A. Fujiwara, H.J. Lee, A. Imada, S. Hasegawa and H. Asahi: Jpn. J. Appl. Phys. 42 (11B) (2003) L1359-L1361. Temperature-Insensitive Wavelength TlInGaAs Semiconductor Lasers, S. Gonda, H. Asahi, A. Fujiwara and H.J. Lee: Recent Research Developments in Applied Physics 6 (2003) 649-661. Two-dimensional Characterization of Carrier Concentration in Metal-oxide-Semiconductor Field-effect Transistors with the Use of Scanning Tunneling Microscopy, H. Fukutome, H. Arimoto, S. Hasegawa, and H. Nakashima: J. Vac. Sci. Technol. B 22 (2004) 358-363. Review Papers Room Temperature Ferromagnetic Nitride Semiconductors Doped with Transition-metal and Rare-earth Atoms, H. Asahi and Y.K. Zhou: Osaka University Low Temperature Center News, 124 (2003) 18-21. Division of Solid State Physics and Applications, H. Asahi: Oyo Butsuri 72 (2003) 624-625. Present and Future Views of Division of Solid State Physics and Applications, H. Asahi: JSAP International No.8 (2003) 3 Books Molecular Beam Epitaxy, H. Asahi, In: Handbook of Thin Film Depositions and Applications ed. by S. Gonda (NTS, Tokyo 2003) pp.288-305. International Conferences New III-V-based Magnetic Semiconductors and Their Optical and Magnetic Properties (Invited), *H. Asahi, Y.K. Zhou, M. Hashimoto, R. Asano and H. Tanaka, SPIE Optoelectronics 2003 International Symposium, San Jose, CA, USA, January 25-31, 2003. Temperature-dependence of lasing spectrum for TlInGaAs/InP DH laser diodes and 77K CW operation, *A. Fujiwara, H.J. Lee, A. Imada and H. Asahi, 15th International Conference on Indium Phosphide and Related Materilas, Santa Barbara, California, USA, May 12-16, 2003.

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Optical Properties of the Quantum Dot Structures Self-formed in GaAs/InAs Short-period Superlattices Grown on InP(411)A Substrates, *J. Mori, T. Nakano, S. Hasegawa and H. Asahi, 15th International Conference on Indium Phosphide and Related Materilas, Santa Barbara, California, USA, May 12-16, 2003. Structural and Magnetic Properties of Rare-earth-doped Diluted Magnetic Semiconductor GaGdN, *M. Hashimoto, S. Emura, R. Asano, H. Tanaka, Y.K. Zhou, N. Teraguchi, A. Suzuki, Y. Nanishi, T. Honma, N. Umesaki and H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. Optical and Magnetic Properties of DyN/GaN Superlattice, *Y.K. Zhou, N. Teraguchi, M. Hashimoto, H. Tanaka, A. Suzuki, Y. Nanishi, and H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. Magnetic Properties of Rare-earth-doped Semiconductor GaEuN, *H. Tanaka, M. Hashimoto, R. Asano, Y. K. Zhou, H. Bang, K. Akimoto, H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. Electric Field Emission from Nitride Semiconductor Grown on Mo Substrate, *S. Nishida, T. Yamanaka , S. Hasegawa and H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. Spectral Evidence of High Crystallinity with Uniform Solid Solution of Ga1-xMnxN, *H. Harima, N. Hasuike, T. Ryoki, E. Kurimoto, M. Hashimoto, Y.K. Zhou, and H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. X-ray Absorption Studies of Combustion Synthesized Cu/CeO2 Catalysts, *K.R. Priolkar, P. Bera, P.R. Sarode, M.S. Hegde, S. Emura, and R. Kumashiro, International Symposium on Recent Advances in Inorganic Materials, India Institute of Technology Bombay, Mumbai, India, December 11-13, 2002. Size Effect on X-ray Absorption Spectra of Iron Nitride Nano Particles, *T. Nakagawa, M. Kano, K. Nishimaki, T. Yamamoto, and S. Emura, 6th International Conference on Nanostructured Materials, Orlando, Florida, USA, June 16-21, 2002. High-temperature structure of Sc2O3-doped ZrO2, *Y. Arachi, M. Suzuki, T. Asai, S. Emura, T. Kamiyama, and F. Izumi, 14th International Conference on Solid State Ionics, Monterey, California, USA, June 22 – 27, 2003. Possibility of XAFS Spectra Detection by NEET – Nuclear XAFS -, *S. Emura, Carl B. Collins, N.C. Zoita, A.C. Rusu, F. Davanloo, T. Uruga, Y. Yoda, J.M. Pouvesle, C.A. Ur, I.I. Pepescu, V.I. Kirischuk, N.V. Strilchuk, and F.J. Agee, 12th International

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Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22-27, 2003. Local Environments of Cu+ in Dilute System NaCl:Cu+ and the first Principal Calculation of Its environment, *S. Emura and Y. Nakata, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22-27, 2003. Orbital Ordering in Pr0.5Sr0.5MnO3: Pr K-edge XAFS Study, *K.R. Priolkar, V.D. Kulkarmi, P.R. Sarode, R. Kumashiro, and S. Emura, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003. Pseudo Jahn – Teller Effect Observed in Eu@C60, *S. Emura, K. Shirai, and Y. Kubozono, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003. XAFS Study on Li1-xNi0.5Mn0.5O2 Cathode Material for Lithium-Ion Batteries, *Y. Arachi, H. Kobayashi, S. Emura, Y. Nakata, M. Tanaka, and T. Asai, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003. Site-selective and Valence-selective Structural Analysis around Monovalent Copper-Ion Exchanged in ZSM-5-type Zeolite by Synchrotron-light-induced XEOL Detection Method, *Y. Kuroda, S. Emura, R. Kumashiro, T. Uruga, and M. Nagao, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003. Adsorption Site of Cs+ in Smectite Hydrate: Dertermination by XAFS, *M. Nakano, K.Kawamira, S. Emura, H. Tanida, and K.Uchida, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003. On XAFS Spectra by the Secondary Processes Detection such as Fluorescence, Photo-conductivity, displacement Current and Photo-electron, *S. Emura, Y. Nakata, Y. Nishuhata, and Y. Ito, 12th International Conference on X-ray Absorption Fine Structure, Malmö, Sweden, June 22 -27, 2003, 1.3-1.6 μm Wavelength Control of Light Emission from the Quantum Dots Self-formed in GaAs/InAs Short-period Superlattices Grown on InP(411)A Substrates, *J. Mori, T. Nakano, S. Hasegawa, H. Asahi, 11th International Conference on Modulated Semiconductor Structures, Nara, Japan, July 14-18, 2003. Electric Field Emission from Nitride Semiconductor Grown on Mo Substrate, *S. Nishida, T. Yamanaka, S. Hasegawa, and H. Asahi, 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-31, 2003. Optical Properties of the Quantum Dot Structures Self-formed in GaAs/inAs Short-

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period Superlattices Grown on InP(411)A Substrates, *J. Mori, T. Nakano, S. Hasegawa, and H. Asahi, 15th International Conference on Indium Phosphide and Related Materials, Santa Barbara, California, USA, May 12-16, 2003. Temperature-dependence of Lasing Spectrum for TlInGaAs/InP DH Laser Diodes and 77 K CW Operation, *A. Fujiwara, H. J. Lee, A. Imada, S. Hasegawa, K. Oe, S. Gonda, and H. Asahi, 15th International Conference on Indium Phosphide and Related Materials, Santa Barbara, California, USA, May 12-16, 2003. Two-dimensional Characterization of Carrier Concentration in MOSFETs with the Use of Scanning Tunneling Microscopy, *H. Fukutome, H. Arimoto, S. Hasegawa, and H. Nakashima, The 7th Int. Workshop On Fabrication, Characterization, and Modeling Of Ultra-Shallow Doping Profiles In Semiconductors, Santa Cruz, USA, 2003. Delineation of Electrostatic Potential in 0.1-μm MOSFETs by Cross-sectional Scanning Tunneling Microscopy, *S. Hasegawa, T. Okui, and H. Nakashima, 2003 International Conference on Characterization and Metrology for ULSI technology, Austin, USA, March 24-28, 2003. New III-V-based Magnetic Semiconductors and Their Optical and Magnetic Properties, *H. Asahi, Y.K. Zhou, M. Hashimoto, H. Tanaka, M.S. Kim, S. Emura and S. Hasegawa, Gordon Research Conference on the Chemistry of Electronic Materials, Conneticut College, New London, CT, USA, July 13-18, 2003. Migration Enhanced Epitaxy (MEE) Growth of Five-Layer Asymmetric Coupled Quantum Well (FACQW) and its Cross-sectional STM Observation, *J.H Noh, S. Hasegawa, T. Suzuki, T. Arakawa, K. Tada and H. Asahi, Fifth International Workshop on Epitaxial Semiconductors on Patterned Substrates and Novel Index Surfaces (ESPS-NIS), Max-Planck-Institute Stuttgart, Stuttgart, Germany, October 13-14, 2003. Magnetic, Optical and Transport Properties of Magnetic Semiconductor Heterostructure DyN/GaN, *M.S. Kim, Y.K. Zhou, X.J. Li, and H. Asahi, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnClera2003, CUP-10), Gamagori, Shizuoka, November 10-12, 2003. MBE Growth of Magnetic Semiconductor GaCrN and Their Magnetic and Optical Properties, *Y. Osumi, M. Hashimoto, H. Tanaka, Y.K. Zhou, S. Hasegawa and H. Asahi, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnClera2003, CUP-10), Gamagori, Shizuoka, November 10-12, 2003. Barrier Height Control for Electron Field Emission by Growing Ultra Thin AlN Layer on GaN/Mo, *S. Nishida, T. Yamashita, S. Hasegawa and H. Asahi, The 7th International Conference on Atomically Controlled Surfaces, Interfaces and

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Nanostructures, Nara, Japan, November 16-20, 2003. Fabrication of Cr-doped GaN/AlN Quantum Dots by RF Molecular Meam Epitaxy, *Y. Osumi, H. Munakata, S. Hasegawa and H. Asahi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003. Optical Properties of TlInGaAs Films Grown on (100) InP Substrates, *A. Imada, H. J. Lee, A. Fujiwara, T. Mukai, S. Hasegawa and H. Asahi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003. Electric Field Emission Properties of GaN Films on Mo Substrates, *T. Yamashita, S. Nishida, S. Hasegawa and H. Asahi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003. Optical Characterization of New GaN-based Ferromagnetic Semiconductor GaCrN Grown by Molecular Beam Epitaxy, *S. Kimura, Y.K. Zhou, M.S. Kim, X.J. Li, A. Kaneta, Y. Kawakami, Sg. Fujita, S. Emura, S. Hasegawa and H. Asahi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003. Evaluation of Device Configurations of 0.1 µm MOSFETs by Scanning Tunneling Microscopy, *W. Doi, S. Hasegawa, T. Okui, H. Nakashima, and H. Asahi, 11th International Colloquium on Scanning Probe Microscopy, Izu-Atagawa, Shizuoka, December 11-13, 2003. Cross-sectional STM Study of Five-layer Asymmetric Coupled Quantum Well (FACQW) Grown by Migration Enhanced Epitaxy (MEE), *J.H. Noh, S. Hasegawa, T. Suzuki, T. Arakawa, K. Tada and H. Asahi, 11th International Colloquium on Scanning Probe Microscopy, Izu-Atagawa, Shizuoka, December 11-13, 2003. Growth and Characterization of New III-V-based Magnetic Semiconductors for Application to Semiconductor Spintronics Devices (Invited), *H. Asahi, Y.K. Zhou, M. Hashimoto, H. Tanaka and S. Emura, 12th International Workshop on The Physics of Semiconductor Devices (IWPSD-12), Chennai, India, December 16-20, 2003. Accelerated Decay of The 31-yr Isomer of Hf-178 Induced by Low-Energy Photons and Electrons, *C.B. Collins, N.C. Zoita, F. Davanloo, S. Emura, Y. Yoda, T. Uruga, B. Patterson, B. Schmitt, J.M. Pouvesle, I.I. Popescu, V.I. Kirischuk, and N.V. Strilchuk, The Twelfth International Laser Physics Workshop (LPHYS’03), Hamburg, Germany, August 25-29, 2003. Accelerated Emission from Isomeric Nuclei, *C.B. Collins, N.C. Zoita, F. Davanloo, S. Emura, Y. Yoda, T. Uruga, B. Patterson, B. Schmitt, J.M. Pouvesle, I.I. Popescu, V.I.

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Kirischuk, and N.V. Strilchuk, The ISRP9 Conference, Cape Town South Africa July 2003. Tunneling Magnetoresistance Effect in Magnetic Semiconductor Heterostructure DyN/GaN, *M.S. Kim, Y.K. Zhou, X.J. Li and H. Asahi: Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science”, Osaka, Japan January 13-14, 2004. Temperature-stability of Lasing Wavelength for TlInGaAs/InP DH Laser Diodes and 77K CW Operation, *A. Fujiwara, H.J. Lee, A. Imada, K. Mukai, S. Hasegawa, and H. Asahi: Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science”, Osaka, Japan, January 13-14, 2004. 1.3-1.5 µm Wavelength Quantum Dot Light Emitting Diodes by Growing GaAs/InAs Short-period Superlattices on InP(411)A, *T. Shimada, J. Mori, S. Hasegawa and H. Asahi: Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science”, Osaka, Japan, January 13-14, 2004. Luminescence from the Gd Site in the GaGdN Dilute Magnetic Semiconductor, *S. Emura, Y.K. Zhou, M. Hashimoto, H. Tanaka, M.S. Kim, S. Kimura, S. Shanthi, X.J. Li, N. Teraguchi, A. Suzuki, A. Yanase, and H. Asahi: Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science”, Osaka, Japan, January 13-14, 2004. Contributions to International Conferences and Journals H. Asahi 15th International Conference on Indium Phosphide and Related

Materials (International Steering Committee Co-chair, Program Committee)

H. Asahi 4th International Conference on Nitride Semiconductors (Program Committee)

H. Asahi 11th International Colloquim on Scanning Probe Microscopy (Organizing Committee, Management Committee General Affairs, Publication Committee)

H. Asahi The Seventh International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (Program Committee)

H. Asahi 16th International Conference on Indium Phosphide and Related Materials (International Steering Committee, Organizing Committee)

H. Asahi International Conference on Nanospintronics Design and Realization (Organizing Committee)

H. Asahi International Workshop on Nitride Semiconductors (IWN-2004)

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(International Steering Committee) H. Asahi Japan. J. Appl. Phys. (Editor) H. Asahi Current Applied Physics (Editor) H. Asahi J. of Materials Science: Materials in Electronics (Editor) H. Asahi e-Journal of Surface Science and Nanotechnology(Advisary Board) Publications in Domestic Meetings The Japan Society of Applied Physics 23 papers Electronic Materials Symposium 4 papers Symposium on PASPS 1 paper The Physical Society of Japan 1 paper Academic Degrees

Master Degree of Engineering A. Imada Study on Optical Properties of TlInGaAs on InP Substrates H. Tanaka Study on Crystal Growth and Characterization of GaN-Based Diluted

Magnetic Semiconductors Master Degree of Science Y. Osumi Study on Fabrication of Cr-Doped GaN Quantum Dots by MBE and

Their Characterization S. Nishida Field Emission from Nitride Semiconductors on Metal Substrates Doctor Degree of Engineering J. Mori Fabrication of III-V Semiconductor Short Period Superlattice

Quantum Dot Structures on High Index Plane Substrates and Their Device Applications

H.J. Lee Study on Tl-Based Semiconductors and Their Device Applications Doctor Degree of Science M. Hashimoto Study on Properties of GaN-Based Diluted Magnetic Semiconductors Sponsorship Grant-in-Aid for Scientific Research on the Priority Area (A) (2) H. Asahi Study on Temperature-Independent Lasing Wavelength

Semiconductor Laser Diodes in the Wide Wavelength Region

¥3,000,000

Y.K. Zhou Study on Synthesis of GaN-Based Transparent Ferromagnetic Semiconductors

¥2,200,000

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Grant-in-Aid for Scientific Research (B) (2) H. Asahi Study on Applications of Polycrystalline Nitride

Semiconductors to Field Emission Electron Source and Visible Fluorescent Substance

¥9,300,000

S. Hasegawa Nano-Magnetic Characterization of Diluted Magnetic Semiconductors by Spin-Polarized Scanning Tunnel Spectroscopy

¥8,200,000

Grant-in-Aid for Scientific Research (C) (2) S. Emura Study on the Local Atomic Arrangement and the Origin

of Magnetism of GaN-Based Ferromagnetic Semiconductors by XAFS and XMCD

¥3,100,000

Grant-in-Aid for Scientific Research on Special Research Fellow J. Mori Study on Quantum Dot Structures Self-Formed in the

Short-Period Superlattices on High-Index Surface Substrates and their Application to Infrared Region Lasers

¥900,000

Entrusted Research S. Hasegawa Nanoscale Profiling of Sub-Micron Si Devices by

Scanning Probe Microscopy ¥8,400,000

Other Research Fund H. Asahi MEXT Special Coordination

Funds for Promoting Science and Technology (H. Kasai)

Design and Invention of Spintronics

¥25,395,000

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Department of Semiconductor Electronics Professor: Kazuhiko MATSUMOTO Associate Professor: Koichi INOUE Research Associates: Kenzo MAEHASHI, Yasuhide OHNO Under Graduate Students: Kazuki NARUMI, Yasuyuki FUJIWARA Supporting Staff: Ayumi OKANO Outlines

Quantum-effect devices are expected to show superior properties. In order to realize these quantum-effect devices, we study the basic problems in the carbon nanotube, physics of quantum structures and surfaces and interfaces using Raman spectroscopy, photoelectron spectroscopy, electron diffraction, scanning probe microscopy, and photoluminescence. The research activities include formation and characterization of single electron devices using carbon nanotube, coherent ballistic transport of carrier, and atomic and electronic structures of surfaces and interfaces. Current Research Programs

1, The growth control of the carbon nanotube by the patterned catalyst was performed

for the fabrication of the field effect transistor and single electron transistor, which was used to investigate the transfer property of the nanotube. The characterization of thermally grown carbon nanotube was examined by the Raman shift spectroscopy. The bundle of the hydrogen terminated carbon nanotube was found to show the photoluminescence characteristics even at room temperature.

2, The chirality of the carbon nanotube was first controlled by the irradiation of the

laser beam with the specific wave length in atmosphere. The laser power was selectively absorbed by the carbon nanotube with the specific chirality, i.e., the specific energy band gap and burned out in the air. This method could selectively remove the carbon nanotube with the specific chirality. Publications Original Papers Magnetoresistance in a GaAs-AlGaAs Two-dimensional Periodic Potential Fabricated by AFM Local Anodization, K. Oto, K. Shibuya, K. Matsumoto and K. Murase, : Microelectronic Engineering, 63 (2003) 253-258. Single Electron Transistor with Ultra-High Coulomb Energy of 5000K Using Position Controlled Grown Carbon Nanotube as Channel, K. Matsumoto, S. Kinoshita, Y. Gotoh, K. Kurachi, T. Kamimura, M. Maeda, K. Sakamoto, M. Kuwahara, N. Atoda and Y. Awano : Jpn.J. Appl. Phys.,Vol.42, [Part 1, No.4B], (2003) 2415-2418.

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International Conference

Defective Carbon Nanotube Devices,(Invited), *K. Matsumoto, Device Research Conference (DRC) , Utah University, Utah,USA,July 2,2003. Temperature Dependence of Carbon Nanotube Channel Single Elewctron Transistor, K. Matsumoto and *T. Kamimura, The 11th International Conference on Modulated Semiconductor Structures (MSS 11), Naraken New Public Hall,Nara,Japan,July 17,2003. Carbon Nanotube Nanoelectron Devices, *K. Matsumoto, CREST & QNN03 Joint International Workshop, Awaji Yumebutai International Conference Center, Hyogo,Japan,July 21,2003. High Sensitive Photo-detectors by the Combination of Carbon Nanotubes and Photo-materials, *Y. Nagamune, T. Kamimura, and K. Matsumoto, CREST & QNN03 Joint International Workshop, Awaji Yumebutai International Conference Center, Hyogo,Japan, July 21 2003. Improvement of Carbon Nanotube Channel Single Electron Transistor Characteristics by Ultra-low Energy Nitrogen-ion Irradiation, *T. Kamimura, .K. Yamamoto, and K. Matsumoto, CREST & QNN03 Joint International Workshop, Awaji Yumebutai International Conference Center, Hyogo,Japan, July 21 2003. Low-temperature Transport Properties of Carbon Nanotubes Grown by Thermal Chemical Vapor Deposition, *T. Yamaguchi, K. Ono, S. Tarucha, T. Kamimura, and K.Matsumoto,CREST & QNN03 Joint International Workshop, Awaji Yumebutai International Conference Center, Hyogo,Japan, July 21 2003. Single Electron Transistor with Ultra-High Coulomb Energy of 5000K using Position Controlled Grown Carbon Nanotube as Channel, *T. Kamimura, K. Yamamoto, K. Matsumoto, The 2003 International Conference on Solid State Devices and Materials, Tokyo, Sep.17,2003. Defective Carbon Nanotube Channel Single Electron Transistor with Ultra-High Coulomb Energy of 5000K(Invited), K. Matstumoto, TNT03 (Trend in Nano Technology 2003), Samaranka, Spain, Sep.15,2003. Defective Carbon Nanotube Channel Single Electron Transistor with Ultra-High Coulomb Energy of 5000K and its Applications(Invited), K. Matstumoto, 50th American Vacuum Society Meeting, Baltimore Convention Center ,USA, Nov.5,2003. Ultra-low Energy Nitrogen-ion Irradiation for Quantum Dots Size Control in Carbon Nanotube Channel Room Temperature Single Electron Transistor, *T. Kamimura, K. Yamamoto, K. Matsumoto, The 2nd Internationa Symposium on "Future-oriented Interdisciplinary Materials Science" FIMS2003,Epochal Tsukuba International Congress Center,Tsukuba,Japan, Nov.10,2003.

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Carbon Nanotube Single Electron Transistor with Ultra-High sensitivity for Optical and Bio-Sensor, K. Matsumoto,International Workshop on Multi Processing Technology 2003 (IWMPT 2003), World Convention Center “Summit”,Miyazaki,Japan,Nov.10,2003 Application of RT Carbon Nanotube Single Electron Transistor to Methanol Sensor, *K.Kurachi, M.Torigoe, K.Matsumoto,Functional Semiconductor Nano Structure 2003 (FSNS 2003), NTT Basic Research Laboratories,Japan,Nov.14,2003. Application of Carbon Nanotube Single Electron Transistor with Ultra-High Coulomb Energy(Invited), K. Matsumoto,Functional Semiconductor Nano Structure 2003 (FSNS 2003, NTT Basic Research Laboratories,Japan, Nov 14,2003. Application of Carbon Nanotube Quantum Dot to Single Electron Transistor with Ultra-High Coulomb Energy of 5000K(Invited), K. Matsumoto, ACSIN-7 (7th International Conference on Atomically Controlled Surface, Interface and Nanostructures), Naraken New Public Hall,Nara,Japan, Nov.19,2003 Optical Sensor and Bio Sensor Applications using Carbon Nanotube Channel Single Electron Transistor,K.Matsumoto, Y. Nagamune, A. Kojima, NPMS-6/SIMD-4 2003,Six International Conference on new phenomena in Mesoscopic Structures, Fourth International Conference on Surface and Interface of Mesoscopic Devices,Wailea Marriot Resort,USA,Dec.3,2003. Carbon Nanotube FET/SET with Ultra-High Sensitivity for Sensor Application, K. Matsumoto, K. Inoue, K. Maehashi, Y. Ohno,SANKEN COE/Nanotechnology Symposium,ISIR,Osaka,Japan,Dec.9-10,2003. Polarization Control of Vertical Cavity Surface Emitting Laser Structure by Using Self-organized Quantum Wires Grown on (775)B-oriented GaAs Substrate by Molecular Beam Epitaxy, *Y. Ohno, Y. Takasuka, M. Ogura,K. Komori, S. Shimomura, S. Hiyamizu, 2003 North American Conference on Molecular Beam Epitaxy, keystone,Colorado,USA. Sep.28,2003. Contributions to International Conference and Journals K. Matsumoto CREST & QNN Joint International Workshop(the vice chairperson) K. Matsumoto The 11th International Conference on Modulated Semiconductor

Structures(MSS 11)(Organizing committee) K. Matsumoto Functional Semiconductor Nano Structure 2003(Organizing committee) K. Matsumoto 7th International Conference on Atomically Controlled Surface, Interface and

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Nanostructures (Organizing committee) Publications in Domestic Meetings The Japan Society of Applied Physics Physical Society of Japan

17 papers 1 paper

Sponsorship Cooperative Research K. Matsumoto Mitsubishi Chemical Bio-sensor by carbon nanotube ¥20,000,000 Corpration single electron transistor at room

temperature Other Research Fund K.Matsumoto Japan Science and Carbon nanotube single electron ¥92,000,000

Technology Agency single spin measurement systems

K.Matsumoto Special Coordination Fund For Promoting Carbon nanotube electronics ¥30,000,000 Science and Technology

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Department of Condensed Matter Physics Professor: Associate Professors: Visiting Scientist: Research Technical Experts:

Post Doctoral Fellows:

Research Student: Graduate Students:

Under Graduate Student: Support Staff:

Hiroshi KATAYAMA-YOSHIDA Hisatomo HARIMA, Yoshitada MORIKAWA Shunichi YANAGIYA Kiichi AMAYA, Ayao OKIJI, Mitsuhiro MOTOKAWA Akira MASAGO, Van An DINH, Hiroyuki NAKAYAMA, Ikutaro HAMADA YunHee CHANG Takayoshi MATSUMURA, Naoki MITSUDA, Kunihiko YAMAUCHI, Hiroki FUNASHIMA, Hideyuki MATSUOKA, Yuki OHISHI, Michito SUZUKI, Masayoshi SEIKE, Toshiyuki MICHIKITA, Hidetoshi KIZAKI, Kazuhide KENMOCHI, Masayuki TOYODA, Tetsuya FUKUSHIMA Hideaki MOTOSHIMA Mika ASADA

Outlines The primary activities of this department are theoretical study of electronic properties of condensed matters, and materials design, which predicts novel materials possessing desired properties for applications. In addition to model analyses which extract the essence of materials properties, quantum simulations are used for the study, with the methods of computational physics reflecting a recent remarkable progress of computing ability. Theoretical approaches are tried to predict materials which meet requirements from application areas by first-principles calculations using atomic numbers only as parameters. Current Research Programs 1. Ab intio Molecular Dynamic Simulation of Electronic Excitation-induced Atomic Migration. We have developed new simulation method for the application of the electronic excitation-induced atomic migration, and applied for the materials design to use the atomic migration through the metastable atomic position. We have designed new fabrication process from graphite to diamond at the normal condition by using the core electron excitations. 2. Materials Design for the High-efficient Amorphous Silicon Solar Cells. We have proposed a mechanism of photo-induced degradation for amorphous silicon solar cells based upon ab initio molecular dynamics simulation. In this mechanism, the conversion from the negative effective U dangling bond to the positive effective U dangling bond is the key point to understand the mechanism. We proposed a new

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mechanism of the CN treatment to avoid the photo-induced degradation in silicon-based solar cells. 3. Spintronics and Materials Design Using Semiconductor Nanostructures. Based upon ab initio electronic structure calculation, we have proposed the materials design to control the spin interaction for II-VI and III-V compound semiconductors. We have designed the transparent half-metallic ferromagnets for GaN-, AlN-, ZnO-, ZnS-based diluted magnetic semiconductors. We also design the p-type and n-type carrier-concentration dependence of Curie temperature (Tc) and 3d transition atom dependence of Tc in above diluted ferromagnetic semiconductors. New functional 4d-transition-metal (4d-TM)-doped K2S diluted magnetic semiconductors with transparent and half-metallic ferromagnetism are designed based upon the first principles calculations. We have systematically investigated the magnetism in 4d-TM-doped K2S DMSs. K2S is a transparent semiconductor with anti-CaF2 crystal structure and has large lattice spacing due to its large ionic radius of K. It is found that Zr-, Nb-, Tc-, Ru- and Rh-doped K2S show the half-metallic and high-spin ferromagnetism and that Zr- or Nb-doped K2S are promising candidate for high-Tc ferromagnetic DMSs with transparecy and large magneto-optical effect. 4. Materials Design and Valence Control of Wide Band-gap Semiconductors. Based upon ab initio electronic structure calculation, we have proposed codoping method for the fabrication of the low-resistive p-type CuAlO2, and n-type diamond. Our predictions of co-doping for the valence control are confirmed by the experiment. We have calculated the formation energy of P, N, and B in diamond, and oxygen-interstitial, Cu-vacancy, Al-vacancy, Be-acceptor, Mg-acceptor in CuAlO2.We also proposed the possibility of high efficient thermo-electric material (ZT>3) and transparent superconductivity upon slightly p-type or heavily p-type doped CuAlO2. 5. Materials Design of Spin and Charge Control Method in Heme-protein. We proposed a new model to describe the spin (high-spin vs. low-spin ground state) and charge control (multiple charged states) in heme protein. We have studied the magnetic interaction of spins in this system and proposed a materials design for biological sensors. 6. First Principle Calculation of Electric Field Gradients The first principle calculations of electric field gradients at nucleus sites performed based on the FLAPW-LDA method for many materials. The results have been compared with the measured NQR frequencies. 7. Electronic Structure of LaRh3B2 The Fermi surfaces of LaRh3B2, which is a reference material of ferromagnetic CeRh3B2 with TC=120K, are investigated and determined. 8. Electronic Structures of Newly Reported Superconductors Electronic bandstructures have been calculated for new superconductors Y2C3 and KOs2O6. From the result, in Y2C3, C-p electrons should play a significant role in its

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superconductivity. Publications Original Papers MBE growth and properties of GaCrN, H. Hashimoto, Y.K. Xhou, M. Kanamura, H. Katayama-Yoshida and H. Asahi: J. Crystal Growth. 251 (2003) 327-330. Materials Design for Semiconductor Spintronics by Ab initio Electronic-structure Calculation (Invited), H. Katayama-Yoshida and K. Sato: Physica B327 (2003) 337-343. Engineering of Nested Fermi Surface and Transparent Conducting p-type Delafossite CuAlO2: Possible Lattice Instability or Transparent Superconductivity?, H. Katayama-Yoshida, T. Koyanagi, H. Funashima, H. Harima and A. Yanase: Solid State Commun. 126 (2003) 135- 139. Curie Temperatures of III-V Diluted Magnetic Semiconductors Calculated from First-Principles in Mean Field Approximation (Invited), K. Sato, H. Katayama-Yoshida and P. H. Dederichs: J. Supercond. Inc. Novel Magnetism, 16 (2003) 31-35. Spin and Charge Control Method of Ternary II-VI and III-V Magnetic Semiconductors for Spintronics: Theory vs. Experiment (Invited), H. Katayama-Yoshida and K. Sato: J. Phys. Chem. Solid. 64 (2003) 1447-1452. A Structural Study of CN Treated Amorphous Silicon, Y. Yamazaki, K. Shirai and H. Katayama-Yoshida: Solid State Commun. 126 (2003) 597-600. Direct Conversion of Graphite into Diamond Through Electronic Excited States (Invited), H. Nakayama and H. Katayama-Yoshida: J. Phys:Condens. Matter 15 (2003) R1077-R1091. Charge and Spin States of Transition-Metal Atoms in a Hemoprotein Based on the Extended Haldane-Anderson Model, K. Yamauchi, H. Maehashi and H. Katayama-Yoshida: J. Phys. Soc. Japan, 72 (2003) pp.2029-2032. Materials Design of 4d-Transition-Metal-Doped Transparent and Half-Metallic Ferromagnets with K2S-Based Diluted Magnetic Semiconductors, M. Seike, A. Yanasse, K. Sato and H. Katayama-Yoshida: Jpn. J. Appl. Phys. 42 (2003) L1061 -L1063. Tc-Enhanced Codoping Method for GaAs-Based Dilute Magnetic Semiconductors, Van An Dinh, K. Sato and H. Katayama-Yoshida: Jpn. J. Appl. Phys. 42 (2003) L888-L891. Theoretical Aspect of Doping of Photovoltaic Materials (Invited), H. Katayama-Yoshida: Mat. Res. Soc. Symp. Proc. 763 (2003) B1.1, 3-12. Magnetic Impurities and Materials Design for Semiconductor Spintronics. (Invited), K.

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Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky: Physica B340-342 (2003) 863-869. Ab initio materials Design and Curie Temperature of GaN-based Ferromagnetic Semiconductors, K. Sato, P. H. Dederichs, K. Araki and H. Katayama-Yoshida: Phys. Stat. Sol. c, 7 (2003) 2855-2859. Unique Fermi Surfaces with Quasi-one-dimensional Character in CeRh3B2 and LaRh3B2, T. Okubo, M. Yamada, A. Thamizhavel, S. Kirita, Y. Inada, R. Settai, H. Harima, K. Takegahara, A. Galatanu, E. Yamamoto and Y. Onuki: J.Phys. Condens. Matter 15 (2003) L721-L727. Definitive Experimental Evidence for Two-Band Superconductivity in MgB2, S. Tsuda, T. Yokoya, Y. Takano, H. Kito, A. Matsushita, F. Yin, J. Itoh, H. Harima and S. Shin: Phys. Rev. Lett. 71 (2003) 127001-1-4. A de Haas-van Alphen Experiment under Pressure on CeCoIn5: Deviation from the Quantum Critical Region, H. Shishido, T. Ueda, S. Hashimoto, T. Kubol, R. Settai, H. Harima and Y. Onuki: J.Phys. :Condens. Matter 15 (2003) L499-L504. Materials Design of p-type Transparent Conducting Oxides of Delafossite CuAlO2 by Super-cell FLAPW Method, T. Koyanagi, H. Harima, A. Yanase and H. Katayama-Yoshida: J. Phys. Chem. Solids 64 (2003) 1443-1446. Photoemission Study of CeMIn5 (M=Rh, Ir): Nearly Localized Nature of f Electrons, A.-I. Fujimori, T. Okane, J. Okamoto, K. Mamiya, Y. Muramatsu, A. Fujimori, T. Narimura, K. Kobayashi, K. Shimada, H. Namatame, M. Taniguchi, H. Harima , D. Aoki, S. Ikeda, H. Shishido, Y. Tokiwa, Y. Haga and Y. Onuki: Physica B 329-333 (2003) 547-548. De Haas-van Alphen Effect of CeRhIn5 Under Pressure, H. Shishido, R. Settai, S. Araki, T. Ueda, Y. Inada, H. Harima and Y. Onuki: Physica B 329-333 (2003) 526-527. Quadrupolar Ordering in Half-integral Spin Systems, S. H. Curnoe, K. Ueda, H. Harima and K. Takegahara: Physica B 329-333 (2003) 474-475. FLAPW Electronic Band Structure of the Filled Skutterudite ThFe4P12, K. Takegahara and H. Harima: Physica B 329-333 (2003) 464-466. Conduction Bands in the Filled Skutterudites, H. Harima and K. Takegahara: J.Phys.:Condens. Matter 15 (2003) S2081-S2086. High-quality Single Crystal Growth and the Fermi Surface Property of Uranium and Cerium Compounds, Y. Onuki, Y. Haga, E. Yamamoto, Y. Inada, R. Settai, H. Yamagami and H. Harima: J. Phys. Condens. Matter 15 (2003) S1903-S1909. Magnetic Properties and Fermi Surface of YMn2, K. Nakada, H. Shimizu, H. Yamada

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and H. Harima: J Magn. Magn. Mater. 262 (2003) 374-381. Theory of a New Type of Heavy-electron Superconductivity in PrOs4Sb12: Quadrupolar-fluctuation Mediated Odd-parity Pairings, K. Miyake, H. Kohno and H. Harima: J. Phys. Condens. Matter 15 (2003) L275-L284. Fermi Surface of the Filled Skutterudite LaOs4Sb12, H. Harima and K. Takegahara: Physica C 388-389 (2003) 555-556. Possible Type of Heavy-electron Superconductivity in PrOs4Sb12, K. Miyake, H. Kohno and H. Harima: Physica C 388-389 (2003) 553-554. Formation Mechanism of Hybridization Gap in Kondo Insulators based on a Realistic Band Model and Application to YbB12, T. Saso and H. Harima: J. Phys. Soc. Jpn. 72 (2003) 1131-1137. Nearly Localized Nature of f Electrons in CeTIn5 (T = Rh, Ir), S. Fujimori, T. Okane, J. Okamoto, K. Mamiya, Y. Muramatsu, A. Fujimori, H. Harima, D. Aoki, S. Ikeda, H. Shishido, Y. Tokiwa, Y. Haga and Y. Onuki: Phys. Rev. B 67 (2003) 144507-1-5. Systematic Study of Electronic Band Structures for Binary Skutterudite Compounds, K. Takegahara and H. Harima: Physica B 328 (2003) 74-76. de Haas-van Alphen Effect in LaRu4P12, S. R. Saha, H. Sugawara, R. Sakai, Y. Aoki, H. Sato, Y. Inada, H. Shishido, R. Settai, Y. Onuki and H. Harima: Physica B 328 (2003) 68-70 . X-dependence of Electronic Bandstructures for LaFe4X12 (X=P,As,Sb), H. Harima and K. Takegahara: Physica B 328 (2003) 26-28. High Magnetic Field Study of CePd2Si2, I. Sheikin, A. Groger, S. Raymond, D. Jaccard, D. Aoki, H. Harima and J. Flouquet: Phys. Rev. B 67 (2003) 094420-1-10. Origin of the Metal-Insulator Transition in PrRu4P12, H. Harima, K. Takegahara, K. Ueda and S.H. Curnoe: Acta Physica Polonica B 34 (2003) 1189-1192. Single-Crystal Growth and de Haas-van Alphen Effect in Yb4Sb3, M. Shirakawa, M. Ona, H. Aoki, A. Ochiai and H. Harima: Acta Physica Polonica B 34 (2003) 1157-1160. Heavy Fermion Behavior of Pr 4f Electrons in Filled Skutterudites Studied by Bulk-Sensitive Photoemission, A. Yamasaki, S. Imada, T. Masuda, T. Nanba, A. Sekiyama, H. Sugawara, T.D. Matsuda, H. Sato, C. Sekine, I. Shirotani, H. Harima and S. Suga: Acta Physica Polonica B 34 (2003) 1035-1038. Correlations and Semimetallic Behaviors in Pyrochlore Oxide Cd2Re2O7, Z. Hiroi, M. Hanawa, Y. Muraoka and H. Harima: J. Phys. Soc. Jpn. 72 (2003) 21-24.

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Mechanism of Suppression of Light-induced Degradation in Amorphous Silicon by CN Treatment, Y. Yamazaki, K. Shirai and H. Katayama-Yoshida: Proc. 26th Int. Conf. Phys. Semicond., Edinburgh 2002, eds. A. R. Long and J. H. Davies, IOP Conf. 171 (2003) L.3.6. Pressure-induced Phase Transitions of BNs, K. Shirai, H. Fujita, and H. Katayama-Yoshida: Physica Status Solidi (b) 235 (2003) 526-530. Association Simulation by a Metallic Car-Parrinello Dynamics, S. Kawamoto, T. Oda and I. Hamada: International Journal of Quantum Chemistry 91, (2003) 165 Structure and Magnetism on Iron Oxide Clusters FenOm(n=1-5): Calculation from First Principles, H. Shiroishi, T. Oda, I. Hamada and N. Fujima: Euro. Phys. J. D. 24, (2003) 85. Possibility of Pressure-induced Superconductivity by Phonon Mechanism in Pd, K. Yanai, T. Takezawa, I. Hamada, N. Suzuki: Physica C 388-389 (2003) 596. The Electronic Structure of Beta-boron and the Pressure Dependence, K. Shirai, A. Masago and H. Katayama-Yoshida: Physics of Semiconductors 2002, 171(2003) D210. Patents “Magnetic Random Access Memory (MRAM)” H. Katayama-Yoshida, K. Sato, TW 92116467 “Magnetic Random Access Memory (MRAM)” H. Katayama-Yoshida, K. Sato, PCT/JP03/07447 “Transparent Ferromagnetic Alkali-chalcogene Compound Containing Transition Metal or Rare-earth Metal, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, M. Seike, K. Sato, A. Yanase, JP2003-127602 “Ferromagnetic VI-th Semiconductor, Ferromagnetic III-V Compound Semiconductor, or Ferromagnetic II-VI Compound Semiconductor, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Araki, K. Sato, PCT/JP03/07161 “Ferromagnetic VI-th Semiconductor, Ferromagnetic III-V Compound Semiconductor, or Ferromagnetic II-VI Compound Semiconductor, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Araki, K. Sato, TW 92115303 “Fabrication Method of Diamond from Graphite by Electronic Excitations” H. Katayama-Yoshida, H. Nakayama, PCT/JP03/06426 “Fabrication Method of Diamond from Graphite by Electronic Excitations” H. Katayama-Yoshida, H. Nakayama, TW 92114330 “Circular-polarized Semiconductor Laser by Using Magnetic Semiconductors, and

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Method of Circular-polarized CW-lasing” H. Katayama-Yoshida, K. Sato, WO 03/065525A1 “Gettering Method of Transition Atom Impurities in Crystalline Silicon” H. Katayama-Yoshida, WO03/060981A1 “II-VI Group or III-V Group Based Single Crystal Ferromagnetic Compound and Method for Adjusting Its Ferromagnetic Characteristics” H. Katayama-Yoshida, K. Sato, Korea 2003-7011104 “Fabrication Method of Highly-light Emitting Semiconductor Materials” H. Katayama-Yoshida, S. Nakajima, JP Patent No.3464618 “Transparent Ferromagnetic Compound Doped by Incomplete Shell without Magnetic Transition Metal and Magnetic Rare-earth Metal Impurities, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Kenmochi, M. Seike, K. Sato, JP2004-055017 “Transparent Ferromagnetic Compound Doped by Incomplete Shell without Magnetic Transition Metal and Magnetic Rare-earth Metal Impurities, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Kenmochi, M. Seike, K. Sato, PCT/JP04/003373 “Thermoelectric materials using natural super-lattices and its control method” H. Katayama-Yoshida, H, Funashima, I. Hamada, H. Harima, A. Yanase, JP2004-085615 International Conferences

Theoretical Aspects of Doping of Photovoltaic Materials (Invited), *H. Katayama-Yoshida, 2003 MRS Spring Meeting, San Francisco, California, April 21-25, 2003 Ab initio Materials Design and Curie Temperature of GaN Compound-based Ferromagnetic Semiconductors, K. Sato, P. H. Dederichs, *H. Katayama-Yoshida, ICNS-5: 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-30, 2003 Codoping Methods of Mn and N for GaAs-based Diluted Magnetic Semiconductors, *Dinh Van An, K. Sato, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Materials Design of 4d-Transition-Metal Doped Transparent and Half-metallic Ferromagnetism with Diluted Magnetic Semiconductors in Anti-CaF2 structures of K2S, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003

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Effects of Anti-site Defects on Half-metallicity in Zinc-blends CrAs, *M. Shirai, M. Seike, K. Sato, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Material Design of the Powerful Faraday Rotator, *A. Yanase, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Magnetic Mechanism and Materials Design of Diluted Magnetic Semiconductors from First Principles ~Guideline for High-Tc and Application to II-VI, III-V, IV, and I2-VI Semiconductors (invited), *H. Katayama-Yoshida, K. Sato and P. H. Dederichs, International Workshop on Diluted Magnetic Semiconductors, CECAM, Lyon, June 12-14, 2003 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors (invited), *K. Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky, International Workshop on Diluted Magnetic Semiconductors, CECAM, Lyon, June 12-14, 2003 Band Structure Calculation and Fermi Surfaces for LaRh3B2, *H Harima and K Takegahara, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1, 2003 Group Theoretical Classification of the Electronic Structure of LiNiO2, *A. Masago, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1, 2003 Mechanism of Enhanced Ferromagnetism in Delta-doped(Ga, Mn)As Studied by ab initio Electronic Structure Calculation, *Y. Ohishi, K. Sato, H. Katayama-Yoshida, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Theoretical Study on Anti-site Defects in Half-metallic Zinc-blende Ferromagnets, *M. Shirai, M. Seike, K. Sato and H. Katayama-Yoshida, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Electronic Structures and CDW of Transition Metal Dichalcogenides, *M. Suzuki and H. Harima, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Magnetic Impurities and Materials Design for Semiconductor Spintronics, *K. Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky, ICDS-22: International Conference on Defects in Semiconductors, Aarhus, Denmark, July 28-August1, 2003 Materials Design of 4d-transition-metal Doped K2S Diluted Magnetic Semiconductors with Transparent and Half-metallic, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, SPINTECH2: International Conference and School Semiconductor Spintronics

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and Quantum Information Technology, Brugge, Belgiujm, August 4-8, 2003 Mechanism of Enhanced Ferromagnetism in Delta-doped (Ga,Mn)As Studied by ab initio Electronic Structure Calculation, *Y. Ohishi, K. Sato, H. Katayama-Yoshida, SPINTECH2: International Conference and School Semiconductor Spintronics and Quantum Information Technology, Brugge, Belgiujm, August 4-8, 2003 Electronic Structure, Ferromagnetic Mechanism, and Curie Temperature of 3d- and 4d-Transition Atom Doped Diluted Magnetic Semiconductors (invited), *H. Katayama-Yoshida, The 4th Korea-Japan Workshop on Strongly Correlated Systems and The First Japan-Korea-Taiwan Workshop on Condensed Matter Physics “Spectroscopy of Correlated Materials and their Nano-Structures”, Nagano, Japan, September 24-26, 2003 Band Structure Calculations and Fermi Surfaces of YNi2B2C, *Y. Yamauchi, H. Katayama-Yoshida, A. Yanase, H. Harima, 16th International Symposium on Superconductivity, Tsukuba, Japan, October 27-29, 2003 Symmetry of the Conduction Bands in the Pyrochlore Lattice, *H Harima and K Takegahara, The 3rd International Workshop "Novel Quantum Phenomena in Transition Metal Oxides" and The 1st Asia-Pacific Workshop on "Strongly Correlated Electron Systems", Sendai, November 5-8, 2003 Diamond Transition from Graphite Induced by Electronic Excitations, *H. Nakayama and H. Katayama-Yoshida, The 6th Asian Workshop on First-Principles Electronic Structure Calculations, Tsukuba, November 10-12, 2003 Pressure-induced Phase Transitions of BN, *K. Shirai, H. Fujita, and H. Katayama-Yoshida, The 6th Asian Workshop on First-Principles Electronic Structure Calculations, Tsukuba, November 10-12, 2003 Design of High-Tc Curie Temperature with Transparent and Half Metallic Ferromagnetism in Zr- and Nb-doped K2S Diluted Magnetic Semiconductors, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 Design of a Method to Raise Curie Temperature by Delta-doping and Co-doping, *Y. Ohishi, Dinh Van An, K. Sato, H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 An Application of Molecular Dynamics Simulation to Diffusion of Impurity in Solids, *K. Shirai and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 Ab-initio Molecular Dynamics Simulation of CN in Amorphous Silicon, *N. Mitsuda, K. Shirai and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003

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Materials Design for Spin-electronics by Ab-initio Electronic Structure Calculation (invited), *H. Katayama-Yoshida, 31st Conference on The Physics and Chemistry of Semiconductor Interface (PCSI-31), Kailua-Kona, Hawaii, USA, January 18-22, 2004 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors, *K. Sato, International Symposium on the Creation on Novel nanomaterials, Osaka, Japan, January 20-22, 2004 Hyperfine Interactions and Magnetism of 3d Impurities in Magnetic Semiconductors (invited), *K. Sato, International Workshop on Nanomaterials, Magnetic Ions and Magnetic Semiconductors studied mostly by Hyperfine Interactions (IWNMS-2004), Vadodara (Baroda), Gujarat, India, February 10-14, 2004 Electric Field Gradients Obtained by the FLAPW Method, *H. Harima, K. Betsuyaku and K. Takegahara, Magnetism and Superconductivity in f-electron systems, Tokai, Japan, February 23-24,2003 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors, *K. Sato, P. H. Dederichs, H. Katayama-Yoshida, APS(American Physical Society) March Meeting, Montreal, Quebec, Canada, March 22-26, 2004 Contributions to International Conferences and Journals

H. Katayama-Yoshida 3rd International Conference on Physics and Application of Spin-related Phenomena in Semiconductors: PASPS3 (International Advisory Committee and Program Committee)

H. Katayama-Yoshida 24th International Conference on Defects in Semiconductors : ICDS24 (Chairman)

Publications in Domestic Meetings

The Physical Society of Japan 13papers The Japan Society of Applied Physics 6papers The Magnetics Society of Japan 1paper Academic Degrees Master Degree of Science

M. Suzuki CDW and electronic band structures of Transition metal di-chalcogenides

Master Degree of Engineering

Y. Ohishi Material design on the GaAs-based diluted magnetic semiconductor using first principles calculation.

M. Seike Materials Design of New root Half-Metalic and Room-temperature Ferromagnets in Diluted Magnetic Semiconductors

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T. Michikita Ab initio calculations of Cu Gettering in crystalline silicon Sponsorship Grant-in-Aid for Scientific Research on the Priority Area (2) H. Harima Research for heavy fermion states in the filled

skutterudites ¥36,700,000

Other allocations

Grant-in-Aid for Scientific Research (A) (H. Hirayama) H. Katayama-Yoshida Fabrication and Application of High Density p-type

Nitride Semiconductor Thin Film Crystal by Alternative Codoping

¥500,000

Grant-in-Aid for Scientific Research on the Priority Area (M. Shirai) H. Katayama-Yoshida Design for Opto-spintronics and Spin Prove Entrusted Research Special Coordination Funds for Promoting Science and Technology H. Katayama-Yoshida Design and Fabrication of Nanospintronics

Computational Nanomaterials and Device Design ¥19,964,000

H. Harima Basic Research of the Application of Boron-based New Type Superconductor Mechanism of Function and Materials Design

¥3,750,000

Ministry of Education, Culture, Sports, Science and Technology Grant-in-Aid for the Creation of Innovations through Business-Academic-Public Sector Cooperation H. Katayama-Yoshida Research on selective and low-temperature impurity

diffusion in semiconductor by infra-red laser excitation

¥4,500,000

Japan Science and Technology Corporation H. Katayama-Yoshida Core Research for Evolutional Science and Technology

(H. Kobayashi) Silicon Thin Film Solar Cells with New Chemical Bonds

Japan Science and Technology Corporation H. Katayama-Yoshida Research and development Applying Advanced Computational

Science and Technology (H. Akai) Computational Nano-materials Design

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New Energy and Industrial Technology Development Organization (NEDO) H. Katayama-Yoshida Development of Method for Nano-materials Simulation

(H. Akai) Cooperative Research H. Katayama-Yoshida Institute for Materials Research,

Tohoku Univ. Materials and Device Design for Functional Wide-band Gap Semiconductors

H. Katayama-Yoshida Spring8 Mechanism of New Materials Fabrication Using Electronic Excitation

H. Katayama-Yoshida International Institute of Advanced Study

Materials Science and System Design

H. Katayama-Yoshida Jülich Institute (Germany) Computational Materials and Devices Design for Nanospintronics

H. Harima Japan Atomic Energy Research Institute

Theoretical study on the largely orbital-degenerated many electron system

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Division of Advanced Materials Science and Technology Outline

The Division of Advanced Materials Science and Technology is composed of six departments with research fields: Structural Characterization and Design, Metallic Materials Process, Atomic Scale Science, Functional Ceramic Materials, Structural Ceramic Materials, and Advanced-Energy Materials. This division has a close relationship with Nanoscience and Nanotechnology Center of this Institute founded in 2002. The future highly functionalized materials can be obtained by hybridizing different kinds of materials which are well designed and controlled with respect to their structures, dimensions and physical and chemical properties. We are aiming at design, development and characterization of new functional or high strength and high performance materials by means of highly advanced processes with micro, nano and atomic scale controlled techniques we developed. Achievements

・ Designing, prediction of atomic structure and properties of materials by computer simulation ・ Local structural analysis of amorphous materials ・ Fabrication and physical properties of nano-particles ・ Fabrication of high-performance lotus-type porous metals and its application ・ Diffusion in intermetallic compounds, quasicrystals and metallic glasses with a

wide supercooled liquid region ・ Observation and manipulation of DNA on inorganic substrate by SPM ・ Construction and properties of functional artificial lattices by laser MBE and

atomic layer controlled super-ferroelectric materials ・ Design and development of brain mimetic memory and super five sensor ・ Improvement of Si solar cell characteristics by use of new method of eliminating

defect states ・ Formation of dielectric films by use of new chemical reactions and the application

to MOS devices ・ Development and materials design of strong and tough ceramic-based

nanocomposites ・ Development of new functional ceramics from nanocomposite concept ・ Preparation and design of atomic/molecular-level composites ・ Laser-induced nano-processing of semiconductor surfaces ・ Dynamics of photoinduced phase transitions in low-dimensional crystals

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Department of Structural Characterization and Design Professor: Yoshihiko HIROTSU Associate Professor: Manabu ISHIMARU Research Associates: Kazuhisa SATO, Akihiko HIRATA Research Fellow (COE) Zhi ZANG Research Technical Expert: Atsuo KOREEDA Research Students: In-Tae BAE, Muneyuki NAITO, Jong Han WON, Jun-ichi

KAWAMURA, Mitsuhiro YAMAGUCHI, Takeshi KOTERA, Keisuke YAGI

Support Staff: Shigeko TOMII Outlines

In controlling structures of new functional materials, introduction of new local structure analysis techniques to the materials becomes necessary. Using high-resolution electron microscopy (HREM), electron diffraction and electron energy-loss spectroscopy, we are mainly analysing local atomic structures and electronic states of functional alloy nano-particles, amorphous alloys, ion-irradiated ceramics and multi-layered materials. We are also developing new local structure analysis techniques using nano-sized electron probe, energy-filter and imaging-plate. Molecular dynamics and Monte-Carlo calculations and electronic band structure calculations of new materials are carried out for predicting their structures and physical properties. Current Research Programs 1. Radial Distribution Function Analysis by Advanced Electron Microscopy We examined both multiple-scattering and inelastically-scattering effects on a quantitative analysis of radial distribution function obtained by electron diffraction. Diffraction patterns and electron energy-loss spectra were taken from amorphous Fe70Nb10B20 with different thickness. On the basis of the quantitative analysis of diffraction intensities, it was found that the multiple–scattering effects are negligible for the Fe-based metallic glasses with a thickness of <20 nm. From the experiments using energy-filtered transmission electron microscopy, the exclusion of inelastically-scattered electrons due to plasmon-loss is found to improve the accuracy of electron-beam structure analysis, especially coordination number analysis. 2. Fabrication and Characterization of L10-type Hard Magnetic Nanoparticles We have been developing a new fabrication method of thin films with oriented L10 hard magnetic nanoparticles. The following results are obtained this year: (1) Isolated L10-FePt nanoparticles smaller than 8nm did not show hard magnetic properties in spite of the proceeding of atomic ordering. (2) Long-range order parameter for FePt and FePd isolated nanoparticles were determined by electron diffraction considering the dynamical scattering effects of electrons. Here, it was found that temperature factor and particle height distribution did not seriously affect the derived LRO parameter, while higher acceleration voltage of electrons was useful for determination of the LRO

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parameter in high accuracy. (3) Exchange-coupled Fe/L1o-FePd nano-composite particles were newly synthesized. Large coercivity and high saturation magnetization higher than L10-FePd were achieved due to the exchange coupling between Fe and L10 phase. 3. Local Structure Analysis of Amorphous Materials

We analyzed atomistic structures of functional amorphous materials by transmission electron microscopy and computer simulations. The following results are obtained. (1) Electron-beam-induced amorphization in SiC was examined using a transmission electron microscopy with a field-emission gun. It was found that the amorphization can be induced by the preferential knock-on of carbon atoms. (2) Structural and dynamical properties of amorphous Si-Ge alloys were examined by a molecular-dynamics approach. On the basis of the results obtained by the present simulations, we proposed that the bond length and bond angle around Ge atoms have more distorted than those around Si atoms in amorphous Si-Ge networks. (3) A local atomic structure of an amorphous Ge-Sb-Te thin film in a rewritable optical recording disk was studied using cross-sectional nano-beam electron diffraction and HREM techniques. Atomistic structures of medium range order observed in the amorphous matrix were examined in detail, and the mechanism of functional rapid crystallization in the optical recording was discussed. Publications Original Papers Electron Diffraction and High-resolution Electron Microscopy Study of an Amorphous Pd82Si18 Alloy with Nanoscale Phase Separation, T. Ohkubo and Y. Hirotsu: Phys. Rev. B 67 (2003) 094201(1)-094201(9). Local Atomic Structures of Amorphous Nd4.5Fe77B18.5 Alloys Formed under Different Cooling Rates and Their Relations to the Structures in the Early Stage of Crystallization, T. Hanada, T. Sakamoto, T. Ohkubo, Y. Hirotsu, H. Kanekiyo and S. Hirosawa: Mater. Trans. 44 (2003) 2042-2047. Structure and Magnetic Property Changes of Epitaxially Grown L10-FePd Isolated Nanoparticles on Annealing, K. Sato and Y. Hirotsu: J. Appl. Phys. 93 (2003) 6291-6298. Long-range Order Parameter of Oriented L10-FePt Nanoparticles Determined by Electron Diffraction, K. Sato and Y. Hirotsu: Mater. Trans. 44 (2003) 1518-1522. Effects of Particle Size and Additive Element on the Atomic Ordering Temperature of L10-FePt Nanoperticles, K. Sato, M. Fujiyoshi, M. Ishimaru and Y. Hirotsu: Scripta Mater. 48 (2003) 921-927. Effects of Surface Step and Substrate Temperature on Microstructure of L10-FePt

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Nanoparticles, K. Sato, T. Kajiwara, M. Fujiyoshi, M. Ishimaru, Y. Hirotsu and T. Shinohara: J. Appl. Phys. 93 (2003) 7414-7416. Electron Diffraction Structure Analysis for Amorphous Materials (invited), Y. Hirotsu, T. Ohkubo, I.-T. Bae and M. Ishimaru: Mater. Chem. Phys. 81 (2003) 360-363. Ion-beam-induced Amorphous Structures in Silicon Carbide, I.-T. Bae, M. Ishimaru, Y. Hirotsu, S. Matsumura and K.E. Sickafus: Nucl. Instrum. Meth. B 206 (2003) 974-978. Amorphous Structures of Silicon Carbonitride Formed by High-dose Nitrogen Ion Implantation into Silicon Carbide, M. Ishimaru, M. Naito, Y. Hirotsu and K.E. Sickafus: Nucl. Instrum. Meth. B 206 (2003) 994-998. Electron-beam-induced Amorphization in SiC, M. Ishimaru, I.-T. Bae and Y. Hirotsu: Phys. Rev. B 68 (2003) 144102(1)-144102(4). Molecular-dynamics Study of Structural and Dynamical Properties of Amorphous Si-Ge Alloys, M. Ishimaru, M. Yamaguch and Y. Hirotsu: Phys. Rev. B 68 (2003) 235207(1)-235207(7). Electron Microscopy Study on Amorphous Ge-Sb-Te Thin Film for Phase Change Optical Recording, M. Naito, M. Ishimaru, Y. Hirotsu and M. Takashima: Jpn. J. Appl. Phys. 42 (2003) L1158-L1160. Appearance of the Icosahedral Atomic Cluster in the Formation of the MgCu2-type Structure From the Bcc Structure in Ti-Cr Alloys, A. Hirata, Y. Koyama and M. Tanimura: Phys. Rev. B 67 (2003) 144107(1)-144107(9). Ion Dose Dependence on Solid Phase Epitaxy of Amorphous Silicon Carbide Induced by Ion Implantation, I.-T. Bae, M. Ishimaru and Y. Hirotsu: Proc. Mater. Res. Soc. Symp. 742 (2003) 67-72. Radial Distribution Functions of Amorphous Silicon Carbide, M. Ishimaru, I.-T. Bae and Y. Hirotsu: Proc. Mater. Res. Soc. Symp. 742 (2003) 73-77. Review Papers Atomistic Structure and Its Relaxation Process in Amorphous Silicon Carbide, M. Ishimaru, I.-T. Bae and Y. Hirotsu, J. Crystallogr. Soc. Jpn. 45 (2003) 185-189 (in Japanese). Martenstic Transformation in Nanometer-sized Particles of Au-Cd and Fe-Ni Alloys, K. Asaka, T. Tadaki and Y. Hirotsu: Materia Japan 42 (2003) 725-730 (in Japanese). Cross-sectional Observation of Ge-Sb-Te Amorphous Thin Film for Phase Change Recording, M. Naito, M. Ishimaru, Y. Hirotsu and M. Takashima: Materia Japan 42 (2003) 889 (in Japanese).

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Books Advanced Technoligy and Application of Nano Metals (in Japanese), Y. Hirotsu (subdivision), CMC Publishing Co., Ltd. (2003). International Conferences Structural Studies of Functional Nanomaterials by Modern Electron Microscopy (invited), *Y. Hirotsu, M. Ishimaru and K. Sato, The 41th Symposium on Basic Science of Ceramics, Nanotechnology Symposium for World Young Ceramist, Kagoshima, January 22-23, 2003. New Possibilities in Electron Diffraction Based Phase Analysis in the TEM (invited), *J.L. Lábár, M. Ishimaru and Y. Hirotsu, 6th Multinational Congress on Microscopy – A Regional Meeting with European Extension, Pula, Croatia, June 1-5, 2003. Variation of Short Range Order with the Composition in an Amorphous-Al-Pt Alloy Existing in a Wide Compositional Range, *J.L. Lábár, A Kovács, B.P. Barna, T. Hanada, M. Ishimaru, Y. Hirotsu and I.-T. Bae, 6th Multinational Congress on Microscopy – A Regional Meeting with European Extension, Pula, Croatia, June 1-5, 2003. Formation of Multiply Twinned Nanostructural L10-type FePt Particles, *A. Kovács, G. Sáfrán, K. Sato, P. B. Barna and Y. Hirotsu, 6th Multinational Congress on Microscopy – A Regional Meeting with European Extension, Pula, Croatia, June 1-5, 2003. Local Structural Change of Amorphous Ge-Sb-Te Thin Film during Annealing (Poster), *M. Naito, M. Ishimaru, Y. Hirotsu and M. Takashima, X International Conference on the Physics of Non-Crystalline Solids, Parma, Italy, July 13-17, 2003. Electron Diffraction Study on Chemical Order in Amorphous Silicon Carbide, *M. Ishimaru, I.-T. Bae and Y. Hirotsu, X International Conference on the Physics of Non-Crystalline Solids, Parma, Italy, July 13-17, 2003. Magnetoanisotropy, Long-range Order Parameter and Thermal Stability of Isolated L10 FePt Nanoparticles with Mutual Fixed Orientation (Poster), *K. Sato, T. Kajiwara and Y. Hirotsu, Int’l Conference on Magnetism, Roma, Italy, July 27-Aug.1, 2003. Atomistic Structures of Amorphous Si1-xGex Alloys: A Molecular-dynamics Study (Poster), *M. Yamaguchi, M. Ishimaru and Y. Hirotsu, The 8th IUMRS-International Conference on Advanced Materials, Yokohama, Oct. 8-13, 2003. Fabrication and Structure of Oriented L10-FePd Nanoparticles (Poster), *K. Sato and Y. Hiortsu, Int’l Symposium on Advanced Magnetic Materials, Yokohama, Oct. 8-10, 2003. Nanoscale Phase Separation in Metallic Glasses Studied by Advanced Electron

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Microscopy Techniques (invited), *Y. Hirotsu, T. Hanada, T. Ohkubo and T. G. Nieh, 3rd International Conference on Bulk Metallic Glasses, Beijing, China, Oct 12-16, 2003. The Glass Forming Ability, Microstructure and Magnetic Properties of NdAlNiCuFe Alloys, *Z. Zhang, Y. Hirotsu and W. H. Wang, 3rd International Conference on Bulk Metallic Glasses, Beijing, China, Oct 12-16, 2003. Effect of Cu Addition on the Annealing Process of FeNbSiB Glass (Poster), *T. Hanada, T. Matsumoto, Y. Hirotsu, T. Ohkubo, S. Fijii and Y. Yoshizawa, 3rd International Conference on Bulk Metallic Glasses, Beijing, China, Oct 12-16, 2003. Structural Analysis of Amorphous Ge-Sb-Te Thin Film Using Nano-Beam Diffraction and High-Resolution Electron Microscopy (Poster), *M. Naito, M. Ishimaru, Y. Hirotsu and M. Takashima, International Symposium on Optical Memory 2003, Nara, Nov. 3-7, 2003. Transmission Electron Microscopy Study on Amorphous Structures of Phase Change Optical Recording Material (Poster), *M. Ishimaru, M. Naito, Y. Hirotsu and M. Takashima, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Dec. 8-9, 2003. Fabrication of Exchange-coupled Fe/L10-FePd Nanocomposite Isolated Particles (Poster), *J. Kawamura, K. Sato and Y. Hirotsu, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Dec. 8-9, 2003. Contributions to International Conferences and Journals Y. Hirotsu 8th Asia-Pacific Conference on Electron Microscopy (Organizing

Committee) Y. Hirotsu 16th International Conference on Electron Microscopy (Organizing

Committee) Y. Hirotsu International Conference on New Frontiers of Process Science and

Engineering in Advanced Materials (Advisory Committee) Y. Hirotsu 5th Japan-Polish Joint Seminar on Materials Analysis (Organizing

Committee) Y. Hirotsu 8th IUMRS International Conference on Advanced Materials

(Symposium Chairperson) Publications in Domestic Meetings The Japan Institute of Metals 11 papers The Japan Society of Applied Physics 3 papers The Japanese Society of Electron Microscopy 5 papers Others 10 papers Academic Degrees

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Master Degree of Engineering

Jun-ichi Kawamura

Structure and magnetic properties of exchange-coupled Fe/L10-FePd nanoparticles

Mitsuhiro Yamaguchi

Molecular-dynamics study on structural and dynamical properties of amorphous Si-Ge alloys

Sponsorship Grant-in-Aid for Scientific Research on Priority Area (2) Y. Hirotsu In situ observation of atomistic structures in metallic

liquid and metallic glass ¥31,700,000

Grant-in-Aid for Scientific Research (A) Y. Hirotsu Low Temperature Epitaxy and Magnetic Property of

Ferromagnetic Alloy Nanoparticles with Atomic Order ¥10,400,000

Grant-in-Aid for Encouragement of Young Scientists (B) K. Sato Characterization of atomic ordering process and epitaxial

growth mechanism for FePt and FePd nanoparticles with hard magnetic properties

¥1,800,000

Entrusted Research Y. Hirotsu Special Coordination Funds

for Promoting Science and Technology on “Nanohetero Metallic Materials” from Science and Technology Agency

Electron Diffraction Local Structure Analysis of Nanohetero Metallic Materials

¥11,987,000

Y. Hirotsu NEDO (Advanced Materials Technology Utilizing Glassy Metals for Commercial Uses)

Nano-structure Analysis for the Evaluation of Mechanical Properties in Glassy Metals

¥3,150,000

Cooperative Research Y. Hirotsu Japan Society for the

Promotion of Science, Japan-Europe Joint Research Project

Analysis of Growth Mechanisms of Ferromagnetic Ordered Alloy Nano-particles and its Application

¥560,000

Other Research Funds M. Ishimaru Murata Science Foundation Amorphous structure of

phase change optical recording media and its

¥1,000,000

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effects on crystallization mechanism

K. Sato Hosokawa Powder Technology Foundation

Nanostructural characterization and low temperature synthesis of L10 phase of FePt nanoparticles

¥700,000

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Department of Metallic Materials Process Professor: Hideo NAKAJIMA Research Associates: Teruyuki IKEDA, Soong-Keun HYUN Takuji NAKAHATA Research Technical Expert: Yoshitada NAKAI Graduate Students: Yoshitaro NOSE, Zhenkai XIE, Toshihiko KUJIME Hideo HOSHIYAMA, Takuya IDE, Hirofumi ONISHI Minoru FUSEYA Supporting Staffs: Kimi MATSUO, Kayoko YAMAMOTO Outlines

Metals are fundamental materials indispensable to various structural and functional materials. The main purpose of this department is to investigate physics of metallic materials and develop novel processing of the metallic materials. The department has undertaken the following several topics of the metallic materials science and engineering.

Lotus-type porous metals developed by this department are unique materials which exhibit extraordinary superior mechanical strength. The materials are fabricated by unidirectional solidification of the melts under pressurized gases. Main issues are to investigate properties of lotus-type porous metals and to develop the engineering applications. In this year, we have established the fabrication method for porous metals using continuous zone melting technique, fabricated porous intermetallic compounds and silicon and developed medical devices using the porous metals.

Fundamental study on atomic diffusion is also being carried out for understanding of various processes occurring in materials and synthesizing of advanced metallic materials. Main issue to be solved is elucidation of dynamic behavior of the point defects and atom movements.

Current Research Programs

1. Fabrication of Lotus-type Porous Metals and Alloys

In our research group, porous metals with cylindrical pores extending in one direction have been fabricated by unidirectional solidification under pressurized gas atmosphere utilizing the solubility gaps of gas atoms in metals at melting points. Lotus-type porous metals are superior in mechanical strength to conventional sphere-type porous metals, since the stress concentration around pores does not occur by the stress parallel to the pore growth direction. In this year, we have fabricated lotus-type porous silver and magnesium alloys and have established the fabrication technique for porous metal plates.

Some characteristics such as distorted shape of pores and broad distribution of pore size are observed in porous silver fabricated through unidirectional solidification by casting in oxygen atmosphere. It is considered that the formation of such characteristic

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pores are caused by the redissolution of oxygen gas in pores to the molten silver with insufficient oxygen. We also tried to fabricate porous silver by the Czochralski method, where oxygen is expected to be supplied from the gas phase to the solidification interface, and obtained porous silver with pores with good circularity and more uniform pore size.

The influence of the concentration of alloy elements and the temperature gradient in solidification on the pore morphology was investigated on porous magnesium alloys. It was found that lotus-type porous magnesium alloys with homogenious distribution of cylindrical pores can be fabricated by unidirectional solidification under a large temperature gradient.

We have also fabricated plates of lotus-type porous nickel-based superalloys and stainless steel by applying continuous zone melting technique. This achievement is expected to lead to the application of lotus metals in more various fields.

2. Fabrication of Lotus-type Porous Intermetallics

Lotus-type porous Ni3Al intermetallics whose long cylindrical pores are aligned in one direction have been fabricated by unidirectional solidification of the melt in a pressurized hydrogen gas. The porosity and the pore size decreases with increasing aluminum content. An increase of solidification velocity leads to the decrease of pore diameter and the increase of pore number.

3. Fabrication of Lotus-type Porous Silicon by Unidirectional Solidification in Hydrogen.

We have fabricated lotus-type porous silicon by unidirectional solidification in a pressurized hydrogen atmosphere. The pores are elongated to the solidification direction and the size of the pores ranges from 10 µm to 1 mm in diameter. The porous silicon fabricated in the present work is the first one with unidirectional long pores.

4. Animal Tests on Artificial Bones and Artificial Tooth Roots of Lotus Metals

Pieces of lotus stainless steel and titanium were implanted to beagle dogs. It has been found that new bones grow into pores. Especially on titanium, the implants were bonded to new bones in the early stage of the tests. Thus, lotus metals were found to have good biocompatibility and are expected to be used as artificial bones or artificial tooth roots.

5. Corrosion Resistance of Lotus-type Porous Stainless Steel.

Corrosion resistance of lotus-type porous stainless steel was investigated. By dynamic polarization analysis with water solution of 0.1 mol/l sulfuric acid, it is proved that the electric current density of the polarization curve around -100 mV increases with increasing the ferrite phase formed during solidification.

6. Diffusion Mechanism in L10 and L12-type Ordered Alloys

Ordered alloys FePt and Fe3Pt, which have recently attracted much attention as a

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magnetic material for memory and a structural material, take the L10 and L12-type ordered structure, respectively. The tracer diffusion coefficients of constituent elements in these alloys have been measured by radioactive isotope method. By the comparison of the experimental results with the point defect concentration calculated by a statistical thermodynamic model, the diffusion mechanism has been clarified. Publications Original papers Fe Tracer Diffusion in L10 Ordered FePt, Y. Nose, T. Ikeda, H. Nakajima, K. Tanaka and H. Numakura: Mat. Res. Soc. Symp. Proc., 753 (2003), 381-386. Weld Fusion Property of Lotus-type Porous Cooper by Laser Beam Irradiation, T. Murakami, K. Nakata, T. Ikeda, H. Nakajima and M. Ushio: Mater. Sci. Eng., A357 [1-2] (2003), 134-140. Tracer and Chemical Diffusion in L12-ordered Pt3Fe, Y. Nose, T. Ikeda, H. Nakajima and H. Numakura: Mater. Trans., 44 [1] (2003), 34-39. Fabrication of Lotus-type Porous Brass by Zinc Diffusion into Porous Copper, T. Aoki, T. Ikeda and H. Nakajima: Mater. Trans., 44 [1] (2003), 89-93. Self-diffusion of Titanium in Single Crystalline γ-TiAl, T. Ikeda and H. Nakajima: Defect and Diffusion Forum, 213-215 (2003), 133-141. Diffusion of 59Fe in γ-TiAl Single Crystals, N. Terashita, Y. Nose, T. Ikeda, H. Nakajima, H. Inui and M. Yamaguchi: Mater. Lett., 57 [22-23] (2003), 3357-3360. Re-examination of The Phase Diagram of Fe-Pt system, Y. Nose, A. Kushida, T. Ikeda, H. Nakajima, K. Tanaka and H. Numakura: Mater. Trans., 44 [12] (2003), 2723–2731. Anisotropic Compressive Properties of Porous Copper by Unidirectional Solidification, S.K. Hyun and H. Nakajima: Mater. Sci. Eng. A, 340 [1-2] (2003), 258-264. Effect of Solidification Velocity on Pore Morphology of Lotus-type Porous Metals Fabricated by Unidirectional Solidification, S.K. Hyun and H. Nakajima: Mater. Lett., 57 [21] (2003) 3149-3154. Fabrication of Lotus-type Porous Iron and Steel and The Mechanical Properties, S.K. Hyun, H. Nakajima and T. Ikeda: Proc. 8th Japan Int. SAMPE Sym., ed. N. Takeda, H. Hamada, S. Ogihara and A. Nakai, Japan Chapter of SAMPE, Tokyo, (2003) 753-756. Fabrication of Lotus-type Porous Metals and Physical Properties, H. Nakajima, T. Ikeda

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and S.K. Hyun: Cellular Metals: Manufacture, Properties and Applications, ed. J. Banhart, N. Fleck and A. Mortensen, Verlag MIT Publ. (2003), 191-202. Anisotropic Elastic Constants of Lotus-Structured Porous Metals, M. Tane, T. Ichitsubo, H. Ogi, M. Hirao, T. Ikeda and H. Nakajima: Cellular Metals: Manufacture, Properties and Applications, ed. J. Banhart, N. Fleck and A. Mortensen, Verlag MIT Publ. (2003), 351-354. Measurement and Analysis of Effective Thermal Conductivities of Lotus-type Porous Copper, T. Ogushi, H. Chiba, H. Nakajima and T. Ikeda: Cellular Metals: Manufacture, Properties and Applications, ed. J. Banhart, N. Fleck and A. Mortensen, Verlag MIT Publ. (2003), 493-498. Melting of Lotus-type Porous Copper in Laser Beam Welding, T. Murakami, K. Nakata, T. Ikeda, H. Nakajima and M. Ushio: Cellular Metals: Manufacture, Properties and Applications, ed. J. Banhart, N. Fleck and A. Mortensen, Verlag MIT Publ. (2003), 531-534. Internal Friction in Lotus-structured Porous Copper with Hydrogen Pores, K. Ota, K. Ohashi and H. Nakajima: Mater. Sci. Eng., A341 [1-2] (2003), 139-143. Diffusion in α-Ti and Zr, R. A. Perez, H. Nakajima and F. Dyment: Mater. Trans., 44 [1] (2003), 2-13. Compressive and Bending Properties of Lotus-type Porous Copper, S. K. Hyun and H. Nakajima: J. JRICu, 42 [1] (2003), 77-82. Anisotropic Elastic Constants of Lotus-structured Porous Copper, M. Tane, T. Ichitsubo, H. Ogi, M. Hirao, T. Ikeda and H. Nakajima: J. JRICu, 42 [1] (2003), 83-86. Fabrication of Hydroxyapatite Ultra-thin Film/Lotus-type Porous Metal Hybrid Implant, M. Kawashima, S. Hontsu, H. Nishikawa, Y. Hosoi, Y. Higuchi, T. Ikeda and H. Nakajima: Orthopaedic Ceramic Implants, 22 (2003), 23-27. Elastic-constant Measurement for Lotus-type Porous Magnesium with Resonant Ultrasound Spectroscopy, M. Tane, T. Ichitsubo, R. Takeda, M. Hirao, T. Ikeda and H. Nakajima: J. Japan Inst. Metals, 67 [9] (2003), 417–419. Pore Morphology and Microstructure of Porous Magnesium Alloys Fabricated by Unidirectional Solidification under Hydrogen Atmosphere, H. Hoshiyama, T. Ikeda, K. Murakami and H. Nakajima: J. Japan Inst. Metals, 67 [12] (2003), 714–720. Characteristic of Absorbing Sound in Lotus-type Porous Magnesium, Z. Xie, T. Ikeda, Y.

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Okuda and H. Nakajima: J. Japan Inst. Metals, 67 [12] (2003), 708-713.

Review papers Lotus-type Porous Metals — Fabrication, Strength and Application —, H. Nakajima: J. Soc. Powder. Technol., Japan, 40 [2] (2003), 108–114. Fabrication Technique and Mechanical Properties of Lotus-type Porous Metals, H. Nakajima: The Heat Treatment, 43 [2] (2003), 87-92. Report on 3rd International Conference on Cellular Metals and Metal Foaming Technology, MetFoam2003, T. Ikeda and S. K. Hyun: Materia Japan, 42 [11] (2003), 836. Books ‘Proceedings of 17th University Science Open Symposium — Utilization of Hydrogen towards 21th Century — New Materials and Clean Energy’ Ed. symposium committee, H. Nakajima, Kubapro Corp., Tokyo (2003), 49–60. Patents Tokugan 2003-023887, Machining apparatuses, H. Nakajima et al. Tokugan 2003-050448, Gas turbine parts of porous metals and their fabrication

method, H. Nakajima et al. Tokugan 2003-121606, Sound absorption materials, H. Nakajima, Y. Okuda, Z. Xie

and T. Ikeda Tokugan 2003-119647, Fabrication method for lotus-type porous metals, H. Nakajima

and S. K. Hyun Tokugan 2003-208949, Grinding tools, H. Nakajima et al. Tokugan 2003-359017, Golf club heads, H. Nakajima et al. Tokugan 2003-363529, Heat sink, H. Nakajima et al. Tokugan 2003-432602, Fabrication method for porous semiconductors, H. Nakajima

and Takuji Nakahata.

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International Conferences Anisotropic Fusion Zone of Lotus-type Porous Metals by Laser Welding, *T. Murakami, T. Tsumura, K. Nakata, T. Ikeda, H. Nakajima and M. Ushio, International symposium on Novel Materials Processing by Advanced Electromagnetic Energy Sources (MAPEES’04), Osaka University, March 19–22, 2004. Development of Porous Metals for Medical Devices (Poster), *T. Ikeda, S. Hyun and H. Nakajima, Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience", 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka University, January 13-14, 2004. Analysis of Heat Transfer Characteristics of Lotus-type Porous Copper Heat Sink, *H. Chiba, T. Ogushi, T. Ikeda and H. Nakajima, International Symposium on Micro-Mechanical Engineering — Heat Transfer, Fluid Dynamics, Reliability and Mechatronics — (ISMME 2003), Tsuchiura, Japan, December 1–3, 2003. Fabrication of Lotus-type Porous Iron and Steel and The Mechanical Properties, *S. K. Hyun, T. Ikeda and H. Nakajima, 8th Japan International SAMPE Symposium & Exhibition (SAMPE JAPAN 2003), Tokyo, November 18-21, 2003. Measurement and Analysis of Sound Absorption of Porous Magnesium, *Z. K. Xie, Y. Okuda, S. K. Hyun, T. Ikeda and H. Nakajima, 3rd International Symposium on Designing and Properties of Advanced Engineering Materials (ISAEM-2003), Jeju Island, Korea, November 5–8, 2003. Fabrication of Lotus-type Porous Metals by Unidirectional Solidification in Pressurized Gas Atmosphere and Physical Properties (Invited), *H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Formation and Growth of Gas Pores during Unidirectional Solidification of Water Containing Carbon Dioxide (Poster), *K. Murakami, Y. Nakai, H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Melting Property of Lotus-type Porous Copper by Laser Beam Welding, *T. Murakami, K. Nakata, T. Ikeda, H. Nakajima, M. Ushio, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. (poster) Measurement and Analysis of Effective Thermal Conductivity of Lotus-type Porous Copper, *T. Ogushi, H. Chiba, T. Ikeda and H. Nakajima, 3rd International Conference

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on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Fabrication and Mechanical Property of Lotus-type Porous Magnesium (Poster), *T. Ikeda and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Fabrication of Lotus-type Porous Stainless Steel Bars and Their Microstructure (Poster), *T. Ikeda, T. Aoki and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Mechanical Properties of Lotus-type Porous Iron Fabricated by Unidirectional Solidification in Nitrogen Atmosphere (Poster), *S. K. Hyun, T. Ikeda and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Fabrication and Mechanical Properties of Sotus-type Porous Nickel by Unidirectional Solidification (Poster), Y. Suematsu, *S. K. Hyun, T. Ikeda and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Structure and Mechanical Properties of Lotus-type Porous Magnesium (Poster), *H. Seki, M. Otsuka, T. Ikeda and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Anisotropic Elastic Constants of Lotus-structured Porous Metals (Poster), *M. Tane, T. Ichitsubo, H. Ogi, M. Hirao, T. Ikeda and H. Nakajima, 3rd International Conference on Cellular Metals and Metal Foaming Technology (MetFoam 2003), Berlin, Germany, June 23-25, 2003. Contributions to International Conferences and Journals Hideo Nakajima Materials Letters (Principal Editor) Hideo Nakajima High Temperature Materials and Process (Editorial Board) Hideo Nakajima Diffusion and Defect Data (Editorial Advisory Board) Hideo Nakajima Materials Science Foundations (Editorial Advisory Board) Hideo Nakajima First International Symposium on Point Defect and Nonstoichiometry

(Organizing Committee Member) Hideo Nakajima Third International Conference on Cellular Metals and Metal Foaming

Technology (Organizing Committee Member) Hideo Nakajima International Symposium on Structural and Functional Materials

Design (Organizing Committee Member)

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Hideo Nakajima International Conference on New Frontiers of Process Science and Engineering in Advanced Materials (Organizing Committee Member)

Hideo Nakajima THEMEC’2006 Symposium on Metallic Foams (Organizing Committee Member)

Hideo Nakajima International Conference on Diffusion in Materials (Organizing Committee Member)

Hideo Nakajiima Forth International Conference on Porous Metals and Metal Foaming Technology (MetFoam2005) (Organizing Committee Chairman)

Publications in Domestic Meetings The Japan Institute of Metals 30 Papers The Iron and Steel Institute of Japan 1 Paper High Temperature Society of Japan 2 Papers The Japan Copper and Copper Alloys Research Association 1 Paper The Japan Institute of Light Metals 1 Paper Japanese Society for Biomaterials 1 Paper Japan Society of Refrigerating and Air Conditioning Engineers 1 Paper Academic Degrees Master Degree of Engineering H. Hoshiyama Fabrication and mechanical properties of lotus-type porous

magnesium alloys Sponsorship Grant-in-Aid for Scientific Research on Exploratory Research Hideo Nakajima Fabrication of the light iron with 4 times ¥1,900,000 higher strength than iron Entrusted Research Hideo Nakajima Tsuchiyama Industry Corporation ¥800,000 Development of porous metals by special casting technique Hideo Nakajima Asahi Intecc Co., Ltd. ¥3,630,000 Fabrication and Processing of Porous Metals Hideo Nakajima Engineering Research Association for Supersonic ¥18,117,000 Transport Propulsion System Development of Innovative Multifunctional Foundry Process Other Research Funds Hideo Nakajima The Ministry of Education, Culture, Sports, ¥62,400,000 Science and Technology Grant-in-Aid for Development of Innovative

Collaboration between University and Industry

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Commercialization of Lotus-type Porous Metals Teruyuki Ikeda The Iron and Steel Institute of Japan ¥500,000 Development of Lotus-type Porous Stainless Steel

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Department of Atomic Scale Science Professor: Tomoji KAWAI Associate Professor: Hidekazu TANAKA Adjunct Associate Prof: Michael HERRMANN Research Associates: Katsuki KITAHAMA, Hiroyuki TANAKA, Hea-Yeon LEE Post Doctoral Fellows: Run-Wei LI, Jong-Wan PARK,

Akther AKM Hossain, Choopun SUPAB, Youhei YAMAMOTO, Takeshi YANAGIDA, Bertrand VILQUIN, Jong-Min KIM, Ho-Sup JUNG, Hideaki TOUYAMA

Visiting Researcher Kaoru OJIMA, Toshihito OHTAKE, Takeshi UNO, Keiichi ADACHI, Masaki KANAI, Eriko MIKAMO, Toshihiko MATSUURA, Yusuke YOSHITA, Takao KUSAKA, Takashi KAWABE, Naoki KAWAZOE Graduate Students: Takashi KANNO, Teruo KANKI, Yasushi HOTTA,

Shinichi TANAKA, Tomomi TABUCHI, Koji SUZUKI, Masafumi NAKAMURA, Chikako TAKATO, Munetoshi SEKI, Yoichi OHTSUKA, Masatoshi OHNISHI, Tomohisa SUGIYAMA,Tomohiko NAKAMURA, Ayumu TERAWAKI, Tomoko YAKABE, Toshiyuki KOBAYASHI, Itsuki YAMAMOTO, Fumihiko YAMADA, Ryujiro YAMAZAKI, Makoto KATAOKA, Motoyuki HIROOKA, Suguru NAKAZATO

Under Graduate Students: Yoshihiro NOJIMA, Kazuko FUJIKAWA, Eriko MIZUNO, Research Student: Chiho HAMAI Support Staff: Noriko FUJIBAYASHI, Yukako SAKAMOTO, Chiemi TAKAMORI Outlines

The research group directs toward nano- and bio-science and technology based on material and device science. Main subjects are (1) Preparation of Function Harmonized Artificial Lattices, (2) Atomic Scale Surface Science, (3) Bio-nanosensor by using nanowell electrode. By use of a laser molecular beam epitaxy technique under layer by layer growth conditions, we are challenging in development of highly sensitive IR –sensor by functional transition metal oxide films. Observation and manipulation of a single atom and a molecule are undertaken on DNA molecules with Scanning Probe Microscopic (SPM) methods. We have developed the ultrasensitive electrochemical gene sensing system by using nanowell array electrodes.

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Current Research Programs and Achievements Function harmonized superlattices and thin films. ・Construction of ferromagnetic-(La,Ba)MnO3/ferroelectric- Pb(Zr,Ti)O3 field effect

transistor and realization of electric field control of ferromagnetism at room temperature.

・Development of highly sensitive IR –sensor by functional transition metal oxide films

・Achievement of high resolution lithography (minimum line width of 48nm) on the ferromagnetic transition metal oxide thin film.

Nano-science by using Scanning Probe Microscopes. ・ High resolution scanning tunneling microscopy(STM) and spectroscopy of

individual nucleic acid base molecules of single-straned DNA molecule on clean metal surfaces deposited by a pulse injection method under ultrahigh vacuum condition. ・Observation of single nucleotide resolution differences in density of states and

polarization between DNA bases and a single fluorophore deposited on a clean Cu(111) substrate by measurements of topographic, density of states, barrier height using STM.

Bio-Nanoscience by nanowell electrode ・Development of the ultrasensitive electrochemical gene sensing system by using

nanowell array electrodes. ・Observation of 20 times higher sensitivity compared with the sensitivity on the

electrode with 200 µm diameter with good reproducibility. ・

Publications Original Papers Electrical-Field Control of Metal-Insulator Transition at Room Temperature in a Pb(Zr0.2Ti0.8)O3/La1-xBaxMnO3 Filed Effect Transistor, T. Kanki, Y.-G. Park, Hide. Tanaka, and T. Kawai:Appl. Phys. Lett., 83(2003) 4860-482. Nanoscale Observation of Room-Temperature Ferromagnetism on Ultrathin (La,Ba)MnO3 Films, T. Kanki, R.-W. Li, Y. Naitoh, Hide. Tanaka, T. Matsumoto, and T. Kawai:Appl. Phys. Lett., 83 (2003) 1184-1186. Magneto-Transport Properties of La0.8Ba0.2MnO3/Antiferromagnetic LaMO3 (M=Cr, Fe) Perovskite Tri-Layered Films., T. Kanki, Hide. Tanaka, and T. Kawai:J. Appl. Phys., 93(2003) 4718-4721. Appearance of Magnetic Blocking Temperature in Zinc Magnesium Ferrite Thin Films., Y. Yamamoto, Hide. Tanaka, and T. Kawai:J. Magn. Magn. Mater., 261(2003) 263-268.

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Influence of Microstructures on Exchange Bias Behaviors of La0.7Sr0.3MnO3/La0.33Ca0.67MnO3 Bilayers, D.-W. Kim, T.-W. Noh, Hide. Tanaka, T. Kawai:Solid State Commun., 125 (2003) 305-309. CuPc/PbZr0.2Ti0.8/(La, Ba)MnO3 Field Effect Transistor Heterojunction Photomemory, Y.-G. Park, T. Kanki, H.-Y. Lee, Hide. Tanaka, and T. Kawai:Solid State Electronics Lett., 47(2003) 2221-2224. Invetigations on the Nature of Observed Ferromagnetism and Possible Spin Polarization in Co-doped Anatase TiO2 Thin Films, D.-H. Kim, J.-S. Yang, K.-W. Lee, S.-D. Bu, D.-W. Kim, T.-W. Noh, S.-J. Oh, Y.-W. Kim, J.-S. Chung, Hide. Tanaka, H.-Y. Lee, T. Kawai , J.-Y. Won, S.-H. Park, and J.-C. Lee:J. Appl. Phys., 93 (2003) 6125-6132. Electrical Properties of Poly(dA)-Poly(dT) and Poly(dG)-Poly(dC) DNA Doped with Iodine Molecules, M. Taniguchi, H.-Y. Lee, Hide. Tanaka, and T. Kawai:Jpn. J. Appl. Phys., 42 (2003) 215-216. Near-Field Optical Imaging of Abasic Sities on a Single DNA Molecule, J.-M. Kim, H.- Y. Lee, H. Muramatsu, and T. Kawai: FBBS LETTER, 555(2003) 611-615. Photoinduced Ferroelectric Hysteresis Curve in Organic Photoconductor / Inorganic Ferroelectric Heterojunction Photomemory, Y.-G. Park, H.-Y. Lee, Hiro. Tanaka, H. Tabata, and T. Kawai:J. Kor. Phys. Soc., 42 (2003) S1382-S1385. Atomic Force Microscopy Observation of Stretched DNA on Graphite Surfaces, I. Yamamoto, T. Kanno, Hiro. TANAKA, and T. KAWAI :Jpn.J.Appl.Phys.Vol.42 (2003) 559 - 560 High-Resolution Scanning Tunneling Microscopy Imagin of Escherichia Coli Lysine Transfer Ribonucleic Acid, M. Nishimura, Hiro. Tanaka, and T. Kawai:J. Vac. Sci. Technol., B21(4) (2003 )1265-1267. Visualization of Detailed Structures within DNA, Hiro. Tanaka, and T. Kawai:Surf. Sci. Lett., 539(2003)531-536. La0.7Ce0.3MnO3 Epitaxial Films Fabricated by a Pulsed Laser Deposition Method, T.Yanagida, T. Kanki, B. Vilquin, H. Tanaka and T.Kawai:Solid State Commu., 129 (2004) 785-790.

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Review Papers Highly Sensitive Sensor/Bio-Mimetic Sensor (in Japanese), Hide. Tanaka and T. Kawai:Kagaku-Souch, (2003) 59-61. Visualization of Molecular Structures of DNA by Scanning Probe Microscopy, Hiro. Tanaka and T. Kawai:Protein Nucleic Acid and Enzyme, 48(5) (2003) 614-620. Books Dictionary of Nanotechnology (in Japanese), T. Kawai (Editorial), Kogyo-Chosakai Publishing, (2003) Nanotechnology (in Japanese), T. Kawai, PHP Pocketbook, (2003) Introduction of Nanotechnology:Nano-Fabrication Technique、New Functional and Advanced Devices, Hide. Tanaka (assignment writing) and T. Kawai (assignment writing), Kagaku-Dojin, (2003) Nanotechnology Handbook (in Japanese), Hide. Tanaka (assignment writing) and T. Kawai (assignment writing), Ohm-Sha., (2003). Patents Ferromagnetic Semiconductor Junction Jevice, Hide. Tanaka and T. Kawai, International Patent No.IPPCT/JP03/030604 Field Effect Transistor, Hide. Tanaka, T. Kanki, Y.-G. Park and T. Kawai, International Patent No. PCT/JP03/11300 Nonvolatile Photomemory, How to Memorize and Read the Photo-Information, Hide. Tanaka, Y.-G. Park, H.-Y. Lee, T. Kanki and T. Kawai, JP2003-010746 Biosensor Using Protein DNA Chip and Protein Chip, H.-Y. Lee, J.-W. Park, J.-M. Kim, H.-S. Jung and T. Kawai, JP2003-403398 Biosensor Using Protein DNA Chip and Protein Chip, H.-Y. Lee, J.-W. Park, J.-M. Kim, H.-S. Jung and T. Kawai, JP2003-403408 A Method for Polymers Fixed Substrates and the Substrates Obtained from This Method, Hiro. Tanaka and T. Kawai, JP2003-203163 A Fabrication Method of Substrate on Which Chained Molecules are Stretched and

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Fixed by Using Molecular Interactions, the Substrates Obtained from This Method and Application of Them., Hiro. Tanaka, T. Kanno, I. Yamamoto, S. Tanaka and T. Kawai, JP2003-204981 International Conferences Nanobiology and Nanodevices(Invited), *T.Kawai, Osaka University・EU・LMU Forum 2003 on Nanoscience and Nanotechnology in cooperation with CeNS, Germany, 2003.1.16. Toward DNA Electronics (Invited), *T.Kawai, Third International Symposium on Biomimetic Materials Processing (BMMP-3), Nagoya, 2003.1.27. Artificially Structured Materials Which Show Giant Properties at Room Temperature (Invited), *T.Kawai, The 4th France - Japan Workshop on Nanomaterials, Toshi Centre Hotel, Tokyo, Japan, 2003.3.3. Nanoscience and Nanotechnology using Quantum Beams (Plenary), *T.Kawai, 13th International Conference on Positron Annihilation, Kyoto, Japan, 2003.9.7. Laser MBE for Construction of Multilayered Metal Oxide Devices Sensitive to External Fields (Invited), *T.Kawai, COLA’03(7th International Conference on Laser Ablation, Greece, 2003.10.5. Molecular and Nanowire Interconnects (Invited), *T.Kawai, International Workshop on Smart Interconnects (IWSI), T.Kawai, Atami,Japan, 2003.11.6. DNA Based Electronic and Magnetic Devices (Invited), *T.Kawai, Sweden-Japan Workshop on Bionanotechnology, Kyoto, Japan, 2003.11.9. Nanotechnology toward Human Body Building (Plenary), *T.Kawai, ITRI(Industrial Technology Research Institute)30th Anniversary Celebrations-International Nanotechnology Forum, Taiwan, 2003.11.19. DNA Nanotechnology Toward Biomolecular Electronics (Invited), *T.Kawai, 7th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-7), Nara, Japan, 2003.11.16. Nanotechnology toward Human Building (Invited), *T.Kawai, Nanoscience and Nanotechnology and Quantum Particles (NNQP2003), Tokyo, Japan, 2003.12.15. Biomolecular Electronic Devices (Invited), *T.Kawai, Interdisciplinary Nanoscience Center, CAMP and Department of Physics and Astronomy, University of Aarhus Seminar, Denmark, 2004.1.160.

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Nanotechnology in Japan (Invited), *T.Kawai, IBC EUROFORUM, Denmark,

2004.1.27. Characterization of Artificial Nanostructures and Nanomaterial (Invited), *T.Kawai, The 9th International Symposium on Advanced Physical Fields (APF-9), Tsukuba, Japan, 2004.3.1. Future Trend’s in Nanotechnology (Plenary), *T.Kawai, The 3rd National Congress on Science and Technology for Development “Thailand’s S&T Future Trends in the Coming Decade”, Thailand, 2004.3.15. DNA Nanotechnology Toward Nano-Electronics (Invited), *Hide. Tanaka and T. Kawai International Symposium of Dry Process 2003, Tokyo, 2003.11.14 Nano-Scale Characterization of the Ultra thin (La,Ba)MnO3

Film with Room Temperature Ferromagnetism and Their Device Application, *Hide Tanaka, T. Kanki and T. Kawai, 2003 MRS Fall Meeting, Boston, USA, 2003.12.1 Nano-Patterning on Transition Metal Oxides by SPM Lithography, M. Hirooka, R.-W. Li, *Hide. Tanaka and T. Kawai, The 3rd International Workshop on Novel Quantum Phenomena in Transition Metal Oxides, Sendai, 2003.11.8 Magnetic and Electrical Properties of Field Effect Transistor Using Ferromagnetic (La,Ba)MnO3 Channel, *Hide. Tanaka and T. Kawai, 2nd 21st Century COE and 7th SANKEN International Symposium on Hybridization of Chemistry, Biology and Material Science., Osaka, 2004.1.13 Development of Electrochemical DNA Nanochip Protocol for SNPs Assay (Invited), *H.-Y. Lee, and T. Kawai, The Korean Physical Society-2003 Fall Meeting, DeoGu, Korea., 2003.10. 25. SNPs Assay of Nonlabeled Leptin DNA Based on Biofunctional-Modified Surface(Poster), * H.-Y. Lee, J.-W. Park, J.-M. Kim, R.Yamazaki and T.Kawai, 2003 MRS Fall Meeting, Boston, USA, 2003.12.2 SPM Investigation for an Electrochemical or a Micro-Gravimetric DNA-Sensing Procedure (Poster), * H.-Y. Lee, J.-M. Kim, J.-W. Park, H.-S. Jung, and T.Kawai , 2003 MRS Fall Meeting, Boston, USA, 2003.12.2 High Resolution SPM Imaging of DNA(Invited), *Hiro. Tanaka and T. Kawai, The 8th IUMRS International Conference on Advanced Materials, Yokohama, Oct. 8-12, 2003

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Visualization of Detailed Structures within DNA, *Hiro. Tanaka and T.Kawai, Scanning Probe Microscopy in Life Sciences, Berlin, Germany , Sep.18, 2003 Visualization of Detailed Structures within DNA, *Hiro. Tanaka and T. Kawai, SPM and Organic Materials XII, Mainz, Germany, Sep. 24-26, 2003 Metal-Insulator Transition Phenomena of La0.7Ce0.3MnO3 Thin Films (Poster), *T. Yanagida, T. Kanki, B. Vilquin, Hide. Tanaka and T. Kawai, The 3rd International Workshop on Novel Quantum Phenomena in Transition Metal Oxides, Sendai, Japan, Nov. 5-8, 2003 Nature of Phase Transition Phenomena of La0.7Ce0.3MnO3 Thin Films (Poster), *T. Yanagida, T. Kanki, B. Vilquin, Hide. Tanaka and T. Kawai, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec. 8-9, 2003 Origin of Metal-insulator Transition and Ferromagnetism Phenomena of La0.7Ce0.3MnO3 Thin Films (Poster), *T. Yanagida, T. Kanki, B. Vilquin, Hide. Tanaka and T. Kawai, Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium, Osaka, Japan, Jan. 13-14, 2004 Phase Transition Phenomena of La0.7Ce0.3MnO3 Thin Films, *T. Yanagida, T. Kanki, B. Vilquin, Hide. Tanaka and T. Kawai, American Physics Society March Meeting, Montreal, Canada, Mar. 22-26, 2004 Hall Effect in Strained La0.85Ba0.15MnO3 Thin Films, *T. Yanagida, T. Kanki, B. Vilquin, Hide. Tanaka and T. Kawai, American Physics Society March Meeting, Montreal, Canada, Mar. 22-26, 2004 Metal-Insulator Transition Phenomena in (La, Sr)TiO3 Thin Films (Poster), *B. Vilquin, T. Kanki, T. Yanagida, Hide. Tanaka, T. Kawai, The 3rd International Workshop on Novel Quantum Phenomena in Transition Metal Oxides, Sendai, Japan, Nov. 5-8, 2003 Exemples de Transistor pour L’electronique de Spin (Poster), *B. Vilquin, T. Kanki, T. Yanagida, Hide. Tanaka, T. Kawai, Journees Scientifiques Francophones 2003, Tokyo, Japan, Nov. 24-26, 2003, Metal-Insulator Transition Phenomena in (La, Sr)TiO3 Thin Films (Poster), *B. Vilquin, T. Kanki, T. Yanagida, H. Tanaka, T. Kawai, International Symposium of Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec. 8-9, 2003 Metal-Insulator Transition Phenomena in (La, Sr)TiO3 Thin Films (Poster), *B. Vilquin, T. Kanki, T. Yanagida, H. Tanaka, T. Kawai, American Physical Society March Meeting, Montreal, Canada, Mar. 22-26, 2004

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Nano-Scale Modification of Electrical and Magnetic Properties of Fe3O4 Thin Film by AFM Lithography, M. Hirooka, *B. Vilquin, R. Li, H. Tanaka, T. Kawai, American Physical Society March Meeting, Montreal, Canada, Mar. 22-26, 2004 DNA-Templated Assembly of Gold Nanoparticles, *F. Yamada, Y. Otsuka, T. Matsumoto, H. Tanaka and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Shizuoka, Japan, Dec. 11, 2003 Nano-Patterning on Transition Metal Oxides by SPM Lithography (Poster), *M. Hirooka, Hide. Tanaka, R. Li, and T. Kawai, Novel Quantum Phenomena in Transition Metal Oxide, Sendai, Japan, Nov. 5-8, 2003 Nano-Patterning on Transition Metal Oxides by SPM Lithography (Poster), *M. Hirooka, Hide. Tanaka, R. Li, and T. Kawai, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec. 8, 2003 Nano-Scale Mosdification of Electrical and Magnetic Properties on Fe3O4 Thin Film by AFM lithography, *M. Hirooka, Hide. Tanaka, R. Li, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, Dec. 11, 2003 Contributions to International Conferences and Journals T. Kawai Electronics society (Editorial committee) T. Kawai IEICE (Institute of Electronics, Information and Communication

Engineers) Electronics Express (Editorial committee) T. Kawai e-JSSNT (e-Journal of Surface Science and Nanotechnology)

(Advisory board) T. Kawai The 19th Kyoto Prizes commemoration workshop "new

development of the self-organization of an organic molecule, and nanotechnology" (Special committee)

T. Kawai New Energy and Industrial Technology Development Organization "nano tech 2003 + Future" (Chairman)

Hiro. Tanaka 7th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures(Local arrangement committee)

Publications in Domestic Meetings The Physical Society of Japan 1 paper The Japan Society of Applied Physics 17 papers The Chemical Society of Japan 3 papers The Protein Science Society of Japan 2 papers The Magnetics Society of Japan 4 papers Others 17 papers

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Academic Degrees Master Degree of Science T. Sugiyama Conductance Measurement of DNA Molecule Adsorbed on A Solid

Surface T. Nakamura Studies on The Recognition of Cpg DNA By Toll-Kike Receptor 9 T. Yakabe Formation of Dye-DNA Complexes and Their Optical and Electrical

Properties I. Yamamoto SPM Observation of Cisplatin-Modified and DIG-Modified DNA Master Degree of Engineering Science T. Kobayashi Dielectric Characteristics of Polar Polymer and The Effect on

Organic Field-Effect Transistors

F. Yamada DNA Templated Assembly of Nanoparticle A. Terawaki Electrical Conductivity Measurement of Doped DNA Doctor Degree of Science S. Tanaka Studies on Synthesis of Long Strand DNA with Specific Sequences

Using Enzymatic Reaction and Application To Nano Materials Y. Hotta Relaxor Phenomena in Order-Controlled Complex-Perovskite

Superlatices T. Kanno Atomic Force Microscopy Studies of Structure of Vesicle And

Formation Mechanism of Amyloid Fibril Doctor Degree of Engineering Science T. Kanki Control of Physical Properties of Manganese Oxide thin Films and

Application To Room Temperature Spin Devices Sponsorship Grant-in-Aid for Promoted Research(2) T. Kawai Atom Scale Processing for the Creation of Highly

Harmonized Functional Materials ¥203,000,000

21st Century Center of Excellence T. Kawai Toward Creating New Industries Based on Inter-

Nanoscience ¥330,000,000

Grant-in-Aid for Scientific Research (A) Hide. Tanaka Creation of opt-magnetic materials by programmed self-

assembly using DNA molecules and nano-particles ¥7,700,000

Grant-in-Aid for Scientific Research for Young Scientist (B) Hiro. Tanaka Control of Orientation of Macro Linear Molecules by a

Pulse Injection Method ¥1,900,000

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Fund for JSPS Research fellowships for Young Scientist Y.Yamamoto Fabrication of Orgniac/inoprganic Superlattice and

Their Photo-induced Magnetic Properties. ¥1,000,000

R.-W. Li Construction of Highly Sensitive Photo/magnetic Sensor by Artificial Lattices.

¥800,000

J.-W. Park Development of DNA Devices by using Nanogap-Electrode.

¥800,000

T. Kanki Creation of spin-Controlable Functional Artificial Lattices

¥1,000,000

Y. Hotta Control and evaluation of electric properties in perovskite-type ferroelectric relaxor

¥900,000

B. Vilquin Growth of novel materials using ferroelectric thin films ¥1,200,000 A. Hossain Novel opto-magneto materials by oxide artificial super

lattice ¥1,200,000

Entrusted Research

T. Kawai Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency

Creation of bio-mimetic intellectual material based on programmed self-assembly

amount of acceptance:

¥9,360,000

〔TORAY〕Research and Development of High Through Put Protein Chip: Analysis of Protein Synthesis Mechanism

amount of acceptance:

¥11,340,000

〔Matsushita Electric Industrial Co., Ltd.〕Research and Development of Iimmobilization Method of Biomolecules

amount of acceptance:

¥10,500,000

T. Kawai NEDO: Focus 21 Advanced nanobio device project

〔Shimaz Co.〕Development of Single Molecular DNA Analysis System

amount of acceptance:

¥11,093,000 T. Kawai Leading Project --

Human Body Buling, Construction of artificial five sense sensor ---

Development of The Artificial Internal Organs and Artificial Sensors by Use of Nano-Technology. (Development of The Super Five Senses Sensor)

¥28,000,000

Other Research Funds T. Kawai Core Research for

Evolutional Science and Technology (CREST), Japan Science and Technology Agency

Creation of bio-mimetic intellectual material based on programmed self-assembly

¥56,000,000 (The trust research cost to a university is included)

Hidekazu Tanaka PRESTO21-JST Construction of Strongly Correlated Electron Devices by Nano-scale Function Harmonized

¥8,000,000

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80

Artificial Lattices Hidekazu Tanaka Asahi Glass

Foundation Construction of Novel Magnetoresisitve Material Working at Room Temperature by Oxide Artificial Lattices

¥1,300,000

Hidekazu Tanaka The Shimadzu Science Foundation

Development of Novel Spintronics Devices Evaluation System by Suing Magneto-Optics

¥800,000

Hidekazu Tanaka Hosokawa Powder Technology Foundation

Construction of Photomagnetic Nano-particles Materials by Programmed Self-assembly with DNA Molecule.

¥700,000

Hidekazu Tanaka Research fund for young scientist (Sanken)

A Trial Systematization of Nanotechnology Knowledge Through Ontology Engineering

¥660,000

Hidekazu Tanaka Osaka university (ISIR-Corporative Research for young scientists)

A Trial Systematization of Nanotechnology Knowledge Through Ontology Engineering

¥660,000

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Department of Functional Ceramic Materials Professor: Hikaru KOBAYASHI Associate Professor: Masao TAKAHASHI Research Associates: Kohji NOBUGAI, Osamu MAIDA Hitoo IWASA, Sumio TERAKAWA, ASUHA,

Tadao NAKAMURA Graduate Students: Takuya KOBAYASHI, Naozumi FUJIWARA, Yukio ISHIKAWA, Liu Yueh-Ling, Im Sung-Soon,

Akiko UCHIDA, Kazuki TANAKA, Kenji MATSUBA, Takeshi YOKOTANI, Asako OKAFUJI

Undergraduates: Kanunori KOBAYASHI, Kenichi FUKAYAMA Support Staff: Nao NISHIKAWA, Reiko NOZAKURA Outlines

The modern society is based on semiconductor technology. Our research is aiming to improve the characteristics of semiconductor devices and to develop semiconductor devices with new structure. For this purpose, we have developed new methods of the low temperature formation of insulating layers, a method for the observation of semiconductor interfaces with high sensitivity, and a method of controlling semiconductor interfacial properties. Semiconductor devices studied in this department are as follows: 1) solar cells, 2) metal-oxide-semiconductor (MOS) devices for LSI, 3) thin film transistors (TFT) for display devices. Current Research Programs 1. Low temperature fabrication of MOS diodes by use of chemical method Leakage current flowing through ultrathin silicon dioxide layers is one of the most serious and urgent problems for a further increase in the number of components per IC chips. We have developed a new method for the formation of ultrathin silicon dioxide layers by use of nitric acid (i.e., nitric acid oxidation of Si method, NAOS method). NAOS method simply involves immersion of Si in the azeotropic mixture of nitric acid and water (i.e., 68 % nitric acid) followed by the post-metallization annealing treatment in hydrogen at 200 °C. Using this NAOS method, the leakage current density of the MOS diodes with the 1.3 nm silicon dioxide layers becomes 1/4~1/20 of those for conventional thermally grown silicon dioxide layers (i.e., 0.4 A/cm2 at the forward gate bias voltage of 1 V). In this academic year, the electrical and spectroscopic properties of the NAOS SiO2 layers have been investigated in detail. 2. Development of a semiconductor cleaning method by use of a new chemical

reaction We have developed a new chemical semiconductor cleaning method which can remove metal contaminants below 3×109/cm2. This chemical cleaning method does not accompany etching of materials, and even at room temperature, metal contaminants can be removed. Moreover, this cleaning method can passivate defects in the

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semiconductors, resulting in the improvement of semiconductor devices. Even in the presence of high concentration of metal contaminants in the cleaning solution, the solution possesses the same ability for the metal removal as that in the absence of the contaminants, indicating that the cleaning solution can be repeatedly used. In this academic year, we have found that the cleaning ability of the solutions greatly increases with an increase in pH, and by setting the pH at 10, the Cu contaminants with a 1013/cm2 order surface concentration can be removed below 3×109/cm2 only taking 10 s. 3. Improvement of amorphous Si solar cell characteristics by the use of a new

defect passivation method An abundant amount of materials for the production of amorphous Si solar cells is present on the earth, and moreover amorphous Si films of thickness less than 1 µm are sufficient to absorb light. Therefore, amorphous Si solar cells can be regarded as the cheapest solar cells and are expected to apply to large-scale solar cells for the electricity production. We have developed a new method of eliminating defect states in amorphous Si band-gap, i.e., cyanide treatment. The cyanide treatment is a simple and room-temperature method which only includes immersion of Si in KCN solutions followed by a rinse. We have succeeded in the improvement of energy conversion efficiency of pin-junction amorphous Si solar cells by the use of aqueous cyanide treatment. It is concluded that this improvement results from the elimination of defect states by the reaction of cyanide ions, forming Si-CN bonds. In this academic year, microscopic properties of amorphous Si films with the cyanide treatment have been investigated in detail. 4. High sensitivity observation of SiC/SiO2 interfaces by use of XPS

measurements under bias XPS measurements under bias developed in this laboratory can observe interface states in almost entire band-gap, which cannot be achieved using conventional electrical measurements. Using this method, interface states for SiC, i.e., wide-gap semiconductor with band-gap energy of 2.9 eV, are observed. Interface state spectra were found to depend on the oxidation method. In the case of wet oxidation, a broad structure was observed at ~2 eV above the SiC valence band maximum and it was attributed to Si dangling bonds. In the case of dry oxidation, an additional sharp peak was observed at 1.8 eV and it was attributed to graphitic carbon. Electrical characteristics of SiC-based MOS diodes became poor by the presence of the 1.8 eV interface state peak. Publications Original Papers Nitiric Acid Oxidation of Si to Form Ultrathin Silicon Dioxide Layers with a Low Leakage Current Density, H. Kobayashi, Asuha, O. Maida, M. Takahashi, and H. Iwasa, J. Appl. Phys., 94 [11] (2003) 7328-7335. Experimental and Theoretical Studies of Si-CN Bonds to Eliminate Interface States at Si/SiO2 Interface, O. Maida, A. Asano, M. Takahashi, H. Iwasa, and H. Kobayashi, Surf. Sci., 542 (2003) 244-252.

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Spectroscopic and Electrical Properties of Ultrathin SiO2 Layers Formed with Nitric acid, Asuha, T. Kobayashi, M. Takahashi, and H. Kobayashi, Surf. Sci., 547 (2003) 275-283. Interface states at SiO2/6H-SiC(0001) interfaces observed by x-ray photoelectron spectroscopy measurements under bias: Comparison between dry and wet oxidation, H. Kobayashi, T. Sakurai, M. Takahashi, and Y. Nishioka, Phys. Rev. B, 67 [11] (2003) 115305. Elimination of interface states in the GaAs band-gap by cyanide treatment: XPS measurements under bias, T. Kubota, J. Ivanco, M. Takahashi, K. Yoneda, Y. Todokoro, and H. Kobayashi, Surf. Sci., 529 (2003) 329-337. Passivation of defects in nitrogen-doped polycrystalline Cu2O thin films by crown-ether cyanide treatment,Y. Okamoto, S. Ishizuka, S. Kato, T. Sakurai, N. Fujiwara, H. Kobayashi, and K. Akimoto, Appl. Phys. Lett., 82 [7] (2003) 1060-1062. Passivation of defects in polycrystalline Cu2O thin films by hydrogen or cyanide treatment, S. Ishizuka, S. Kato, Y. Okamoto, T. Sakurai, K. Akimoto, N. Fujiwara, and H. Kobayashi, Appl. Surf. Sci., 216 (2003) 94-97. Photoluminescence properties of a-Si:H based thin films and corresponding solar cells, E. Pincik, H. Kobayashi, H. Gleskova, M. Kucera, L. Ortega, M. Jergel, C. Falcony, R. Brunner, T. Shimizu, V. Nadazdy, M. Zeman, M. Mikula, M. Kumeda, and R. A. C. M. M. van Swaaij, Thin Solid Films, 433 (2003) 344-351. Passivation of defect states in Si and Si/SiO2 interface states by cyanide treatment: improvement of characteristics of pin-junction amorphous Si and crystalline Si-based metal-oxide-semiconductor junction solar cells, N. Fujiwara, T. Fujinaga, D. Niinobe, O. Maida, M. Takahashi, and H. Kobayashi, Acta Physica Slovaca, 53 [3] (2003) 195-205. Ultrathin silicon oxynitride formed by low-energy electron impact plasma nitridation and chemical oxidation methods, M. Takahashi, M. Tamura, Asuha, T. Kobayashi, and H. Kobayashi, J. Appl. Phys., 94 [1] (2003) 726-731. Silicon Nitride and Silicon Dioxide, H. Kobayashi, T. Kobayashi, A. Asano, O. Maida, and M. Takahashi, Thin Insulating Films, 7 (2003) 199-210. On Optical, Electrical and Structural Properties of Amorphous Silicon Based semiconductors, E. Pinčík, H. Kobayashi, J. Müllerová, K. Gmucová, M. Jergel, R. Brunner, M. Zeman, and M. Zahoran, Acta Physica Slovaca, 53 [4] (2003) 267-278. Patents Method of Fabrication of Si Solar Cells and Fabricated Solar Cells, Y. Yonekura, S. Goya, S. Morita, and H. Kobayashi, Tokugan 2003-028206. Method of cleaning of semiconductor apparatus, cleaning method of semiconductor

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production machines, and cleaning apparatus, H. Kobayashi, Tokugan 2003-178855. Photovoltaic devices, their production method, and apparatus for their production, H. Kobayashi, Tokugan 2004-092281. Semiconductor apparatus, their production method, and their production apparatus, H. Kobayashi, Tokugan 2003-271590 Production method of Si solar cells and produced solar cells H. Kobayashi, Tokugan 2003-382764 Solar cell devices and their production method H.Kobayashi, M. Takahashi, K. Rai, T, Watsuji, Tokugan 2003-166349 Formation method of oxide layers, semiconductor devices, fabrication method of semiconductor devices, and production apparatus for semiconductor devices, H. Kobayashi, Tokugan 2004-093695 Formation method of oxide layers, semiconductor devices, fabrication method of semiconductor devices, and production apparatus for semiconductor devices, H. Kobayashi, Tokugan 2004-093689 Thin film transistors, fabrication method, display devices, and method of improvement of oxide properties, H. Kobayashi, S. Imai, K. Inoguchi, Tokugan 2004-093703 Production method of substrates for semiconductor apparatus, production method of semiconductor apparatus, and apparatus for the production of semiconductor apparatus, H. Kobayashi, PCT/JP03/15063 Formation method of silicon dioxide layers on silicon substrates and production method of semiconductor appatus, PCT/JP03/06348 International Conferences Cyanide Treatment to Improve Electrical Characteristics of Si-based MOS Diodes with an Ultrathin Oxide Layer,* H. Kobayashi, 203rd Meeting-Paris, Paris, France, Apr. 27-May 2, 2003. Semiconductor Surface and Interface Passivation by Cyanide Treatment, *H. Kobayashi, O. Maida, M. Takahashi, K. Akimoto, III International Workshop on Semiconductor Surface Passivasion-SSP’ 03, Ustron, Poland, Sep. 14-17, 2003. Defect Passivation Cleaning of Si by Use of Cyanide Solutions, *M. Takahashi, N. Fujiwara, I. Ryu, O. Maida, H. Kobayashi, III International Workshop on Semiconductor Surface Passivasion-SSP’ 03, Ustron, Poland, Sep. 14-17, 2003. Defect Passivation by Cyanide Treatment and Improvement of Silicon device Characteristics,* H. Kobayashi, Technical Forum of Silicon Materials and Science,

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Shonan, Japan, Nov. 25-27, 2003. New Si cleaning method for removal of Cu and Ni contaminants without chemical etching (Poster), *Masao Takahashi, Yueh-Ling Liu, Naozumi Fujiwara, Tadao Nakamura, Kenichi Fukayama, Hitoo Iwasa, and Hikaru Kobayashi, Second 21st Century COE"Towards Creating New Industries Based on Inter-Nanoscience" & 7th SANKEN International Symposium, Suita, Osaka, Jan. 13-14, 2004. Defect Passivation etch-less cleaning of Si at room temperature by use of new surface reactions, *H. Kobayashi, SNST 2004 Conference, Bratislava, Slovakia, Feb. 27-Mar. 4, 2004. Contributions to International Journals H. Kobayashi Applied Surface Science, Editor Publications in Domestic Meetings

The Physical Society of Japan 2 papers The Japan Society of Applied Physics 10 papers Amorphous Seminar 1 paper

Academic Degrees Master Degree of Science A. Uchida Surface reaction of Si and aluminum and application to solar cell

electrode material K. Tanaka Formation and properties of ultrathin insulating layer/Si structure K. Matsuba Low temperature oxidation of Si by use of electrochemical method T. Yokotani Formation of Cu2O thin films by means of sputtering evaporation

method and their properties Doctor Degree of Science N. Fujiwara Interaction of Cyanide Ions with Si: Passivation of Defects and

Removal of Surface Copper Sponsorship Grant-in-Aid for Scientific Research (B) O. Maida Control of threshold voltage of MOSFET by inclusion

of fixed charges in insulators ¥2,500,000

Asuha Low temperature formation of SiO2/Si structure and

decrease in leakage current density ¥1,200,000

Entrusted Research H. Kobayashi Japan Science and

Technology Corporation

Silicon Thin Film Solar Cells with New Chemical Bonds

¥4,550,000

H. Kobayashi New Energy and Industrial Technology

Development of Solar Cell Fabrication Technology by

¥13,529,000

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Development Organization

the Use of Cat-CVD

M. Takahashi Japan Science and Technology Corporation

Suppression of Charge Carrier Recombination in Polycrystalline Si by Cyanide Treatment

¥1,216,000

H. Kobayashi Frontier Associates Practical study of defect passivation etch-less semiconductor cleaning technology

¥19,950,000

Other Research Funds H. Kobayashi Core Research for

Evolutional Science and Technology

Silicon Thin Film Solar Cells with New Chemical Bonds

¥65,290,000

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Department of Structural Ceramic Materials Professor: Koichi NIIHARA Associate Professor: Tohru SEKINO Research Associates: Takafumi KUSUNOSE, Tadachika NAKAYAMA Research Technical Experts: Yamato HAYASHI, Yo YAMAMOTO, Hao WANG,

Rajagopalan RAMASESHAN, Masaaki NAGASHIMA Graduate Students: Bum-Sung KIM, Akio HIKASA, Takuya NOMOTO,

Masashi WADA, Rak-Joo SUNG, Yoon-Ho KIM, Ari HIRVONEN, Seung-Ho KIM, Kazunori TANAKA, Noriaki KAWAGUCHI, Tomoaki SAWADA, Hiroaki MIZOGUCHI, Takeshi UKAI, Takumi OKAMOTO, Masahiro SASAKI

Research Students: Yoshitaka SAIJO, Yutaka TAWADA Support Staffs: Emiko KITAURA, Rie SUEHIRO Outlines Ceramics material is one of the most promising key materials for supporting the science and technology of the coming 21st century. It is now required to be a multi-functional material to meet the future demand. It is over 15 years since we proposed a new materials design concept "nanocomposite technology", that realizes the dominant improvement of mechanical properties of ceramics by controlling nano- and atomic-scale structure of the polycrystalline ceramics. Based on this concept, this department has been focusing mainly on the basic researches for developing high-performance ceramic-based materials with multiple functionalities over the decade. Special emphasis is placed on the understanding of the relation between the nanostructures and mechanical properties. Systematic researches have revealed that the mechanical properties of these nanocomposite ceramics are remarkably enhanced even at high temperatures. In addition excellent functional properties, such as machinability, superplasticity, electric/magnetic properties and so on, are also found to be consistent with the improved mechanical property. Recent studies suggest that the nanocomposite concept is also applicable to metal and organic materials. Thus the target of these researches is to develop new materials, named "intermaterials" which ranges ceramic, metal and organic materials. Current Research Programs 1. Design of Nanocomposite Concept and Development of High Performance Ceramic-based Nanocomposites. To develop high performance ceramic-based materials we focused on the microstructural control of ceramics in nanometer-scale. It realizes "Nanocomposite" in which nanometer-sized second phase exists within several oxide and nonoxide ceramics. These composite materials exhibit superior mechanical properties, i.e., high fracture strength, toughness, creep resistance, thermal shock resistance and so on, not only at room temperature but also at elevated temperature. Development of new ceramic nanocomposites possessing superplasticity, machinability are also achieved by

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synthesizing nanostructured and nanocomposite powders, and/or by using conventional sintering method, novel in-situ sintering, reaction sintering and spark plasma sintering methods. In this study preparation process, micro/nano/interface structure, and properties relation have been investigated. Roles of nanostructures on properties enhancements are also studied in detail. 2. Development of Non-oxide Nanocomposites. Most non-oxide ceramics such as silicon nitride are sintered by assisting of liquid phase during heating, due to the small amount of additives and oxide impurities at the powder surfaces. Sintered bodies thus have grain boundary glassy phases that decrease mechanical performances at elevated temperature. In this study passive control of additives and resultant grain boundary structures, micro- and nano-structures as well are investigated. Selecting suitable additives and sintering methods resulted in high-performance and low-cost non-oxide ceramic nanocomposites, which enlarges the industrial applications of the materials. Relationships between processing-structure-properties are systematically investigated. 3. Fabrication and Properties of Ceramic/Metal Nanocomposites. Dispersing metallic second phase particles into ceramics is suitable to improve mechanical properties of ceramics. Furthermore wide variety of advantages for addition of new function such as magnetic, electric and optical properties can be considered due to the size effect of nano-sized metal dispersion. Conventional powder metallurgical method and solution chemical process like sol-gel, co-precipitation method have been used to prepare the composite powder for ceramic/metal nanocomposites such as Al2O3/W,Mo,Ni,Cu,Co,Fe, ZrO2/Ni,Mo, MgO/Fe,Co,Ni, and so on. They are sintered in a reductive atmosphere that gives homogeneous dispersion of metallic particles within the ceramic matrices. Fracture strength, toughness, and/or hardness are enhanced due to the microstructural refinement by nano-dispersion and their plasticity. For transition metal dispersed oxides ceramic composites, ferromagnetism is also compatible with its excellent mechanical properties. In addition, good magnetic response for the applied stress was found in these ceramic/ferromagnetic-metal nanocomposites, showing the possibility of remote-sensing of fracture/deformation of ceramic materials. 4. Development of Functional Ceramic-based Nanocomposites and Their Properties Improvement. Nanocomposite technology is also applicable to the functional ceramics such as ferroelectric, piezoelectric, varistor and ion-conducting materials. Incorporation of small amount of ceramic or metallic nanoparticles into BaTiO3, ZnO, c-ZrO2 can significantly improve their mechanical strength, hardness and toughness which are very important to realize high reliable electric devices operating in a severe environmental condition. In addition, electric properties can also be enhanced by dispersing nanoparticles. Relationships between nano- and interface-structure, mechanical properties and electric properties have been investigated in detail. Also the nanocomposite technology can be used to the magnetic materials. For the hard magnet materials, nanostructural control has found to realize great improvement of the magnetic properties, which is used to practical application.

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5. Design and Development of Atomic/Molecular-Level Composites. We have proposed new materials design concept which is consisted of structural control in atomic and molecular level. These materials can be prepared by incorporating very small amount of additive into ceramics. The additive segregates at the grain boundary with gradient concentration, or precipitates molecular or cluster seized particles within the grains or at the grain boundaries. In this study relation between preparation process - structural development mechanisms - properties have been investigated by means of detailed TEM observations. 6. Design and Development of Novel Ceramic-Nanocomposites with Pseudoplastic Deformation Properties. Dispersing soft materials into hard ceramic is generally thought to decrease its mechanical properties. However, we discovered that nanocompositing of soft materials with several kinds of ceramics can be improve their mechanical properties. For example addition of hexagonal boron nitride into silicon nitride ceramic can enhance its fracture strength not only at room temperature but also at very high temperature up to 1500°C. In addition, this nanocomposite exhibits superior thermal shock resistance and machinability because of the characteristic pseudoplasticity of the nanocomposites like metallic materials. This is due to the micro-fractures of materials within and around the soft nano-dispersion. These results indicate that ceramic/h-BN nanocomposites can be directly applicable to the high temperature structural materials. In this research optimization of preparation processes, properties and microstructures have been studied for several combination of composites. 7. Development and Properties of Layer by Layer Lattice Composites with Bulky Form. Addition of small amount of oxides was found to form superlattice structure with cyclic period of several angstrom in lithium niobate. In this study bulky sintered body of this material has successively prepared by controlling powder processing and sintering procedure. Detailed TEM investigations revealed that the periodicity of superstructure was varied depending on the amount of additive and sintering condition, and some insulating layer was formed at the phase boundary of each superlattices. Temperature dependence of dielectric constant was performed up to high-temperature and some dielectric relaxation phenomena due to the 1st or 2nd order phase transformation were observed. This is found to be relating with its characteristic superstructure. Present study thus revealed that realizing novel electric properties could be achieved in a bulk material when layer-by-layered superstructures are controlled in an atomic scale. 8. Development of High Performance Organic Polymers by Nanocompositie Technology. To overcome the disadvantage of low mechanical properties of polymer (organic) materials, nano-sized ceramic particles have been incorporated. It is well known that chemical bonding as well as physical properties of ceramic and polymer is quiet different, thus the optimization of preparation process is important. In this study, fabrication processes, microstructure, physical and mechanical properties of the polymer/ceramic composites have been investigated. By optimization of the

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fabrication process and controlling the nano-sized second phase dispersion, thermal stability and mechanical properties such as adhesion resistance, flexural strength, toughness and hardness can be enhanced which exhibits the great advantage of nano-dispersion. More recently, we are introducing nano technology in polymer/ceramic system to investigate the electrical property relationship with microstructure for practical applications, resulted in successive development of novel tactile sensor material. Publications Original Papers Influence of Size Distribution on the Magnetocaloric Effect of Superparamagnetic Gold-magnetite Nanocomposite, T. Kinoshita, S. Seino, H. Maruyama, Y. Otome, K. Okitsu, T. Nakayama, K. Niihara, T. Nakagawa, and T. A. Yamamoto : J. Alloys and Comp., 365 (2004) 281-5. Fabrication and Characteristics of Fine-grained BaTiO3 Ceramics by Spark Plasma Sintering, W. Luan, L. Gao, H. Kawaoka, T. Sekino, and K. Niihara : Ceram. International, 30 (2004) 405-10. Peculiar Surface Deformation of Sapphire: Numerical Simulation of Nanoindentation, R. Nowak, T. Manninen, K. Heiskanen, T. Sekino, A. Hikasa, K. Niihara, and T. Takagi : Appl. Phys. Lett., 83 [25] (2003) 5214-6. Silicon Nitride Ceramics with Sodium Ion Conductive Grain Boundary Phase, H. Kawaoka, T. Sekino, T. Kusunose, and K. Niihara : J. Mater. Res., 18 [12] (2003) 2752-5. Preparation of Multi-Layered Self-Healing Coating by Using Silica and Swelling Clay, A. Hikasa, T. Sekino, Y. Hayashi, and K. Niihara : Trans. Mater. Res. Soc. Japan, 28 (2003) 691-4. Machinability and Contact Damage of Al2O3/BN Composites Fabricated through Chemical Processing, T. Kusunose, T. Nomoto, T. Sekino, B. -S. Kim, Y. Yamamoto, and K. Niihara : J. Ceram. Soc. Jpn., 111 [11] (2003) 821-5. Preparation and Characterization of Metal/Ceramic Nanoporous Nanocomposite Powders, Y. -H. Choa, J. -K. Yang, B. -H. Kim, Y. -K. Jeong, J. -S Lee, T. Nakayama, T. Sekino, and K. Niihara : J. Magnetism and Magnetic Mater., 266 [1-2] (2003) 12-9. Synthesis of Bismuth Sodium Titanate Nanosized Powders by Solution/Sol-Gel Process, C. -Y. Kim, T. Sekino, and K. Niihara : J. Am. Ceram. Soc., 86 [9] (2003) 1464-7. Fabrication of Metastable ZrO2-x Single Nano-sized Particles, M. Nagashima, T.

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Nakayama, S. Yamanaka, M. Fujikane, Y. Hayashi, T. Sekino, T. Kusunose, and K. Niihara : Mater. Lett., 57 [24-25] (2003) 4023-7. Tribological and Microstructural Analysis of Al2O3/TiO2 Nanocomposites to Use in the Femoral Head of Hip Replacement, S. -W. Lee, C. Morillo, J. Lira-Olivares, S. -H. Kim, T. Sekino, K. Niihara, and B. J. Hockey : Wear, 255 [7-12] (2003) 1040-4. Mechanical and Magnetic Properties of Alumina/Nickel Nanocomposites Prepared by Pulse Electric Current Sintering, B. –S. Kim, T. Sekino, T. Nakayama, T. Kusunose, J. –S. Lee, and K. Niihara : J. Ceram. Soc. Jpn., 111 [7] (2003) 457-60. Structural Characteristics of Diamond-like Nanocomposite Films Grown by PECVD, W. –J. Yang, Y. –H. Choa, T. Sekino, K. –B. Shim, K. Niihara, and K. -H. Auh : Mater. Lett., 57 [21] (2003) 3305-10. Thermal Stability Evaluation of Diamond-like Nanocomposite Coatings, W. –J. Yang, Y. –H. Choa, T. Sekino, K. –B. Shim, K. Niihara, and K. -H. Auh : Thin Solid Films, 434 [1-2] (2003) 49-54. Microstructural Characterization of Silicon Nitride/Boron Nitride Nanocomposites, T. Kusunose, H. Kondo, Y. Yamamoto, M. Wada, T. Adachi, T. Sekino, T. Nakayama, and K. Niihara : Ceramic Transactions -Ceramic Nanomaterials and Nanotechnology-, 137 (2003) 181-8. Measurement of Microscopic Stress Distribution of Multilayered Composite by X-ray Stress Analysis, T. Adachi, T. Sekino, T. Nakayama, T. Kusunose, and K. Niihara : Mater. Lett., 57 [20] (2003) 3057-62. Synthesis and Structure of Preferred-oriented Li2O-Nb2O5-TiO2 Thin Film with Superstructure, Y. Yamamoto, T. Sekino, H. Hayashi, T. Nakayama, T. Kusunose, and K. Niihara : Mater. Lett., 57 [18] (2003) 2702-6. Phase Stability and Electrical Property of NiO-doped Yttria Stabilized Zirconia, H. Kondo, T. Sekino, T. Kusunose, T. Nakayama, Y. Yamamoto, and K. Niihara : Mater. Lett., 57 [9-10] (2003) 1624-8. Pulse Electric Current Sintering of Alumina/Nickel Nanocomposites, B. S. Kim, T. Sekino, T. Nakayama, M. Wada, J. S. Lee, and K. Niihara : Materials Research Innovation, 7 [2] (2003) 57-61. Microstructure and Dielectric Properties of Sintered Li-Nb-Ti-O Solid Solution Ceramics Having Superstructure, Y. Yamamoto, H. Hayashi, T. Sekino, T. Nakayama, H. Kondo, M. Wada, T. Adachi, and K. Niihara : Materials Research Innovation, 7 [2]

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(2003) 72-4. Solid-Solution Effects of a Small Amount of Nickel Oxide Addition on Phase Stability and Mechanical Properties of Yttria-Stabilized Tetragonal Zirconia Polycrystals, H. Kondo, T. Sekino, T. Kusunose, T. Nakayama, Y. Yamamoto, M. Wada, T. Adachi, and K. Niihara : J. Am. Ceram. Soc., 86 [3] (2003) 523-5. Preparation of Fine Alumina Dispersed Ytterbia Stabilized Cubic Zirconia Based Composites, M. Wada, T. Sekino, Y. -H. Choa, B. -S. Kim, T. Kusunose, T. Nakayama, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 85-9. Fracture and Tribological Behaviors of Al2O3/5 vol.% SiC Nanocomposites, S. -H. Kim, Y. -H. Kim, S. -W. Lee, T. Sekino, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 90-4. Mechanical and Thermal Properties of Hot Pressed Si3N4 Added with AlN, R. J. Sung, S. W. Lee, T. Nakayama, T. Kusunose, T. Sekino, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 119-27. Properties of Hot Pressed AlN/BN Nanocomposites, T. Kusunose, T. Sekino, B. -S. Kim, Y. -H. Choa, T. Nomoto, Y. Yamamoto, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 131-6. Fabrication of Various Nano Noble Metal Composite Materials by Ecological Sono-Process, Y. Hayashi, T. Sekino, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 233-7. Fabrication of Metastable Oxide Ceramics with Oxygen Vacancy, M. Nagashima, T. Nakayama, S. Yamanaka, M. Fujikane, T. Sawada, Y. Hayashi, T. Sekino, T. Kusunose, and K. Niihara : Materials Science Forum, Eco-Materials Processing & Design, 439 (2003) 254-8. Mechanical Properties and Microstructure for 3mol% Yttria Doped Zirconia/Silicon Carbide Nanocomposites, N. Bamba, Y. -H. Choa, T. Sekino, and K. Niihara : J. Eur. Ceram. Soc., 23 [5] (2003) 773-80. Tribological Evaluation of Si-O Containing Diamond-like Carbon Films, W. -J. Yang, Y. -H. Choa, T. Sekino, K. -B. Shim, K. Niihara, and K. -H. Auh : Surface and Coatings Technology, 162 [2-3] (2003) 183-8. Crack Propagation Behavior of Nano-sized SiC dispersed Multilayered Al2O3/3Y-TZP Hybrid Composites, T. Adachi, T. Sekino, T. Kusunose, T. Nakayama, A. Hikasa, Y. -H.

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Choa, and K. Niihara : J. Ceram. Soc. Jpn., 111 [1] (2003) 4-7. Magnetic Evaluation of Nanostructure of Gold–Iron Composite Particles Synthesized by a Reverse Micelle Method, T. Kinoshita, S. Seino, K. Okitsu, T. Nakayama, T. Nakagawa, and T. A. Yamamoto : J. Alloys and Compounds, 359 (2003) 46-50. Magnetic Composite Nanoparticle of Au/γ-Fe2O3 Synthesized by Gamma-Ray Irradiation, S. Seino, T. Kinoshita, Y. Otome, K. Okitsu, T. Nakagawa, and T. A. Yamamoto : Chem. Lett., 32 [8] (2003) 690-1. Review Papers New World of Nanocomposites, K. Niihara, T. Sekino, T. Nakayama, and T. Kusunose : Chemical Engineering, 48 [6] (2003) 409-15. New Prosperity of Engineering Ceramics in the 21st Century, K. Niihara, T. Sekino, T. Kusunose, T. Nakayama, : Bull. Ceram. Soc. Jpn., 38 [4] (2003) 255-63. Fabrication of the Ceria Based Cluster Composites by Gas Condensation Method, T. Nakayama, M. Nagashima, K. Niihara, : Materials Integration, 16 [2] (2003) 54-9.

Multi-functional Ceramics by Nanostructure Control : K. Niihara, T. Sekino, T. Nakayama, and T. Kusunose, : Functional Material, 23 {4} (2003) 47-56. Books Fabrication and Industrial Application of Nanocomposite Materials, K. Niihara, T. Sekino, T. Kusunose, T. Nakayama, and Y. Hayashi : 34th CS Technoseminar “World of Nanotechnology” Supplement”, Toyo Seiki Seisaku-sho, Ltd., (2003)37-60. Patents

“Nanoparticle of a Catalyst and Its Processing,” M. Ito, J. Hasegawa, M. Sato, K. Niihara, T. Nakayama, and Y. Hayashi, Tokugan 2003-366240. “Pressure Electric Sensor”, K. Nihara, T. Sekino, K. Ogawa, and T. Okumura, Tokugan 2004-074498. “Pressure Measurement Equipment”, K. Niihara, T. Sekino, K. Komamizu, M. Iwase, A. Tanaka, Y. Okamoto, Y. Hamahashi, and H. Murata, Tokugan 2004-82818. “Synthesis Method of AlN-BN Composite Powder and Fabrication Method of AlN/BN Composite”, K. Niihara and T. Kusunose, Tokugan 2003-196162. “Fabrication Method of Electrically Conductive AlN and Its Application for Semiconductor Manufacturing Equipment”, K. Niihara and T. Kusunose, Tokugan 2003-275462.

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“Synthesis Method of IIIB Series Nitride”, K. Niihara and T. Kusunose, Tokugan 2003-330777. International Conferences Radiation Induced Synthesis of Au/Fe Oxide Nanocomposite Particles for Magnetic Separation of Biomolecules, *S. Seino, T. Kinoshita, Y. Otome, T. Nakagawa, K. Okitsu, T. Nakayama, T. Sekino, K. Niihara, and T. A. Yamamoto, 2003 International Nano Ceramics / Crystals Forum and International Symposium on Intermaterials (NCF7 & IMA7), Hanyang University, Seoul, Korea, September 25-28, 2003. Synthesis of Metastable Nanomaterials by Gas Condensation Process, *T. Nakayama, M. Nagashima, S. Seino, T. Yamamoto, M. Fujikane, S. Yamanaka, H. Kume, Y. Nishikawa, T. Sawada, T. Shigaki, T. Sekino, T. Kusunose, and K. Niihara, 2003 International Nano Ceramics / Crystals Forum and International Symposium on Intermaterials (NCF7 & IMA7), Hanyang University, Seoul, Korea, September 25-28, 2003. Plasma Behavior of Electrically Conductive Zinc Oxide, *T. Yamamoto, T. Sekino, T. Kusunose, T. Nakayama, K. Niihara, and H. Haneda, 2003 International Nano Ceramics / Crystals Forum and International Symposium on Intermaterials (NCF7 & IMA7), Hanyang University, Seoul, Korea, September 25-28, 2003. Synthesis and Characterization of Self-structuralized TiO2 Nanotube, *T. Sekino, K. Shibata, T. Okamoto, T. Kasuga, H. Kawaoka, Y. Hayashi, T. Nakayama, T. Kusunose, and K. Niihara, 2003 International Nano Ceramics / Crystals Forum and International Symposium on Intermaterials (NCF7 & IMA7), Hanyang University, Seoul, Korea, September 25-28, 2003. Multifunctional Nanocomposites and Their Industrial Applications, *K. Niihara, 2003 International Nano Ceramics / Crystals Forum and International Symposium on Intermaterials (NCF7 & IMA7), Hanyang University, Seoul, Korea, September 25-28, 2003. Radiation-Induced Synthesis of Magnetic Composite Nanoparticle of Iron Oxide and Noble Metal (Poster), *S. Seino, T. Kinoshita, Y. Otome, T. Nakagawa, T. A. Yamamoto, K. Okitsu, T. Nakayama, and K. Niihara, The 8th IUMRS International Conference on Advanced Materials (IUMRS-ICAM 2003), Yokohama, Japan, October 8-13, 2003. Manipulation of Biomolecules by Au/γ-Fe2O3 Composite Nanoparticles, *T. Kinoshita, S. Seino, Y. Otome, T. Nakagawa, K. Okitsu, Y. Mizukoshi, T. Nakayama, T. Sekino, K. Niihara, and T. A. Yamamoto, 2003 MRS Fall Meeting, Boston, MA, USA,

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December 1-5, 2003. Gamma-Ray Synthesis of Nanocomposite Particles Composed of Magnetic Iron Oxide and Noble Metal, *S. Seino, T. Kinoshita, Y. Otome, T. Nakagawa, K. Okitsu, T. Nakayama, T. Sekino, K. Niihara, and T. A. Yamamoto, 28th International Cocoa Beach Conference and Exposition on Advanced Ceramics & Composites, Doubletree and Hilton Hotels, Cocoa Beach, Florida, USA, January 25-30, 2004.

Fabrication of 3Y-TZP/TiNi composites by reduction sintering process, *N. Tanaka, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara, Student Seminar 2003 in Finland, Helsinki, Tampere, and Turku, Finland, January 6-11, 2004. Multi-functional Ceramic Nanocompoites and Their Applications (Invited), *K. Niihara, T. Sekino, T. Kusunose, and *T. Nakayama, The 8th CONFERENCE & EXHIBITION OF THE EUROPEAN CERAMIC SOCIETY 2003 The Istanbul Convention and Exhibition Centre, Istanbul, Turkey, July 1, 2003.

Fabrication and Characterization of Metastable Single Nano Sized Particles (Poster), *T. Nakayama, M. Nagashima, S. Seino, T. Yamamoto, M. Fujikane, S. Yamanaka, H. Kume, Y. Nishikawa, T. Sawada, T. Shigaki, T. Sekino, T. Kusunose, and K Niihara, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003) ISIR, Osaka University, Osaka, Japan, December 9, 2003.

Synthesis of Metastable Single Nanosized Composites by Vapor Deposition Method (Poster), *T. Nakayama, S. Seino, M. Nagashima, T. Shigaki, Y. -H. Choa, T. A. Yamamoto, S. Yamanaka, T. Kusunose, T. Sekino, H. Kume, A. Nishikawa, and K. Niihara, The 5th International Symposium on Eco-Materials Processing and Design (ISEPD2004), Nagaoka Ground Hotel, Nagaoka, Niigata, Japan, January 19 – 21, 2004. Evaluation of Photocatalytic Activity of Zinc Oxide Powders: A Proposal of the Concept of Dye Fading Factor (DFF), *T. Yamamoto, T. Sekino, T. Kusunose, T. Nakayama, K. Niihara, H. Nakamura, and E. Abe, The 5th International Symposium on Eco-Materials Processing and Design (ISEPD2004), Nagaoka Ground Hotel, Nagaoka, Niigata, Japan, January 19 – 21, 2004.

Morphology and Magnetic Properties of Single Nano Sized Composites (Poster), *T. Nakayama, S. Seino, M. Nagashima, T. Shigaki, T. A. Yamamoto, Y. Hayashi, T. Sekino, T. Kusunose, S. Yamanaka, and K. Niihara, IUMRS-ICAM, Pacifico Yokohama, Yokohama, Japan, October 10, 2003, Residual Stress and Thermal Conductivity Control by Surface Nanocomposite Coating, *T. Sekino, T. Adachi, Y. Yamamoto, and A. Hirvonen, The 8th IUMRS International Conference on Advanced Materials (IUMRS-ICAM2003) Yokohama, Kanagawa, Japan,

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October 8-13, 2003. Design and Development of Multifunctional Nanocomposites (Invited), *T. Sekino, H. Kondo, B. S. Kim, T. Nakayama, T. Kusunose, and K. Niihara, The 1st International Symposium on Nanostructured Materials: Structural Applications, KIST, Seoul, Korea, October 30-31, 2003. Electrical Multifunctionalization of Structure Ceramics by Grain-boundary Control, *T. Sekino, T. Ukai, B. S. Kim, M. Wada, T. Nakayama, T. Kusunose, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Aluminum Nitride Based Ceramic Nanocomposites with Multifunctionality, *T. Kusunose, T. Sekino, H. Yotoh, T. Nakayama, and T. Sekino, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Study of Polymer / Clay Nano Composites for Conducting Polymer Sensors, *R. Rajagopalan, T. Sekino, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Study on the Properties and Microstructure of Mullite-Fe2O3 Composite, *H. Wang, T. Sekino, T. Kusunose, T. Nakayama, B. -S. Kim, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Fabrication of Y-TZP/Ferrite Nanocomposites (Poster), *M. Wada, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Decomposition Behavior of Noble Metal Oxide by Ultrasonic Cavitation and its Application (Poster), *Y. Hayashi, T. Sekino, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003. Preparation and Corrosion Phenomena of Self-Healing Multi-Layered Coating by Silica and Swelling Clay (Poster), *A. Hikasa, T. Sekino, Y. Hayashi, T. Kusunose, T. Nakayama, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003.

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Fabrication of Alumina/Nickel Nanocomposite Films by Aqueous Monomer Suspension Coating Method (Poster), *B. -S. Kim, T. Sekino, T. Nakayama, T. Kusunose, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003.

Effect of NiO Addition and Internal Reduction on Phase Development and Properties of Zirconia Ceramics, *T. Sekino, H. Kondo, B. -S. Kim, N. Tanaka, T. Nakayama, T. Kusunose, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Electrical and mechanical Properties of Grain-Boundary-Phase Controlled Silicon Nitride, *Y. -H. Kim, T. Sekino, H. Kawaoka, T. Kusunose, T. Nakayama, and K. Niihara, The 5th International Meeting of the Pacific Rim Ceramic Societies (PACRIM5), Nagoya Congress Center, Nagoya, Japan, September 29 - October 2, 2003.

Residual Stress and Thermal Conductivity Control by Surface Nanocomposite Coating (Poster), *T. Sekino, T. Adachi1, Y. Yamamoto, A. Hirvonen, T. Kusunose, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Tribological Properties of Al2O3/SiC Nanocomposites, *S. -H. Kim, T. Sekino, T. Kusunose, T. Nakayama, S. -W. Lee, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Forming of Ceramic/Metal Nanocomposites by Gelcasting, *B. -S. Kim, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. The effect of Alumina Addition on the Martensitic Transformation in Zirconia-Yttria Ceramics (Poster),*N. Tanaka, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara,

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The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Preparation and Magnetic Properties of Mullite-Fe Nanocomposites (Poster), *H. Wang, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Magnetic Nanocomposite Prticles Composed of Noble Metals and Iron Oxides Synthesized by Gammma-ray Irradiation (Poster), *S. Seino, T. Kinoshita, Y. Otome, T. Nakagawa, K. Okitsu, T. Nakayama, T. Sekino, K. Niihara, and T. A. Yamamoto, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Fabrication of Aluminum Nitride with Electrical Conductivity and High Thermal Conductivity, *T. Kusunose, T. Sekino, H. Yotoh, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Fabrication of Alminum Nitride/Boron Nitride with High Thermal Conductivity (Poster), *T. Kusunose, T. Sekino, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in

the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Production and Evaluation of the Cordierite-Zirconia Nano Composite Ceramics as a Coating Material (Poster), *A. Hirvonen, Y. Yamamoto, T. Sekino, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. High Dimensionally Controlled Microstructure of LiNbO3-based Crystal Composite (Poster), *Y. Yamamoto, J. K. Chung, T. Sekino, T. Kusunose, T. Nakayama, C. J. Kim,

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and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Thermoelectric Characteristics of GeO3-NaCo2O4 Solid Solution (Poster), *M. Sasaki, T. Sekino, T. Kusunose, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Fabrication and Properties of Electrically Conductive ZrO2 Ceramics (Poster), *T. Ukai, T. Sekino, B. -S. Kim, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. The Ionic Conductivity of Grain Boundary-Phase Controlled Silicon Nitride(poster), *Y. -H. Kim, T. Sekino, H. Kawaoka, T. Kusunose, T. Nakayama, and K. Niihara, The 2nd Asian International Symposium on the Science of Engineering Ceramics (EnCera2003), in the conjunction of The 22nd Forum on Basic Science for High-temperature Ceramics and The 10th Seminar on Core University Program (CUP) between Japan and Korea, Gamagohri, Aichi, Japan, November 10-13, 2003. Effect of Synthesis Condition on Structure and Properties of Titania Nanotube, *T. Sekino, T. Okamoto, K. Shibata, Y. Hayashi, T. Nakayama, T. Kusunose, T. Kasuga, and K. Niihara, 28th International Cocoa Beach Conference & Exposition on Advanced Ceramics & Composites In Conjunction with the 8th International Symposium on Ceramics for Energy Storqge and Power Conversion Systems Doubletree/Hilton Hotels, Cocoa Beach, Fla. USA, January 25-30, 2004.

Study of Polymer / Clay Nano Composites for Pressure Sensor, *R. Rajagopalan, T. Sekino, and K. Niihara, The 5th International Symposium on Eco-Materials Processing & Design (ISEPD 2004), Nagaoka, Japan, January 19 -21, 2004.

Toward Creating New Industries Based on Nanocomposite Materials (Invited), *K. Niihara, The 5th International Symposium on Eco-Materials Processing & Design (ISEPD 2004), Nagaoka, Japan, January 19 -21, 2004.

Aqueous Suspension Process of Multi-Dimensional Alumina/Nickel Nanocomposites, *B. -S. Kim, T. Ukai, T. Sekino, T. Nakayama, and K. Niihara, The 5th International

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Symposium on Eco-Materials Processing & Design (ISEPD 2004), Nagaoka, Japan, January 19-21, 2004.

Fabrication and Microstructural Control of Cordierite-MSZ Composites, *Y. Yamamoto, A. T. Hirvonen, T, Sekino, T. Sekino, T. Kusunose, and K. Niihara, The 8th IUMRS International Conference on Advanced Materials, Yokohama, Japan, October 8-13, 2003.

High Dimensionally Controlled Microstructure of LiNbO3-based Crystal Composite (Poster), *Y. Yamamoto, J. K. Chung, T. Sekino, T. Kusunose, T. Nakayama, C. J. Kim, and K. Niihara, The 10th Seminar on Core University Program between Japan and Korea, Aichi, Japan, November 10-12, 2003. Materials with Stress/Microfracture Sensitivity, *K. Niihara, The 8th International Symposium on Synergy Ceramics, Shunagawa Prince Hotel, Tokyo, Japan, February 5-6, 2004. Contributions to International Conferences and Journals Koichi Niihara The International Nano Ceramic Forum and The International

Symposium on Internationals (NCF & IMA) (Co-chairman) Koichi Niihara Seminar on Core University Program between Japan and Korea

(Chairman) Koichi Niihara The 5th International Symposium on Eco-processing and Materials

(Chairman) Koichi Niihara The 3rd International Symposium on the Science of Engineering

Ceramics (Chairman) Koichi Niihara International Symposium on Nanostructured Materials (Organizing

Committee) Koichi Niihara International Symposium on Advanced Ceramic Materials, Indian

Ceramic Society (Internatinal Organizing Committee) Koichi Niihara The Int. Symp. On Synergy Ceramics (Chairman) Koichi Niihara Journal of Korean Ceramics Society (Editorial Board) Koichi Niihara Advances in technology of Materials and Materials Processing

Journal (ATM) (Editorial Board) Koichi Niihara Journal of Nanoscience and Nano Technology (Editorial Board) Koichi Niihara Materials Integration (Editor) Koichi Niihara Journal of the Chinese Ceramic Society (Editorial Board) Koichi Niihara Journal of Ceramic Processing Research (Editorial Board) Koichi Niihara The 3rd International Symposium on Advanced Ceramics

(Internatinal Organizing Committee) Koichi Niihara Int’l Japan-Korea Seminar on Ceramics (Editorial Board) Koichi Niihara 11th International Conference on Fracture (ICF11) (Organizing

Committee) Tohru Sekino The 3rd International Symposium on the Science of Engineering

Ceramics(Organizing Committee)

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Tohru Sekino International Conference on New Frontiers of Processing Science and Engineering in Advanced Materials (PSEA'04)( Scientific Advisory Board)

Tohru Sekino Materials Integration (Editorial Board) Publications in Domestic Meetings The Ceramic Society of Japan 10 papers Japan Society of Powder and Powder Metallurgy 4 papers The Japan Institute of Metals 1 paper The Magnetics Society of Japan 2 papers Others 6 papers Academic Degrees Bachelor Degree of Engineering Yoshitaka Saijo Multi-functionization of Rubber Material by Sono-process

Precipitated Nano Particle Yutaka Tawada Fabrication and Advanced Functionization of Organic-

inorganic Nono-sensor Master Degree of Engineering Noriyuki Kawaguchi Fabrication of New Thermoelectric Materials Based on

Complex Oxide Systems Tomoaki Sawada Synthesis of Oxide Based Ceramic Composites with Thermal

and Electrical Properties Hiroaki Mizoguchi Chemical Synthesis of GaN Nanoparticles Doctor Degree of Engineering Akio Hikasa Multilayered Clay Composite Coatings with Self-

Respoponsiveness Masashi Wada Fabrication and Evaluation of Oxide Based Composite

Materials with Multi-Functionality Takuya Nomoto Development of Biocompatible Calcium Phosphate Composite

Bone Cement Yo Yamamoto Synthesis and Characterization of High-Dimentionally Designed

Ceramic-Based Composites with Superstructure Sponsorship Grant-in-Aid for Scientific Research on Priority Areas (A) (2) Koichi Niihara Development of Multi-functionalized Ceramics

Controlled in Atom, Molecular and Nanometer Scale ¥5,100,000

Grant-in-Aid for Scientific Research on Exploratory Research Tohru Sekino Synthesis, Structure Analysis and Functionalization of

Oxide Nanotube ¥1,000,000

Tadachika Nakayama

Hydrogen Storage Property of Nano Cluster Level Oxide Composites

¥800,000

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Grant-in-Aid for Scientific Research on Special Research Fellow Satoshi Seino Radiation-Induced Synthesis of Single-Nanosized

Composite Nanoparticles with Improved Functionality. ¥1,100,000

Yoon-Ho Kim Fabrication of Grain-Boundary Controlled Electric Conductive Ceramic Nanocomposite

¥1,000,000

Entrusted Research Koichi

Niihara METI (Regional Research & Development Consortium Project)

Research and Development of High-Performance Human-Interface Nano-sensor

¥11,600,000

Tohru Sekino NEDO (Materials Nanotechnology Program, Nanocoating Project)

Development of Nanocomposite Coating by In-situ Structuralization.

¥5,565,000

Cooperative Research Koichi

Niihara Fine Ceramics Technology Cooperative Association

Studies on Remote Sensing of Micro-fractures and Stresses by Nanocomposite Technology

¥10,554,000

Koichi Niihara

Nikkato Corp Development of Grain-boundary Nanostructure Controlled Ceramics

¥5,000,000

Koichi Niihara

Japan Society for the Promotion of Science

Core University Program Between Japan (JSPS) and Korea (KOSEF)

¥31,300,000

Other Research Funds Takafumi

Kusunose NEDO (Industrial Technology Research Grant Program in 2001)

Development of Si3N4/BN Nanocomposites with Multifunctionality

¥7,150,000

Tadachika Nakayama

NEDO (Industrial Technology Research Grant Program in 2002)

Fabrication of the Novel Single Nano Composites Catalysts with High Efficiency

¥15,405,000

Takafumi Kusunose

Tokuyama Science and Tchnology Foundation

Fabrication of AlN/BN Nanocomposite with multifunctionality

¥2,000,000

Takafumi Kusunose

Iketani Science and Technology Foundation

Strengthening and Toughening of Si3N4 by YSiO2N Grain Boundary Phase

¥1,000,000

Takafumi Kusunose

Mazda Foundation Electric Discharge Machining and Insulating of AlN with High Thermal Conductivity and Electrical Conductivity

¥1,200,000

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Department of Advanced-Energy Material Professor: Katsumi TANIMURA Associate Professor: Shin’ichiro TANAKA Research Associates: Tetsuya NISHIURA, Kenichi ISHIKAWA Graduate Students: Ei’ichi INAMI, Support Staff: Emi TANABE, Sachiyo NOZAWA,

Masanobu NUNOGAKI Outlines For fabricating highly functional nano-structured devices in future technology, it is essential to establish the ways to control structures and compositions of materials in atomic levels. In this department, we aim to establish the fundamentals for controlling the atomic binding in epitaxial processes via excitation-induced atomic reactions. For this purpose, we have carried out extensive experimental studies in the following two categories: 1) the primary processes of the structural changes induced at solid excited state, 2) laser-induced structural changes of semiconductor surfaces, As topics in the first category, we have studied the primary processes of Frenkel-pair formation by electronic excitation in ionic crystals, the initial process of photoinduced polymerization of diacetylene crystals, and the dynamics of the photoinduced phase transition in quasi-one dimensional organic crystals. As topics of the second categories, we have studied laser-induced structural changes of clean surfaces of Si and InP by means of not only the direct imaging of the surface atomic structure and its changes by STM, but also highly sensitive detection of Si atoms emitted from surfaces in the time scale of femtoseconds Current Research Programs 1. Dynamics of Photoinduced Phase Transition in Quasi-One Dimensional Organic Crystals The purpose of this subject is to elucidate the mechanisms of photoinduced phase transitions characteristic of quasi one-dimensional organic crystals. The real-time dynamics, studied by femtosecond time-resolved studies, give crucial information for establishing microscopic understanding of the mechanisms. Topics studied in this year and the main results obtained are summarized below. 1) The primary process of photo-induced polymerization of diacetylene crystals For one of typical diacetylene crystals that show photo-induced polymerization, the primary process of di-radical formation has been studied for 5,7-dodecadiyne-1,12-diol bis[phenyl carbamate] (TCDU). By combining luminescence and optical absorption measurements, we have concluded that the di-radical intermediate is formed by fusion of the triplet self-trapped exciton with a mobile free excitons in this crystal. This is the first clear demonstration of the primary process of photo-induced polymerization. 2) Femtosecond time-resolved reflection spectroscopy of poly-diacetylene crystals with

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two different phases In order to elucidate the characteristics of relaxation of photogenerated excited states in polyerized 5,7-dodecadiyne-1,12-diol bis[phenyl carbamate] (ply-TCDU) crystals with A and B phases, we carried out time-resolved reflection spectroscopy studies by using femtosecond laser light. We have found two-step processes of de-excitation of excited species in both A and B phases; time constants of the processes are 300 fs and 2.2 ps. Population recovery is characterized by the slow step, but the structures resulted are not he same as the original ones. The photo-generated structures are characterized by shorter coherent lengths, and they restore the original structures at much longer time delay of ms. There were not essential difference between crystals with A and B phases.

These features observed have given us important clues to understand the mechanisms of photo-induced phase transitions in this type of crystal. 3) The dynamics of neutral-to-ionic phase transition in tetrathiafulvalen-p-chloranil

crystals As a series of studies for this topic, we studied temperature dependent features of the

dynamics of the phase transition. Among the three distinctive steps of the precursor-forming step, local proliferation, and neutral-phase forming step in the transition, the first step is not dependent on temperature. However, the second and the third steps depend strongly on temperature. The temperature dependence has been characterized by an activation energy of 10 meV, which is essentially the same as free-energy difference between neutral and ionic phases at low temperatures. This result reveals an important role of system free energy in governing the dynamics

of the processes following optical excitation to generate charge-transfer excitons int his crystal. 2. Studies of Excitation-Induced Instability on Semiconductor Surfaces We have constructed an experimental set up for detecting desorbed neutral species simultaneously with high sensitivity. This femtosecond non-resonant ionization spectroscopy has a detection limit as low as the order of 10-7 monolayers per pulse. By using this method, together with STM for revealing the structural changes on surfaces from atomic level, we have studied the laser-induced electronic processes of structural changes and desorption for Si(111)-(7x7), Si(001)-(2x1), Si(111)-(2x1) and InP(110)-(2x1) surfaces. Changes induced by the excitation in surface-atomic structures were directly imaged by STM, and desorption of neutral atoms upon excitation were investigated by laser-ionization spectroscopy with high sensitivity. For all surfaces studied, the laser-induced electronic excitation results in surface structural changes associated with bond breaking of constituent atoms incorporated in the intrinsic surface structures. Main results are summarized as follows. 1) The morphology of defects generated by laser-induced bond breaking depends critically on the Fermi level of crystals in III-V semiconductors. On the InP(110)-(1x1) surfaces, P-vacancy clusters are formed predominantly on n-type surfaces, while isolated P-monovacancies are formed exclusively on p-type surfaces. In view of the fact that surface P-monovacancies are charged positively (negatively) on p-type (n-type) surfaces, this anomalous Fermi-level effect has revealed the crucial role of surface holes in the structural instability on the surfaces.

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2) The role of two-hole localization in anion-vacancy formation on the (110) surfaces of III-V semiconductors at the third regime of Langmuir evapolation

We have studied theoretically the significant Fermi-level effects on the formation rate of anion vacancies on vacuum-cleaved III-V semiconductor surfaces revealed by STM observations, by applying the two-hole localization mechanism of bond rupture on semiconductor surfaces. The increasing rate of vacancy formation with hole concentration results from the enhanced rate of two-hole localization at surface anion sites due to reduced energy separations between the Fermi energy and the energy level of the surface state composed of occupied anion dangling bonds.

Thus, the phenomena under laser excitation and those under thermal equilibrium can be understood on the same basis in terms of carrier localization at surface sites.

3) Photoinduced structural instability on the Si(111)-(2x1) surface

We have shown that the top-most Si atoms on the Si(111)-(2x1) surface have been removed electronically under valence excitation of Si crystals. The mechanism of two-hole localization has been proposed for the bond rupture, based on the studies under valence excitation. Here we have shown that the instability is in fact induced under infrared-laser excitation that results only in the surface specific optical transitions without inducing any bulk valence excitations of Si crystals. The results have revealed the crucial role of holes generated in the surface valence state of semiconductor surfaces. 4) Surface-structural instability induced by excitation with low-energy electron beams with high resolution

For establishing new methods of nano-scale fabrication of semiconductor surfaces, the instability of surface structures under low-energy electron excitation has been studied for the Si(111)-(7x7) surface. The excitation of the surface with 30-eV electron beams, which results in the valence excitation of Si, induces site-sensitive bond breaking of adatoms on the surface; the center adatoms are removed three times more efficiently than the corner adatoms, similar to the case of laser excitation. However, the rate of bond breaking is almost in proportion to the intensity of electron beams, showing strong contrast to the super-linear dependence of the rate on laser intensity. The difference suggests that the spatial profiles of excitation densities are not the same for the two ways of excitation; the electron-beam excitation may result in local dence excitation along the tracks of electron beams. 5) Surface carrier dynamics on the Si(001)-(2x1) studied by femtosecond two-photon

photoelectron spectroscopy In order to elucidate the dynamics of photogenerated surface carriers, which play crucial roles in the excitation-induced instability, we have studied the electron dynamics on the surfaces by means of two-photon photoelectron spectroscopy. Use of femtosecond laser pulses for pump and probe pulses has a strong advantage for resolving the carrier dynamics directly. On the Si(001)-(2x1) surface, we show that the decay of the photoelectron peak due to surface un-occupied state of Ddown is essentially the same as the de-population of bulk electrons near the bottom of conduction band. The result shows that the lifetime of the surface Ddown state is shorter than at most 20 ps, and that the transition from bulk-to-surface states is rate-determining of the surface-state

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population. 4. The Primary Processes of Photoinduced Structural Instabilities in Insulating

Solids 1) Temperature-dependent yield of Frenkel pairs generated by valence excitation in

NaCl The dynamics of formation of self-trapped excitons (STEs) and Frenkel pairs upon

band-gap excitation have been studied in NaCl by femtosecond time-resolved spectroscopy at temperatures ranging from 6 to 330 K. We found that the primary yield of Frenkel pairs was governed by the process of exciton relaxation that terminated within 10 ps of excitation for all temperatures studied. The yield increases with temperature, and is anti-correlated with the yield of triplet STEs, showing a strong effect of temperature on branching during exciton relaxation. We discuss the mechanism of the temperature-dependent branching of excitons based on the present results and knowledge accumulated from studies of other crystals. 2) Optical transitions of self-trapped holes in amorphous SiO2

Optical and electron-spin resonance (ESR) spectroscopy studies of low-temperature electron-irradiated amorphous SiO2 were carried out to identify optical transitions of self-trapped holes (STHs). Spectroscopic analysis by means of polarized optical bleaching and thermal annealing has revealed two components comprising an absorption band around 2.2 eV: the low-energy component peaking at 2.16 eV and the high energy component at 2.60 eV. These bands are formed with similar yields in three different samples that include different chemical impurities and native defect concentrations. Based on quantitative correlations between ESR signals and optical absorption strengths, the 2.16-eV band is attributed to the two-center type STH, while the 2.60-eV band is attributed to the one-center STH. The origin of STH optical transitions is discussed based on the results of this work and recent theoretical data. 5. Highly functional Surface-layer formation by Means of Charged-particle Irradiation and Plasma Processing We have developed a multiplex surface processing for creating “a new type metal ceramics” which have the properties of high thermal loading. The multiplex processing is the sequential process of the reactive modification of metal surfaces by irradiation with charged particle beams, followed by plasma processing for carburization, nitridation or oxidation. For establishing the method of this unique processing, we have constructing moving electrodes, which make it possible of ion-beam irradiation and plasma processing for the same samples without breaking high vacuum condition. The electrodes has given a reasonable performance in intensity and in stability. Publications

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Original Papers

Exciton Self-Trapping and Formation of Diradical Intermediates in 5,7-dodecadiyne- 1,12-diol bis[phenylcarbamate](TCDU) Crystals at Low Temperatures,

C. Itoh, T. Kondoh, and K. Tanimura, J. Chem. Phys. 118, 7572-7577 (2003). Bond Rupture of Threefold-Coordinated Si Atoms at Intrinsic Sites on The Si(111)-(2x1) Induced by 1.16-eV Photon Excitation, E. Inami, K. Ishikawa, and K. Tanimura, Surf. Sci. Lett. 540, L587-L592 (2003). Optical Transitions of Self-Trapped Holes in Amorphous SiO2, Y. Sasajima and K. Tanimura, Phys. Rev. B 68, 014204-1-7 (2003). Temperature-Dependent Yield of Frenkel Pairs Generated by Valence Excitation in

NaCl Katsumi Tanimura and Wayne P. Hess, Phys. Rev. B 69, in print. Role of Two-Hole Localization in Anion-Vacancy Formation on The (110) Surfaces

of InP and GaAs at The Third Regime of Langmuir Evaporation, K. Tanimura, Phys. Rev. B 69, 03301-1-4 (2004). Photoinduced Structural Instability of The InP(110)-(1x1) Surface, T. Gotoh, S. Kotake, K. Ishikawa, J. Kanasaki, and K. Tanimura, Phys. Rev. Lett. in print. Femtosecond Time-Resolved Reflection Spectroscopy of Photoinduced Ionic-to-Neutral Phase Transition in Tetrathiafulvalen-p-Chloranil Crystals,

Katsumi Tanimura, Phys. Rev. B, in print.

International Conferences Optical transitions of self-trapped holes in amorphous SiO2, Y. Sasajima and K. Tanimira, the 10th International Conference on the Physics of Non-Crystalline Solids, (Parma, Italy, July 14-17, 2003). A conventional low-energy ion source for light/heavy ion beams, M. Nunogaki, S. Emura, and K. Tanimura, International Symposium on Science and Industrial Nanotechnology, (Osaka, Japan, December 8-9, 2003). Publications in Domestic Meetings Physical Society of Japan 8 papers

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Academic Degrees Bachelor Degree of Engineering J. Tsuruta Photoinduced instability of III-V semiconductor surfaces

Sponsorship Grand-in-Aid for Scientific Research (B) K. Tanimura Mechanisms of photoinduced structural phase

transitions of quasi one-dimensional organic crystals studied by time-resolved Raman-scattering spectroscopy

¥11,100,000

Grand-in-Aid for Scientific Research (B) K. Ishikawa Photoinduced structural changes on the Si(111)-(2x1)

surface ¥2,200,000

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Division of Organic Molecular Science Outline

Division of Organic Molecular Science has five departments: Dep. of Organometallic

Compounds, Dep. of Organic Fine Chemicals, Dep. of Organic Molecular Materials, Dep. of Molecular Excitation Chemistry, and Dep. of Synthetic Organic Chemistry. The research field in the division covers organic chemistry, organometallic chemistry, physical organic chemistry and photochemistry. In each department research on own original subject is going on and in some cases joint projects between several departments are carried out. A special project “Energy and Environment Friendly Materials," supported by the Ministry of Education, Culture, Sports, Science and Technology, Japan, was performed for the past five years. Achievements •Synthesis of giant platinum-acetylide dentrimers having 189 platinum atoms •Synthesis of helical-chiral poly(isocyanide)s in which the metal-porphyrin pendants

are regularly arranged around the helical main chain •Synthesis of helical-chiral poly(isocyanide)s having ferrocenyl pendants which exhibit

reversible conformational change in response to external electric stimulus •Ru-catalyzed carbonylation of allenyl-alcohols and –amines giving lactones and

lactams, respectively, with atom economy of 100% •Stereoselective reactions of planar-chiral cyclopentadienyl-ruthenium complexes • Self-Assembly of transition metal ions with bipyridine ligands • Synthesis of β-strand peptidomimetics bearing an epoxide cross-linker • Synthesis and properties of nano-scale conjugated materials and their application to

molecular electronics • Highly emissive materials based on a phosphorus-bridged bithiophene unit • A study on shielding effects of molecular wires insulated with permethylated

cyclodextrins • Construction of molecular machines “molecular muscles” and “molecular stomas”

based on permethylated cyclodextrins • Beam-controlled chemistry of DNA • Multi-laser multi-step photochemistry • Laser multiple-photon chemistry and isotope separation • Photochemical control of artificial protein • Synthesis and application of new asymmetric ligands • Immobilization of multicomponent consisting asymmetric catalysts • Functionalized nanoparticle as an asymmetric catalyst • Elucidation and design of organic reactions

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Department of Organometallic Chemistry Professor: Shigetoshi TAKAHASHI Associate Professor: Kiyotaka ONITSUKA Research Associate: Da-Yang ZHOU Research Assistant: Fumie TAKEI Research Technical Expert: Yasuhiro YAMAMOTO Graduate Students: Naoko OHARA, Daisuke KODAMA, Satoshi

SUETSUGU, Akira HAYASHI, Tomoko MORI Support Staff: Yoko KAJI Outlines

The main projects of this department are the synthesis of new organometallic

complexes and their application for selective organic synthesis and controlled polymerization with low impact for the environment as well as for the novel hybrid materials having unique functions. Current works are focused on the synthesis of optically active transition-metal complexes with planar and helical chirality, and the precise synthesis of organometallic polymers with characteristic molecular structures. Properties and reactivities of these new complexes are investigated for the development of novel homogeneous catalysts and functional materials. Current Research Programs

1. Synthesis and Properties of Organotransition Metal Polymers

A new route to giant platinum-acetylides dendrimers has been developed by using a divergent method. We prepared the sixth-generation dendrimer having a formula of C6279H10278P378Pt189Si192, the molecular weight of which was as high as 139750. 2. Screw-sense-selective Polymerization of Isocyanides

(1) The living polymerization of phenyl isocyanides possessing chiral ferrocenyl groups was initiated by hetero-dinuclear µ-ethynediyl complexes of Pd and Pt to give one-handed helical polymers, which exhibited reversible change of the helical conformation in response to the redox of the ferrocenyl pendants.

(2) A novel triblock polyisocyanide having free-base- and zinc-porphyrins as pendants was prepared, and the irradiation at 420 or 556 nm in a THF solution led to the intramolecular energy transfer from the zinc-porphyrin to the free-base-porphyrin. 3. Homogeneous Catalysis for Organic Synthesis

Allenyl alcohols and amines with a variety of substituents underwent cyclocarbonylation in the presence of a ruthenium-carbonyl cluster under mild conditions to give lactones and lactams, respectively, in good yields with 100% atom economy. Publications

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Original Papers A Divergent Approach to the Precise Synthesis of Giant Organometallic Dendrimers Using Platinum-Acetylides as Building Blocks, K. Onitsuka, A. Shimizu, and S. Takahashi: Chem. Commun., (2003), 280-281. Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants, F. Takei, S. Nakamura, K. Onitsuka, A. Ishida, S. Tojo, T. Majima, and S. Takahashi: Chem. Lett., 32 (2003), 506-507. Synthesis and Property of Helical-Chiral Polyisocyanides Bearing Ferrocenyl Groups as Pendants, N. Hida, F. Takei, K. Onitsuka, K. Shiga, S. Asaoka, T. Iyoda, and S. Takahashi: Angew. Chem. Int. Ed., 42 (2003), 4349-4352. Chiroptical Properties of Helical Poly(aryl isocyanide)s Bearing m-Substituted Azobenzene Moiety, K. Shiga, K. Ishii, T. Miura, J. Abe, T. Yamagishi, S. Asaoka, T. Iyoda, F. Takei, K. Onitsuka and S. Takahashi: Trans. Mater. Res. Soc. Jpn., 28 (2003), 557-560. Ruthenium-Catalyzed Cyclocarbonylation of Allenyl Alcohols and Amines: Selective Synthesis of Lactones and Lactam, E. Yoneda, S.-W. Zhang, D.-Y. Zhou, K. Onitsuka, and S. Takahashi: J. Org. Chem., 68 (2003), 8571-8576. Review Papers Metallodendrimers Composed of Organometallic Building Blocks, K. Onitsuka and S. Takahashi: Top. Curr. Chem., 228 (2003), 36-63. International Conferences Asymmetric Catalysis of Planar-Chiral Cyclopentadienyl-Ruthenium Complexes in Allylic Substitution (Poster), *K. Onitsuka and S. Takahashi, The 2nd Gratama Workshop 2003, Utrecht University, Utrecht, The Netherlands, May 12-15, 2003. Synthesis and Properties of Polyisocyanides Bearing Porphyrin and Metallo-Porphyrin (Poster), *F. Takei, K. Onitsuka, S. Tojo, T. Majima and S. Takahashi, 10th IUPAC International Symposium on Macromolecule-Metal Complexes, Moscow Sate University, Moscow, Russia, May 18-23, 2003. Ruthenium-Catalyzed Alkoxycarbonylation of Allene (Poster), *D.-Y. Zhou, K. Onitsuka and S. Takahashi, The 9th International Kyoto Conference on New Aspects of Organic Chemistry, Kyoto Park Hotel, Kyoto, Japan, November 10-14, 2003. Synthesis and Properties of Polyisocyanides Bearing Porphyrin and Metallo-Porphyrin as Pendants (Poster), *F. Takei, K. Onitsuka, S. Tojo, T. Majima and S. Takahashi, The 9th International Kyoto Conference on New Aspects of Organic Chemistry, Kyoto Park Hotel, Kyoto, Japan, November 10-14, 2003. Synthesis and Properties of Helical-chiral Poly(ferrocenyl isocyanide)s (Poster), *F. Takei, N. Hida, K. Onitsuka, S. Takahashi and T. Iyoda, International Symposium on

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Scientific and Industrial Nanotechnology 2003, Osaka University, Osaka, Japan, December 8-9, 2003. A Novel Type of Asymmetric Catalyst: Planar-Chiral Cyclopentadienyl-Ruthenium Complexes (Poster), *K. Onitsuka, Y. Matsushima and S. Takahashi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka University, Osaka, Japan, December 8-9, 2003. Ruthenium-Catalyzed Carbonylation of Allene in Alcohols: Direct Synthesized Methacrylate Bearing a Functional Group (Poster), *D.-Y. Zhou, K. Onitsuka and S. Takahashi, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka University, Osaka, Japan, December 8-9, 2003. Mechanistic Study on Asymmetric Allylic Alkylation Catalyzed by Planar-Chiral Cyclopentadienyl-Ruthenium Complexes (Poster), *K. Onitsuka, Y. Matsushima and S. Takahashi, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka University, Osaka, Japan, January 13-14, 2004. Cyclocarbonylation of Azobenzene Derivatives (Poster), *D.-Y. Zhou, T. Koike, S. Suetsugu, K. Onitsuka and S. Takahashi, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka University, Osaka, Japan, January 13-14, 2004. Helical Structural Change in Polyisocyanides Having Ferrocenyl Pendants in Response to Electrochemical Stimuli (Poster), *F. Takei, N. Hida, K. Onitsuka, S. Takahashi and T. Iyoda, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” and 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka University, Osaka, Japan, January 13-14, 2004. Precise Synthesis of Organometallic Macromolecules Composed of Transition Metal Acetylide Units (Invited), *K. Onitsuka and S. Takahashi, The 227th ACS National Meeting, Anaheim Convention Center, Anaheim, USA, March 28-April 1, 2004. Publications in National Meetings The Chemical Society of Japan 6 papers The Society of Polymer Science, Japan 1 paper Division of Organometallic Chemistry, Kinki Chemical Society, Japan 1 paper Academic Degrees Master Degree of Science N. Ohara Synthesis and properties of organoruthenium dendrimers bridged by

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tri(ethynylphenyl)amine D. Kodama Synthesis and properties of poly(phenyl isocyanide)s bearing

porphyrin as pendants S. Suetsugu One-step synthesis of heteroaromatics by cyclic carbonylation of

unsaturated hydrocarbons T. Mori Synthesis and properties of poly(phenyl isocyanide)s bearing a

balkiness group at ortho position. Sponsorship Grant-in-Aid for Scientific Research in Priority Areas (2) S. Takahashi One-step Synthesis of Heteroaromatics by Cyclic

Carbonylation of Unsaturated Hydrocarbons ¥1,900,000

Grant-in-Aid for Scientific Research (A) (2) S. Takahashi Precise Synthesis and Properties of Organometallic

Macromolecules ¥7,400,000

Grant-in-Aid for Young Scientist (B) F. Takei Synthesis and Properties of Helical Poly(isocyanide)s ¥ 2,100,000

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Department of Organic Fine Chemicals Professor: Nobuo KATO Research Associates: Hajime NITTA, Tomikazu KAWANO Research Assistant: Michihiro HARA Outlines

The object of this department is to create lead compounds for drug development, based on chemical proteomic approaches. Currently, we are focusing on the investigation of small organic molecules that can modulate protein-protein interactions in intracellular signal transductions. The stereoselective synthesis of biologically active compounds and the construction of biomimetic supramolecular systems are also investigated. Current Research Programs

1. Self-assembled Supramolecular Complexes

We have synthesized novel multi-dentate ligands having 2-pyridylethynyl function as a core structure. It has been realized that these ligands with Copper(I)/Silver(I) ions form defined three dimensional helical structures in a self-assemble manner. Among them, 2,6-bis[(6-methoxymethyl)-2-pyridylethynyl]pyridine with copper(I) ion formed a supramolecular complex with triple-strand helix like collagen. 2. Chemical Libraries Bearing Cross-linkers

We have interested in a molecule having a cross-linker to provide valuable tools in chemogenomic approaches. This class of compounds are anticipated to be probes for target search and to be mother libraries for derivatizations of bioactive compounds. In this context, we have developed a method providing a chemical library bearing epoxide cross-linker by solid-phase synthesis. 3. Derivatization of Fusicoccin

Fusicoccin (FC) and cotylenin (CN) show not only potent plant-hormone like activities but also exhibit novel effects on animal cells presumably through modulation of protein-protein interactions where 14-3-3 proteins are involved. We have initiated a program to create novel small organic molecules based on FC/CN, which can modulate such interactions. Several semi-synthetic transformations of FC have been achieved to clarify structural requirements for exhibiting novel effects on animal cells. Publications Original Papers High-pressure Cycloaddition Reaction of 1,3-Diphenylisobenzofuran with 6,6-Diphenylfuluvene, K. Kubo, K. Hirowatari, N. Kato, and A. Mori: Heterocycles, 59 (2003) 47-50. A Silver(I) Ion Mediated One-Dimensional Helical Coordination Polymer from

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1,3-Bis(2-pyridylethynyl)-2-methylbenzene, T. Kawano, C.-X. Du, T. Araki, and I. Ueda: Inorg. Chem. Commun., 6 (2003) 165-167. (+)-Menthol and Its Hydroxy Derivatives, Novel Fungal Monoterpenols from the Fusicoccin-producing Fungi, Phomopsis amygdali F6a and Niigata 2, T. Sassa, H. Kenmoku, M. Sato, T. Murayama, and N. Kato: Biosci. Biotechnol. Biochem., 67 (2003) 475-479. Copper(I) Ion Mediated Self-Assembly of Triple-Stranded Helicates from Oligo(2-ethynylpyridines): Synthesis, Structure, and Properties, T. Kawano, T. Kato, C.-X. Du, and I. Ueda: Bull. Chem. Soc. Jpn., 76 (2003) 709-719. Self-Assembly and Substituent Effect of Copper(I) Complexes with 1,2-Bis(2-pyridylethynyl)benzene Ligands, T. Kawano, J. Kuwana, and I. Ueda: Bull. Chem. Soc. Jpn., 76 (2003) 789-797. Photochemical Reactions of 2-Bromotropone and 2,7-Dibromotropone with 9,10-Dicyano- anthracene, A. Mori, H. Kawakami, N. Kato, S.-H. Wu, and H. Takeshita: Org. Biomol. Chem., 1 (2003) 1730-1736. International Conferences Preparation of Fusicoccin Derivatives Utilizing Synthetic/Biosynthetic Transformations (Invited), *N. Kato: 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka, Japan, January 13-14, 2004. Synthesis of β-Strand Peptidomimetics Bearing an Epoxide Cross-linker (Poster), *T. Kawano, M. Kahn, and N. Kato: 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka, Japan, January 13-14, 2004. Rapamycin and Cotylenin A Cooperatively Induce G1 Arrest and Have an Anti-tumor Effect on Human Breast Carcinoma MCF-7 Cells Grown in Nude Mice (Poster), *Y. Honma, Y. Ishii, T. Kasukabe, N. Kato, and T. Sassa: Advances in Cancer Research: Molecular and Cellular Biology, Genomics and Proteomics, Targeted Therapeutics, Novel Clinical Trials, Molecular and Genetic Epidemiology/Prevention, Hawaii, USA, January 25-29, 2004. Clarification of Terpenoid Biosynthesis to Provide Derivatives of Parent Natural Products: Fusicoccin Case Study, *N. Kato: International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. Publications in Domestic Meetings The Japan Society for Analytical Chemistry Joint Symposium on Biofunctional Chemistry and Biotechnology The Chemical Society of Japan

1 paper 1 paper 1 paper

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Japan Society for Bioscience, Biotechnology, and Agrochemistry 1 paper Sponsorship Grant-in-Aid for Scientific Research (B) (2) N.Kato Chemogenomic Approach to Clarify the Intracellular

Signal Transductions ¥8,400,000

Grant-in-Aid for Scientific Research (A) (1) N.Kato Gene-cloning of Enzymes Pertaining to the Biosynthesis

of Fungal Diterpenoids ¥1,200,000

Other Research Funds T. Kawano Monbukagakusho (Program for Oversea Research)

Clarification of the Intracellular Signal Tramsductions by Chemical Genomic Approach

¥1,260,000

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Department of Organic Molecular Materials Professor: Yoshio ASO Associate Professor: Takahiro KANEDA Research Associate: Yutaka IE Research Assistant: Kaori ASANO Graduate Students: Tatsuhiko FUJIMOTO, Gaku FUKUHARA, Wakana YAMAMOTO Under Graduate Student: Susumu TSUDA Outlines

The main subject in the Department of Organic Molecular Materials is development of novel molecular-based materials with promising electronic and photoelectronic properties for molecular electronics and highly organized supermolecules for supramolecular machines, which is based on the study of the relationship between molecular structure and physical properties to elucidate and control the functions. We have focused our research on the design, synthesis, and properties of (1) novel extended conjugation systems for electronic and photoelectronic materials, (2) fully insulated nano-scale conjugated molecules for promising molecular wires, and (3) supermolecules composed of permethylated cyclodextrins and various π-systems especially oligothiophenes, azobenzenes, stilbenes, and tolans. These nano-scale molecular materials have potential use as a fundamental framework for molecular electronic devices. Current Research Programs 1. Molecular Electronics Materials

The synthesis and properties of a novel phosphorus-bridged bithiophene and its extended conjugation derivatives have been investigated, and the compounds showed the significant increase in fluorescence quantum efficiency compared with bithiophene. 2. Molecular Machines

We have developed design and construction of molecular machines based on [n]supercyclodextrins defined as cyclic n-mers of hermaphroditic cyclodextrin derivatives. The supercyclodextrins are a new class of interlocked supermolecules organized by a mechanical bond and have potential use as a fundamental framework for assembling nanoscale molecular devices. Publications Original Papers TTF-porphyrin Dyads as Novel Photoinduced Electron Transfer Systems, S. Sadaike, K. Takimiya, Y. Aso, and T. Otsubo: Tetrahedron Lett., 44 (2003) 161-165. Organic Field-Effect Transistor Using Oligoselenophene as an Active Layer, Y. Kunugi,

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K. Takimiya, K. Yamane, K. Yamashita, Y. Aso, and T. Otsubo: Chem. Mater., 15 (2003) 6-7. Photoexcitation and Electron Transfer Properties of Rod- and Coil-Type Oligo(thienylene-ethynylene)s, M. Fujitsuka, T. Makinoshima, O. Ito, Y. Obara, Y. Aso, and T. Otsubo: J. Phys. Chem. B, 107 (2003) 739-746. Synthetic Studies of Extraordinarily Long Oligothiophenes, T. Otsubo, Y. Aso, K. Takimiya, H. Nakanishi, and N. Sumi: Synth. Metals, 133-134 (2003) 325-328. Oligothiophene/fullerene Dyads as Active Photovoltaic Materials, N. Negishi, K. Yamada, K. Takimiya, Y. Aso, T. Otsubo, and Y. Harima: Chem. Lett., 32 (2003) 404-405. Synthesis and Spectroscopic Properties of a Series of β-Blocked Long Oligothiophenes up to the 96-mer: Revaluation of Effective Conjugation Length, T. Izumi, S. Kobashi, K. Takimiya, Y. Aso, amd T. Otsubo: J. Am. Chem. Soc., 125 (2003) 5286-5287. "Molecular Magic": Formation of a Self-inclusion Complex from a Dumbbell-shaped Permethylated β-Cyclodextrin Derivative, T. Yamada, G. Fukuhara, and T. Kaneda: Chem. Lett. 32 (2003) 534-535. Synthesis and Characterization of the First Pair of an Unlocked and a Locked Self-inclusion Complex from a Permethylated α-Cyclodextrin Derivative, G. Fukuhara, T. Fujimoto, and T. Kaneda: Chem. Lett. 32 (2003) 536-537. Identification of Face-to-Face Inclusion Complex Formation of Cyclodextrin Bearing an Azobenzene Group by Electrospray Ionization Mass Spectrometry, R. Arakawa, T. Yamaguchi, A. Takahashi, T. Fujimoto, and T. Kaneda: J. Am. Soc. Mass Spectrom., 14 (2003) 1116-1122. ESR Studies on Polarons in Long Oligothiophenes, K. Kanemoto, T. Kato, Y. Aso, and T. Otsubo: Phys. Rev. B, 68 (2003) 092302-1-4. International Conferences Synthesis and Spectroscopic Properties of a Series of β-Blocked Long Oligothiophenes up to the 96-mer, *Y. Aso, T. Izumi, S. Kobashi, K. Takimiya, and T. Otsubo, International Symposium on Novel Carbon-Rich Organic Materials, Osaka, September 29-30, 2003. Insulated Molecular Wires from Functionalised Cyclodextrins, Fujimoto (Poster), *T. Fujimoto, A. Nakamura, M. Taniguchi, T. Wada, T. Kawai, Y. Inoue, R. Kuroda, T. Kaneda, and H. L. T. Anderson, International Symposium on Novel Carbon-Rich Organic Materials, Osaka, September 29-30, 2003.

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The First Supramolecular Dual Piston-Cylinder System (Poster), *G. Fukuhara, T. Fujimoto, Y. Sakata, and T. Kaneda, International Symposium on Novel Carbon-Rich Organic Materials, Osaka, September 29-30, 2003. Oligothiophene/fullerene Dyads as Active Photovoltaic Materials, *Y. Aso, N. Negishi, K. Takimiya, T. Otsubo, and Y. Harima, Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Osaka, January 13-14, 2004. Lipophilic Cyclodextrin-based [2]Rotaxane and Janus [2]Rotaxane (Poster), *S. Tsuda, G. Fukuhara, T. Fujimoto, Y. Ie, Y. Aso, and T. Kaneda, Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Osaka, January 13-14, 2004. Synthesis and Properties of Phosphorus-Bridged Oligothiophenes (Poster), *Y. Ie, T. Tanaka, M. Fujitsuka, S. Tojo, T. Majima, and Y. Aso, Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Osaka, January 13-14, 2004. Publications in Domestic Meetings The Chemical Society of Japan 10 papers Cyclodextrin Symposium 1 paper Symposium on Structural Organic Chemistry 3 papers The Physical Society of Japan 2 papers The Society of Polymer Science, Japan 1 paper Symposium on Molecular Structure 1 paper West Japan Meeting, the Chemical Society of Japan 6 papers Annual Meeting on Photochemistry 2 papers Symposium on Heteroatom Chemistry 1 paper Academic Degrees Master Degree of Engineering G. Fukuhara Supramolecular Self-assemblies of Novel Azo Dye-modified

Permethylated Cyclodextrins Doctor Degree of Engineering T. Fujimoto Functionalised Cyclodextrins toward Self-organized Supramolecular

Structures and Insulated Molecular Wires

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Sponsorship Grant-in-Aid for Exploratory Research Y. Aso Synthesis of Nano-Scale Oligothiophenes of a Insulated

Molecular Wire Type ¥500,000

Grant-in-Aid for Exploratory Research T. Kaneda Synthesis of a Two-dimensional Molecular Machine

“Molecular Iris” ¥1,500,000

Grant-in-Aid for JSPS Special Research Fellows T. Fujimoto Synthesis of Self-assembled Cyclodextrin Oligomers ¥1,000,000 Entrusted Research Y. Aso Japan Science and

Technology Corporation Synthesis of Insulated Molecular Wires

¥260,000

Other Research Fund Y. Ie The Ogasawara Foundation

for the Promotion of Science & Engineering

Synthesis and Properties of Insulated Molecular Wires

¥1,000,000

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Department of Molecular Excitation Chemistry Professor: Tetsuro MAJIMA Associate Professor: Mamoru FUJITSUKA Research Fellows: Sachiko TOJO, Kiyohiko KAWAI Post Doctral Researcher: Xichen CAI, Takashi TACHIKAWA Research Technical Expert: Akira SUGIMOTO Graduate Students: Tadao TAKADA, Kohji NAKAYAMA, Ayumi OKADA,

Takumi KIMURA, Masanori SAKAMOTO, Ikue SHIROYAMA, Takashi SHIROYAMA, Shinsuke UEGAKI, Shingo SAMORI, Hiroko YOSHIDA

Research Students: Yasuko OSAKADA, Akihiro YOSHIDA Support Staff: Sanae TOMINAGA Guest Professor Chongjin PAC (Jan. 1-March 31, 2004) Guest Associate Professor Dae Won CHO (Jan. 5-Feb. 27, 2004) Outlines

"Beam-induced molecular chemistry" based on photo- and radiation-induced chemistry of organic compounds has been investigated from both basic and beam-functional points of view. The research topics are underway with respect to developments of new beam-controlled chemistry, new synthetic chemistry, and new molecular devices and functional materials. 1. Formation and reactivities of reactive intermediates in photochemistry and radiation

chemistry, and photochemistry of reactive intermediates 2. Multi-beam chemistry with irradiation by two-color laser-laser and electron pulse-laser

flash 3. Multiple-photon chemistry of organic compounds using UV, visible, and infrared lasers 4. Beam-controlled chemistry of artificial biomolecules such as modified DNA and proteins Current Research Programs 1. Multi-beam Chemistry

Multi-beam chemistry has been studied using pulse radiolysis-laser flash photolysis combined method, two-color two-laser photolysis and three-color three-laser photolysis. Photochemistry of reaction intermediates and short-lived chemical species generated from the reaction induced by the first beam excitation of a starting molecule (two-step excitation method), and moreover, photochemistry of other chemical species generated from the reaction of the short-lived intermediate induced by the second beam excitation (three-step excitation method) can be studied. We clarified the properties of the higher triplet excited states of various organic compounds such as benzophenone and naphthalene using two-

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color two-laser flash photolysis. Furthermore, bond cleavage specific to the higher triplet excited states was found for the first time with a series of dyad molecules of benzophenone and naphthalene. Furthermore, direct observation of the higher triplet excited state became possible using a picosecond laser. In addition, the resonant two-photon ionization process of stilbene derivatives was analyzed quantitatively to elucidate the factors governing the generation yield of the corresponding radical cations. 2. Molecular Photochemistry on Surfaces

One-electron oxidation of various aromatic compounds such as aromatic sulfides and biphenyl derivatives, adsorbed on the surface of TiO2 powder slurried in acetonitrile has been investigated by time-resolved diffuse reflectance spectroscopy. The high efficiency of a one-electron oxidation reaction was observed for substrates strongly coupled with the TiO2 surface, compared with substrates weakly coupled, indicating that the strength of the electronic coupling element between the hole donor and acceptor is a key factor in the one-electron oxidation of a substrate adsorbed on the TiO2 powder. We also observed the formation of pi-type dimer radical cation of aromatic sulfide at high substrate concentration and the cascade hole transfer reaction from the photo-generated holes in the TiO2 particles to free substrates in the bulk solution mediated by the radical cation of p-phenylbenzoic acid adsorbed on the TiO2 surface.

3. Beam-controlled Chemistry of Biomolecules

To understand the kinetic mechanisms involved in the photosensitized DNA damage processes, various DNA covalently attached with photosensitizer were synthesized. Laser flash photolysis (LFP) of these photosensitizer-modified DNA revealed that the hole generated on adenine (A) rapidly migrates through DNA by a hopping mechanism (A-hopping) with a rate constant faster than 108 s−1 over the distance range of 30 Å. These findings prompted us to suggest that a fast hole transfer by A-hopping may help to separate the hole and photosensitizer during the photosensitized one−electron oxidation of DNA, providing the time for DNA damage reaction can take place. A combination of the LFP transient absorption measurement (kinetic analysis) and quantitative HPLC analysis (product analysis) of DNA damage clearly demonstrated that the yield of the DNA damage correlates well with the lifetime of the charge separated state formed by A-hopping during the photosensitized one-electron oxidation of DNA. Thus we found that the hole transfer plays an important role in photosensitized DNA damage processes. Publications Original Papers Formation of Pyrene Dimer Radical Cation in DNA Reflecting DNA Dynamics in the Time Range of 1 µs to 1 ms, K. Kawai, K. Miyamoto, S. Tojo, and T. Majima: J. Am. Chem. Soc., 125 [4] (2003) 912-915.

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A Two-Color Laser Photolysis Methods for Determining Reaction Rates of Short-Lived Intermediates by Product Analysis: Applictaion to the o-inodimethane Problem, A. Ouchi, Z. Li, M. Sakuragi, and T. Majima: J. Am. Chem. Soc., 125 [4] (2003) 1104-1108. Naphthalene in the Higher Triplet Excited State, X. Cai, M. Hara, K. Kawai, S. Tojo, and T. Majima: Chem. Commun., 2 (2003) 222-223. Sensitized Reactions of Benzophenone in the Higher Triplet Excited State, X. Cai, M. Hara, K. Kawai, S. Tojo, and T. Majima: Chem. Phys. Lett., 371 [1-2] (2003) 68-73. Hole Transfer in DNA: DNA as a Scaffold for Hole Transfer between Two Organic Molecules, T. Takada, K. Kawai, S. Tojo, and T. Majima: Tetrahedron Lett., 44 (2003) 3851-3854. Kinetics of Weak Distance Dependent Hole Transfer in DNA by Adenine Hopping Mechanism, K. Kawai, T. Takada, S. Tojo and, T. Majima: J. Am. Chem. Soc., 125 [23] (2003) 6842-6843. Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants, F. Takei, S. N, K. Onitsuka, A. Ishida, S. Tojo, T. Majima, and S.Takahashi: Chem. Lett., 32 [6] (2003) 06-507. Three-color Three-laser Photochemistry of Di(p-methoxyphenyl)methyl Chloride, M. Hara, S. Tojo, and T. Majima: J. Phys. Chem. A, 107 [24] (2003) 4778-4783. Ionization and Fragmentation of Some Chlorinated Compounds and Dibenzo-p-dioxin with an Intense Femtosecond Laser Pulse at 800 nm, H. Harada, M. Tanaka, M. Murakami, S. Shimizu, T. Yatsuhashi, N. Nakashima, S. Sakabe, Y. Izawa, S. Tojo, and T. Majima: J. Phys. Chem. A, 107 [34] (2003) 6580-6586. Transient Phenomena of Dibenz[a,h]anthracene in the Higher Triplet Excited States, X. Cai, M. Hara, K. Kawai, S. Tojo, M. Fujitsuka, and T. Majima: Tetrahedron Lett., 44 [32] (2003) 6117-6120. Photoisomerization of 2’-Deoxyribofuranosyl and Ribofuranosyl 2-Phenylazoimidazole, M. Endo, K. Nakayama, Y. Kaida, and T. Majima: Tetrahedron Lett., 44 [36] (2003) 6903-6906. Rapid cleavage of Naphthylmethyl-O bond in the Higher Triplet Excited States, X. Cai, M. Sakamoto, M. Hara, S. Tojo, M. Fujitsuka, A. Ouchi, and T. Majima: Chem. Commun., (2003) 2604-2605. Benzophenones in the Higher Triplet Excited States, X. Cai, M. Sakamoto, M. Hara, A.

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Sugimoto, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima: Photochem. Photobiol. Sci., 2 (2003) 1209-1214. Tandem Double Helix Nano-Structures Using Interstrand Crosslinked DNA with Maleimide Linkers, M. Endo and T. Majima: Angew. Chem. Int. Ed. Eng., (2003) 5744-5747. Control of A Double Helix Assembly by Use of Crosslinked Oligonucleotides, M. Endo and T. Majima, J. Am. Chem. Soc., 125 [45] (2003) 13654-13655. Long-lived Charge-Separated State Leading to DNA Damage through Hole Transfer, K. Kawai, T. Takada, T. Nagai, X. Cai, A.Sugimoto, M. Fujitsuka, and T. Majima: J. Am. Chem. Soc., 125 (2003) 16198-16199. Effects of Base Pairing on the One-electron Reduction Rate of Cytosine, K. Kawai, A.Yokoohji, S. Tojo, and T. Majima: Chem. Commun., (2003) 2840-2841. One-electron Oxidation of Aromatic Sulfides Adsorbed on the Surface of TiO2 Particles Studied by Time-resolved Diffuse Reflectance Spectroscopy, T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima: Chem. Phys. Lett., 382 (2003) 618-625. Excess Electron Transfer in DNA Studied by Pulse Radiolysis and γ-Radiolysis of Naphthalimide and Iodouridine Containing ODN, K. Kawai, T. Kimura, K. Kawabata, S. Tojo and T. Majima: J. Phys. Chem. B, 107 [46] (2003) 12838-12841. Kinetics of multi-step hole transfer in DNA by Monitoring the Transient Absorption of Pyrene Radical Cation , T. Takada, K. Kawai, S. Tojo, M. Fujitsuka, and T. Majima: J. Phys. Chem. B, 107 [50] (2003) 14052-14057. Review Papers Hole Transfer in DNA using Pyrene-conjugated DNA, K. Kawai and T. Majima: Org. Synth. Chem. (in Japanese) 61 (2003), 614-619. Patents Damaging of Biomolecules and the Instruments, T. Majima and K. Kawai, 2003-338082 International Conferences Photochemical Control of Protein Activity, *T. Majima, The 21 Century COE Symposium -Towards Creating New Industries Based on Inter-Nanoscience- (INS-2003), 2003, Osaka, Japan, March 12, 2003. Photo-regulation of Hole Transfer in DNA Studied by Pulse Radiolysis-laser Flash

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Photolysis Combined Method (Poster), *T. Takada, K. Kawai, and T. Majima, 25th ACS National Meeting, New Orleans, LA, USA, March 22-27, 2003. Photochemitry of Short-lived Molecules (Invited), *T. Majima, CLEO Satelite meeting on Applications of Ultrafast Laser Systems, Baltimore, MD, USA, June 4, 2003. Hole Transfer in DNA by Adenine Hopping Mechanism (Invited), *T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Reactions Sensitized by Aromatic Hydrocarbons in the Higher Triplet Excited States (Poster), X. Cai, M. Hara, K. Kawai, S. Tojo, M. Fujitsuka, and *T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Hole Transfer Causes Long-Lived Charge Separated State which Leads to DNA Damage (Poster), *K. Kawai, and T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Charge Transfer in DNA via Consecutive Adenine Hopping (Poster), *T. Takada, K. Kawai, and T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Hole Transfer in DNA Studied by Pulse Radiolysis, K. Kawai, T. Takada, and *T. Majima, 12th International Congress on Radiation Research, Brisbane, Australia, August 17-22, 2003. Radiation Chemical and Photochemical Study of Z-DNA Modified by 2-Aminopurine and 8-Bromodeoxyguanosine (Poster), *T. Kimura, K. Kawai, and T. Majima, 12th International Congress on Radiation Research, Brisbane, Australia, August 17-22, 2003. Fast Hole Transfer by Adenine-Hopping for DNA Molecular Wire (Invited), K. Kawai, T. Takada, and *T. Majima, 10th Symposium of Intelligent Electrophotonic Materials and Molecular Electronics (SIEMME’10), Beijing, P.R. China, October 31-November 1, 2003. One-electron Oxidation during TiO2 Photocatalytic Reactions Studied by Transient Absorption Measurements (Invited), T. Tachikawa, S. Tojo, M. Fujitsuka, and *T. Majima, 10th Symposium of Intelligent Electrophotonic Materials and Molecular Electronics (SIEMME’10), Beijing, P.R. China, October 31-November 1, 2003. Fast Hole Transfer by Adenine-Hopping for DNA Molecular Wire, K. Kawai, T. Takada, and *T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. DNA Damaging using a Combination of Two-color Pulses (Poster), *K. Kawai, X. Cai, A.

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Sugimoto, S. Tojo, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Hole Transfer Causes Long-Lived Charge Separated State Leading to DNA Damage (Poster), *K. Kawai, T. Takada, T. Nagai, X. Cai, A. Sugimoto, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Charge Transfer in DNA via Adenine Hopping Mechanism (Poster), T. Takada, K. Kawai, and *T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. One-electron Oxidation of Aromatic Sulfides during TiO2 Photocatalytic Reactions Studied by Time-resolved Diffuse Reflectance Measurements (Poster), *T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. One-electron Oxidation of Aromatic Sulfides during TiO2 Photocatalytic Reactions Studied by Time-resolved Absorption Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Photochemistry of Oligothiophenes in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *M. Fujitsuka, Y. Oseki, M. Hara, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Photochemical Regulation of Protein Activity by Manipulating the Dimer Interface (Poster), *M. Endo, K. Nakayama, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Construction of DNA Nanostructures by Control of Double Helix DNA Assembly using Crosslinked Oligonucleotides (Poster), *M. Endo and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Aromatic Hydrocarbons in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *M. Fujitsuka, X. Cai, M. Sakamoto, M. Hara, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Multi-laser Photochemistry (Invited), *M. Fujitsuka and T. Majima, Singapore

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International Chemical Conference 3 Frontiers in Physical and Analytical Chemistry, Singapore, December 8-9, 2003. Oligothiophenes in the Higher Triplet Excited States (Poster), *M Fujitsuka, Y. Oseki, M. Hara, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Rapid Exciton Migration and Fluorescent Energy Transfer in Helical Polyisocyanides with Regularly Arranged Porphyrin Pendants (Poster), *M. Fujitsuka, A. Okada, S. Tojo, F. Takei, K. Onitsuka, S. Takahashi, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. DNA Damaging by Two Lasers (Poster), *K. Kawai, X. Cai, A. Sugimoto, S. Tojo, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Effects of Hole Transfer on Photosensitized DNA Damaging (Poster), *K. Kawai, T. Takada, T. Nagai, X. Cai, A. Sugimoto, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Aromatic Sulfides during TiO2 Photocatalytic Reactions: Part 1. Time-resolved Absorption Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Aromatic Sulfides during TiO2 Photocatalytic Reactions: Part 2. Time-resolved Diffuse Reflectance Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Photochemical Regulation of a Restriction Endonuclease BamHI by Manipulation of the Dimer Interface (Poster), *M. Endo, K. Nakayama, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Construction of DNA Nanostructures Using Crosslinked Oligonucleotides (Poster), *M.

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Endo and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Transient Absorption Measurement of Stilbene Radical Cation in the Higher Excited using ns and ps Two-laser Flash Photolysis (Poster), *M. Hara, S. Samori, X. Cai, M. Fujitsuka; and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Resonant Three Photon Ionization of Stilbene Derivatives using Two-color Two-laser Laser Flash Photolysis (Poster), *M. Hara, S. Samori, X. Cai, M. Fujitsuka; and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Rapid Cleavage of Naphthylmethyl-oxygen Bond in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *X. Cai, M. Sakamoto, M. Hara, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Energy Transfer vs Electron Transfer during the Bimolecular Quenching of Aromatic Hydrocarbons in the Higher Triplet Excited States (Poster), *X. Cai, M. Sakamoto, M. Hara, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Biphenyl Derivatives Strongly Coupled with TiO2 Surface (Poster), *T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Hole Transport to Non-adsorbed Chemicals during TiO2 Photocatalytic Reactions (Poster), *T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Competitive Quenching Processes of Naphthalene Derivatives in the Higher Triplet Excited States – Energy Transfer vs Electron Transfer (Poster), *M. Sakamoto, X. Cai, M. Hara, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, Jan. 13-14, 2004.

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Photochemical Control of Caspase-3 Activity for Induction of Apoptosis (Poster), *K. Nakayama, M. Endo, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. 2-Aminopurine-cytidine-7-deazaguanine (5’-ApCdzG-3’) Trimer as a Fluorescent Unit for a Z-DNA Probe (Poster), *T. Kimura, K. Kawai, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Kinetics of Long-Distance Hole Transfer in DNA (Poster), *T. Takada, K. Kawai, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Long-Lived Charge-Separated State in DNA (Poster), *T. Takada, K. Kawai, M. Fujitsuka, and T. Majima, 7th SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Charge Separation in DNA using the Consecutive Adenine Hopping (Poster), *K. Kawai, T. Takada, and T. Majima, International workshop on Advances in Molecular Electronics: From molecular materials to single-molecule devices, Dresden, BRD, February 23-27, 2004. Photosesitized Oxidation of DNA, *T. Majima, International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. DNA Supramolecular Chemistry, *M. Endo and T. Majima, International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. Manipulation of the Dimer Interface for Photochemical Regulation of the Activity of an Endonuclease BamHI (Poster), *K. Nakayama, M. Endo, and T. Majima, 227th ACS National Meeting, California, USA, March, 2004. Contribution to International Conferences T. Majima, 21st International Conference on Photochemistry (ICP21) (Organizing member) Publications in Domestic Meetings 83rd Japan Chemical Society Meeting 6 papers Photochemistry Meeting 8 papers 45th Radiation Chemistry Meeting 2 papers 51th Organic Reaction Chemistry Meeting 1 paper

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24th Japan Photomedical Science and Photobiology 3 paper 84th Japan Chemical Society Meeting 18 papers Academic Degrees Doctor Degree of Engineering M. Hara, Multi-Photon and Multi-Laser Chemistry of Aromatic Compounds Master Degree of Engineering T. Shiroyama, Synthesis and Properties of Porphyrin-DNA Supramolecules Sponsorship Grand-in-Aid for Scientific Research (A) (2) T. Majima Molecular Devices by Function-control of Conjugated ¥1,300,000 DNA Grand-in-Aid for Scientific Research in Special Area (2) T. Majima Fundamental Science and Technology of ¥24,600,000 Photofunctional Interfaces Grand-in-Aid for Scientific Research (C) (2) S. Tojo Decomposition of Organic Compounds by Photocatalysts ¥2,600,000 -Multi-photon Excitation Methods- Grand-in-Aid for Encouragement of Young Scientists (B) M. Fujitsuka Photoinduced Electron Transfer in Functionalized ¥1,500,000 Fullerene Nanostructures Grand-in-Aid for Encouragement of Young Scientists (B) K. Kawai High Efficient DNA Damage using Two-color ¥1,500,000 Two-laser Irradiation

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Department of Synthetic Organic Chemistry Professor: Hiroaki SASAI Associate Professor: Hiroshi YAMATAKA Research Associates: Junko ICHIHARA, Doss JAYAPRAKASH Post Doctoral Fellows: Mahesh L. PATIL, Chinnasamy MUTHIAH, Toshio

SHINOHARA Guest Researchers: Stefanie KALSOW, Cilamkoti Venkat Laxman RAO, Priti

KORANNE Graduate Students: Takahiro KATO, Katsuya MATSUI, Kazuyoshi

MARUBAYASHI, Kouji YONEZAWA, Yasuaki ASANO, Tetsuo KAWAKUSU, Takahiro KAWASE, Ai SHIMOMOTO, Kazuhiko WAKITA, Tetsuya TSUJIHARA, Tomokazu YOSHIDA, Keigo WATAGUCHI

Research Student: Takashi HARA Support Staff: Mikako NAKASHIMA Outlines

Asymmetric synthesis, a phenomenon fine tuned to perfection by nature, forms the

central theme of our research efforts. We have been interested in the design and syntheses of a novel class of chiral ligands that are unique in promoting new asymmetric reactions. The mechanisms of these organic reactions are also studied by means of physical organic techniques. Novel chiral spiro ionic liquids and organocatalysts have been synthesized with a focus on developing environmentally benign asymmetric processes. Current Research Programs

1. Development and Immobilization of Bimetallic Asymmetric Catalysts

Heterobimetallic catalysts such as Al-Li-bis(binaphthoxide) complex (ALB) function like an enzyme by activating two different substrates to facilitate a chemical reaction. In a similar manner, a homo-dinuclear catalyst should be able to activate two identical substrates in a homolytic coupling reaction. Chiral dinuclear vanadium(IV) complexes have been synthesized and found to promote the enantioselective oxidative coupling of 2-naphthol derivatives through a dual activation mechanism affording the product with up to 93% ee. The dual activation mechanism in this system was supported by the kinetic analysis and catalyst loading effects.

Immobilization of catalysts on macromolecular supports facilitates environmentally benign processes by enabling their recovery and reuse. We have employed a comprehensive approach for the effective immobilization of the bimetallic catalysts (e.g. ALB) utilizing polymers, dendrimers and dendronized polymers containing 1,1’-bi-2-naphthols (BINOL). To obtain highly active catalysts the position and orientation of each ligand in the resulting polymers were controlled by the use of novel “Catalyst Analogue” approach or by using bis-BINOL ligands. The resulting heterogeneous

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catalysts promoted the asymmetric Michael reaction affording the products with high enantioselectivities and could be reused subsequently. These polymeric ligands were also employed in asymmetric carbonyl-ene reaction and asymmetric epoxidation. 2. New Asymmetric Isoxazoline Ligands with Spiro Skelton On the basis of ab initio calculations, we had great interest in the chelating ability of isoxazolines. We have designed, and synthesized the first chiral bis(isoxazoline) ligands (SPRIXs) containing rigid spiro skeleton. The ligands showed great affinity towards Pd(II) salts and the resulting chiral Pd(II)-spiro bis(isoxazoline) catalysts promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols. Furthermore, a new catalytic asymmetric tandem cyclization of dialkenyl alcohol took place, affording unique bicyclic ether in one step with up to 95% ee. New type of bis(isoxazoline) ligand, 2,2’-bis(isoxazolinyl)propane and (R)-2,2’-bis(isoxazolinyl)-1,1’-binaphthyl have been prepared and strong ligand-acceleration effects were demonstrated in Pd(II)-catalyzed Wacker-type cyclization of alkenyl alcohol. The lack of acceleration effects with oxazoline ligands clearly shows the crucial role of isoxazoline moiety on the Wacker-type cyclization of alkenyl alcohols. In the presence of carbon monoxide the Pd(II)-spiro bis(isoxazoline) catalyst also promoted the asymmetric aminocarbonylation of alkenyl amines to give pyrrolidine derivatives with moderate enantioselectivtiy. To fully exploit the unique asymmetric environment afforded by the spiro backbone novel spiro bis(oxazoline), bis(oxazole) and bis(pyrazole) ligands have been synthesized. 3. Highly Effective Synthesis of Functionalized Particles

Spherical particle such as a dendrimer has attracted much attention due to the great potential of applications in material science. However preparation of dendrimer often results in very low yields. Despite unique shape, various difficulties should be overcome for their practical applications.

Taking advantage of the facile adsorption of thiols to the surface of gold cluster, the disulfide bearing (R)-BINOL moieties at each terminal positions has been successfully introduced on monolayer-protected metal cluster (MPC). Treatment of the metal cluster with Ti(O-i-Pr)4 afforded an insoluble Ti-BINOLate complex with high catalyst activity in the asymmetric alkylation of aldehyde with dialkylzinc. As an alternate approach, dendrimer-like catalyst was synthesized by immobilization of (R)-BINOL derivative on the polymer obtained by micellar polymerization system. The polymer-supported Ti-BINOLate complex generated with this polymer also exhibited high catalytic activity. 5. Chiral Ionic Liquids and Organocatalysts

Ionic liquids have proved to be good alternatives for conventional solvents as they offer recyclable and greener reaction media. Spiro imidazolium salts, spiro pyridinium salts and spiro ammonium salts have been designed and synthesized for use as chiral ionic liquids and chiral phase transfer catalysts respectively.

New asymmetric BINOL derivatives with Lewis base unit, which can act as organocatalysts in the aza-MBH reaction, have been developed. Synergistic cooperation between Brønsted acid units (BINOL) and Lewis base unit in active sites of the catalyst has been found to play an important role in realizing highly stereoselective

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reactions. 6. Solvent-free Catalytic Epoxidation Using Green Solid Disperse Phase

The search for environmentally benign alternatives to the conventional reaction process using organic solvents has been of great significance in green chemistry. We have developed a new approach to environmentally benign reaction system using solid disperse phase. We found a new catalytic solid phase system for epoxidations using urea-hydrogen peroxide complex (urea-H2O2) and cetylpyridinium dodecatungstate ((CetylPy)10[H2W12O42]) catalyst on fluorapatite. In the solid phase system epoxidations of cyclic alkenes and allylic alcohols proceeded without solvent at room temperature to afford the corresponding epoxides in good yields. The recovered solid catalyst phase was reusable for the reaction. 7. Dynamics-driven Reaction Pathway Demonstrated by Direct Dynamic Simulations The present research develops a quantum mechanics (QM)-based molecular dynamics (MD) method, which enables to simulate chemical reactions and to elucidate possible pathways of organic reactions. By means of the direct MD simulations, it was found that the route of some intramolecular organic reaction is affected by temperature, suggesting that a transition state of a given character may have only limited significance with respect to the actual mechanism. The results provide new insight that will be important to more accurately characterize reactions and ultimately control them. Publications Original Papers Design and Synthesis of Novel Spiro Pyridinium and Quinolinium Salts. M. L. Patil, S. Takizawa, and H. Sasai, Heterocycles 61, (2003), 581.

Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support. S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, Angew. Chem. Int. Ed. 42, (2003), 5711.

Monolayer-protected Au Cluster (MPC)-supported Ti-BINOLate Complex. K. Marubayashi, S. Takizawa, T. Kawakusu, T. Arai, and H. Sasai, Org. Lett. 5, (2003), 4409.

Synthesis of Novel Chiral Spiro Bis(pyrazole) Ligands. S. Takizawa, Y. Honda, M. A. Arai, T. Kato, and H. Sasai, Heterocycles 60, (2003), 2551.

Polymer Supported BisBINOL Ligands for the Immobilization of Multicomponent Asymmetric Catalysts. T. Sekiguti, Y. Iizuka, S. Takizawa, D. Jayaprakash, T. Arai, and H. Sasai, Org. Lett. 5, (2003), 2647.

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Enantioselective Synthesis of α-Methylene-γ-butyrolactones Using Chiral Pd(II)-SPRIX Catalyst. C. Muthiah, M. A. Arai, T. Shinohara, T. Arai, S. Takizawa, and H. Sasai, Tetrahedron Lett. 44, (2003), 5201.

Enantioselective Epoxidation of α,β-Unsaturated Ketons Using Polymer-supported Lanthanoid-BINOL Complexes. D. Jayaprakash, Y. Kobayashi, S. Watanabe, T. Arai, and H. Sasai, Tetrahedron: Asymmetry 14, (2003), 1587.

Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketons Using Polymeric BINOL. D. Jayaprakash, Y. Kobayashi, T. Arai, Q.-S. Hu, X.-F. Zheng, L. Pu, and H. Sasai, J. Mol. Catal. A: Chem. 196, (2003), 145.

"Catalyst Analogue": A Concept for Constructing Multicomponent Asymmetric Catalysts (MAC) Using a Polymer Support. T. Arai, T. Sekiguti, K. Otsuki, S. Takizawa, and H. Sasai, Angew. Chem. Int. Ed. 42, (2003), 2144.

Synthesis of New Chiral Bis(isoxazoline) Ligands Containing Spiro[5.5]undecane Skelton. M. A. Arai, M. Kuraishi, T. Arai, and H. Sasai, Chirality 15, (2003), 101.

The First Enantioselective Intramolecular Amino-carbonylation of Alkynes Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst. T. Shinohara, M. A. Arai, K. Wakita, T. Arai, and H. Sasai, Tetrahedron Lett. 44, (2003), 711.

Synthesis and Character of New Bis(isoxazoline) Ligands. T. Shinohara, K. Wakita, M. A. Arai, T. Arai, and H. Sasai, Heterocycles 59, (2003), 587.

Dynamics-driven Reaction Pathway in an Intramolecular Rearrangement. S. C. Ammal, H. Yamataka, M. Aida, and M. Dupuis, Science 299, (2003), 1555.

Nitroalkane Anomaly: Computational Study with Cluster and Continuum Modeling. H. Yamataka and S. C. Ammal, ARKIVOC (2003), 59.

Ab Initio Molecular Dynamics Studies on Substitution vs. Electron Transfer Reactions of Substituted Ketyl Radical Anions with Chloroalkanes: How Do the Two Products Form in a Borderline Mechanism? H. Yamataka, M. Aida, and M. Dupuis, J. Phys. Org. Chem. 16, (2003), 475.

The 1-N-(methoxycarbonyl-2-phenylethyl)imino-2,2,2-trifluoroethanephosphonate Systems Are Not Stable Enols of Carboxylic Esters. J. Song, H. Yamataka, and Z. Rappoport, J. Fluor. Chem. 124, (2003), 119.

Linear Free Energy Relationship and Kinetic Isotope Effects as Measures for the Transition State Variation. A Computational Study. S. C. Ammal, M. Mishima, and H. Yamataka, J. Org Chem. 68 (2003), 7772.

The Catalytic Activities of Nanoclusters Dispersed on Apatite. J. Ichihara, K. Iteya, H. Kawaguchi, Y. Sasaki, H. Nakayama, and S. Yamaguchi, J. Ceram. Process. Res. 4, (2003), 42.

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Cetylpyridinium Dodecatungstate on Fluorapatite: Efficient and Reusable Solid Catalyst for Solvent-Free Epoxidation. J. Ichihara, A. Kambara, K. Iteya, E. Sugimoto, T. Shinkawa, A. Takaoka, S. Yamaguchi, and Y. Sasaki, Green Chem. 5, (2003), 491.

New Approach to Environmentally Benign Epoxidation: The Solid-Phase-System Using Urea-H2O2 and Recyclable Dodecatungstate on Apatite. J. Ichihara, K. Iteya, A. Kambara, and Y. Sasaki, Catal. Today, 87, (2003), 163.

Book Addition of Lithium Derivatives to Doubly-bonded Compounds. H. Yamataka, K. Yamada, and K. Tomioka, In Chemistry of Functional Groups, Vol. 104, Z. Rappoport and I. Marek, Eds., Wiley. International Conferences

Development of Multifunctional Asymmetric Catalysts (MAC) for Morita-Baylis-Hillman (MBH) Reaction (Poster), *K. Matsui, S. Takizawa, and H. Sasai, 12th Symposium on Organo-metallic Chemistry Directed Toward Organic Synthesis (OMCOS 12), Toronto, Canada, July 6-10, 2003. Design and Synthesis of Novel Spiro-Type Ligands (Poster), *T. Kato, K. Wakita, T. Shinohara, C. Muthiah, M. A. Arai, S. Takizawa, and H. Sasai, 12th Symposium on Organo-metallic Chemistry Directed Toward Organic Synthesis (OMCOS 12), Toronto, Canada, July 6-10, 2003. Development of Novel Multifunctional Asymmetric Catalysts (Poster), *S. Takizawa, H. Somei, K. Murai, T. Arai, D. Jayaprakash, and H. Sasai, The International Symposium on Dynamic Complexes (ISDC 2003), Tokyo, Japan, August 4, 2003. Enantioselective Catalysis Using Novel Spiro-type Ligands (Poster), *K. Wakita, M. A. Arai, T. Shinohara, T. Kato, C. Muthiah, S. Takizawa, T. Arai, and H. Sasai, The 15th International Symposium on Chirality (Chirality 2003), Shizuoka, Japan, October 20-23, 2003. Enantioselective Catalysis Using Novel Spiro-type Ligands (Poster), *K. Wakita, T. Kato, T. Shinohara, C. Muthiah, M. A. Arai, S. Takizawa, T. Arai, and H. Sasai, The 9th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-9), Kyoto, Japan, November 10-14, 2003. Effective Immobilization of Mulitifunctional Asymmetric Catalysts. (Poster), *D. Jayaprakash, T. Sekiguti, Y. Iizuka, S. Takizawa, T. Arai, and H. Sasai, The 9th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-9), Kyoto, Japan, November 10-14, 2003. Dual Activation in a Homolytic Coupling Reaction Promoted by an Enantioselective Dinuclear Vanadium(IV) Catalyst (Poster), H. Somei, Y. Asano, T. Yoshida, *S.

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Takizawa, H. Yamataka, and H. Sasai, The 9th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-9), Kyoto, Japan, November 10-14, 2003. Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts (MACs) with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support (Poster), *S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Monolayer-protected Au Cluster (MPC)-supported Ti-BINOLate Complex (Poster), *T. Kawakusu, K. Marubayashi, S. Takizawa, T. Arai, and H. Sasai, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts (MACs) with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support (Poster), *S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, International Symposium on Organic Reactions 2003 (ISOR-2003), Osaka, Japan, December 19-21, 2003. Immobilization of Enantioselective Catalysts onto the Surface of Spherical Nanoparticles (Poster), *K. Marubayashi, S. Takizawa, F. Yonezawa, T. Kawakusu, D. Jayaprakash, M. L. Patil, T. Arai, T. Hanada, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. The aza-Morita-Baylis-Hillman (aza-MBH) Reaction Promoted by Chiral Phosphine-BINOL as an Organocatalyst (Poster), *K. Matsui, S. Takizawa, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Design and Synthesis of Novel Spiro Chiral Phase Transfer Catalysts (Poster), *M. L. Patil, C. V. L. Rao, S. Takizawa, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Enantioselective Reactions Promoted by Pd(II)-SPRIX Catalysts (Poster), *C. Muthiah M. A. Arai, T. Shinohara, T. Arai, S. Takizawa, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. New Approach for the Immobilization of Multicomponent Asymmetric Catalysts with

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High Enantiocontrol (Poster), *S. Takizawa, D. Jayaprakash, H. Somei, T. Sekiguti, K. Otsuki, T. Arai, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Effective Immobilization of Multifunctional Asymmetric Catalysts (Poster), *D. Jayaprakash, T. Sekiguti, Y. Iizuka, T. Arai, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Dual Activation in a Homolytic Coupling Reaction Promoted by an Enantioselective Dinuclear Vanadium(IV) Catalyst (Poster), H. Somei, Y. Asano, *T. Yoshida, S. Takizawa, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Design and Synthesis of Novel Spiro-Type Ligands (Poster), *T. Tsujihara, K. Wakita, T. Kato, T. Shinohara, M. A. Arai, S. Takizawa, T. Arai, and H. Sasai, Second 21st Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science -Perspectives in Nanoscience-, Osaka, Japan, January 13-14, 2004. Immobilization of Multicomponent Asymmetric Catalysts (Oral), *S. Takizawa and H. Sasai, International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. Some Enantioselective Reactions Using Spiro Chiral Compounds (Oral), *H. Sasai, International Workshop on Recent Progress in Organic Chemistry (Oral), Osaka, Japan, March 1-3, 2004. Immobilization of Multifunctional Asymmetric Catalysts (MACs) (Oral), D. Jayaprakash, S. Takizawa, T. Arai, and *H. Sasai, 227th ACS National Meeting, California, USA, March 28 - April 1, 2004. Enantioselective Catalysis Using Novel Spiro-type Ligands (Oral), *H. Sasai, 227th ACS National Meeting, California, USA, March 28 - April 1, 2004. Dynamics-driven Reaction Pathway: In What Case Is a Reaction Controlled by Dynamics? (Oral), *H. Yamataka and S. C. Ammal, 9th European Symposium on Organic Reactivity, Oslo, Norway, July12-17, 2003. Can Enol of Carboxylic Acid Halides Be Prepared? (Oral), Z. Rappoport, S. C. Ammal, and *H. Yamataka, 10th Kyushu International Symposium on Physical Organic Chemistry, Fukuoka, Japan, September 30 - October 3, 2003.

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Theoretical Study on the Mechanism of Halogen Exchange Reaction of Alkyl Halide in Aqueous Solution (Oral), M. Ohisa, M. Aida, and *H. Yamataka, 10th Kyushu International Symposium on Physical Organic Chemistry, Fukuoka, Japan, September 30 - October 3, 2003.

Cetylpyridinium Dodecatungstate Dispersed on Apatite: A Reusable, Efficient Solid-catalyst-phase in the H2O2-epoxidations (Poster), Y. Sasaki, *A. Kanbara, K. Iteya, J. Ichihara, and S. Yamaguchi, The 9th Korea-Japan Symposium on Catalysis, Pohang, Korea, May 20-21, 2003. Catalytic Activities and Active Species in Phosphomolybdate/Urea-H2O2/Apatite Solid-phase System (Poster), J. Ichihara, *K. Iteya, K. Ushimaru, H. Kawaguchi, Y. Sasaki, S. Yamaguchi, and H. Nakayama, The 9th Korea-Japan Symposium on Catalysis, Pohang, Korea, May 20-21, 2003. Clean Polyoxometalate/Apatite Solid-Phase-System for Oxidation of Sulfides to Sulfoxides and Sulfones (Poster), *J. Ichihara, K. Ushimaru, and Y. Sasaki, 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka, Japan, January 13-14, 2004. Are Kinetic Isotope Effects a Good Measure of Transition State Variation? A Combined Experimental-theoretical Study (Invited), *H. Yamataka and S. C. Ammal, 3rd International Isotope Effect Conference, Uppsala, Sweden, June 22-27, 2003. The Effect of Dynamics in Molecular Rearrangements and Isomerizations (Invited), *H. Yamataka, S. C. Ammal, Y. Ohga, and T. Asano, 10th Kyushu International Symposium on Physical Organic Chemistry, Fukuoka, Japan, September 30 - October 3, 2003. Publications in Domestic Meetings National Meeting of Chemical Society of Japan 17 papers Symposium on Progress in Organometallic Chemistry 1 paper Symposium on Fundamental Organic Chemistry 3 papers Symposium of Theoretical Chemistry 1 paper Symposium on Organic Synthesis 1 paper Catalysis Society of Japan (CatSJ) Meeting GSC Symposium Symposium on Rare Earths Symposium on Organic Chemistry -The Next Generation- Symposium on Polymer Science Congress of Heterocyclic Chemistry Symposium of Molecular Structure Symposium on Progress in Organic Reactions and Syntheses Symposium on Progress in Organic Reactions

3 papers 2 papers 1 paper 1 paper 1 paper 2 papers 1 paper 2 papers 4 papers

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Academic Degrees Master Degree of Science Y. Asano Dual Activation Catalysis Using a Chiral Dinuclear Complex and Its

Application to Enantioselective Reactions T. Kawakusu MPC-supported Enantioselective Catalysts T. Kawase Enantioselective Aldol-type Reaction Utilizing Diketene A. Shimomoto Novel Chiral Ammonium Salts with Spiro Skelton and Their

Applications to Asymmetric Catalysis K. Wakita Development of Novel Chiral Ligands with Spiro Skelton and Their

Applications to Asymmetric Catalysis Doctor Degree of Science T. Kato Development of Novel Chiral N-Ligands with Spiro Skelton and Their

Applications to Asymmetric Catalysis K. Matsui Asymmetric Morita-Baylis-Hillman (MBH) Reaction Promoted by Novel

Multifunctional Catalysts Sponsorship Grant-in-Aid for Scientific Research (A)(2) H. Sasai H. Sasai (C)(2) H. Yamataka

Functionalized Heteroatomic Compound Utilizing New Synthesis Method for Nanoparticle Development of Artificial Enzyme with Synergistic Multi-cooperation in Active Sites Study of Reaction Mechanism Considering the Effect of Organic Solvents

¥2,300,000

¥1,900,000

¥2,400,000

Grant-in-Aid for JSPS Fellows H. Sasai Development of Catalytic Asymmetric Reaction Using

Chiral Spiro Ligands ¥1,000,000

H. Sasai Novel Asymmetric Catalytic Synthesis ¥1,200,000

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COE Fund T. Kato K. Matsui K. Marubayashi K. Yonezawa M. L. Patil C. Muthiah

Development of Novel Spiro Ligands and Their Applications to Asymmetric Catalysis Development of Novel Multifunctional Catalysts for Enantioselective aza-Morita-Baylis-Hillman (MBH) Reaction Development and Application of Functionalized Nano-particles Development of Novel Chiral Ionic Liquid with Spiro Skelton Dynamic Analysis of Quaternary Ammonium Salts as Catalysts in Reaction Media by Using Laser Light Synthesis of Novel Bio-materials Utilizing Pd(II)-SPRIX Catalyst

¥400,000

¥400,000

¥400,000

¥400,000

¥500,000

¥500,000

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Division of Intelligent Systems Science Outline

The advent of the digital society where tremendous amount of information is

electronically accessible has brought the intelligent information processing technologies indispensable. This division, consisting of four departments, challenges the task of computerizing the intelligent human information processing capability to help solve difficult engineering problems and assist intellectual activities. The major research targets include ontology engineering and knowledge reuse/sharing (Knowledge Systems Dept.), use of multi-dimensional information sources and their multi-purpose processing (Intelligent Media Dept.), human-computer interfaces and agents (Architecture for Intelligence Dept.) and data mining, knowledge discovery and machine learning (Advanced Reasoning Dept.). While pursuing its own research target, each department works closely together to similar problems from different perspectives. The division as a whole collaborates with other divisions in the institute by providing the tools we have developed to help them solve their problems and also is benefited by the feedback to open up new research frontiers.

Achievements

• Distributed ontology development environment • Systematization of functional knowledge using ontological engineering and its deployment • Advanced knowledge management and learning support • Analysis of collaborative learning interaction and meta-cognitive skill modeling • Authoring task ontology and an innovative architecture of an authoring system • Creation of omnidirectional vision and its image processing • 3D modeling and visualization • Omnidirectiomal surveillance system and human behavior analysis • Feature construction for inductive learning • Predicate Invention • Constructive adaptive user interfaces • Adaptive agents • Web-based learning environments • Sharing navigation knowledge • Meta cognition in hyperspace • Instructional design support for collaborative learning • Knowledge acquisition from human experts • Knowledge discovery from graph structured data • Information retrieval under various data format • Discovery of time dependent law equations from data • Derivation of association rules for data with numeric attributes

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Department of Knowledge Systems Professor: Riichiro MIZOGUCHI Associate Professor: Yoshinobu KITAMURA Research Associates: Kaoru SUMI, Akiko INABA (from Oct. 1) Post Doctoral Fellow: Larisa SOLDATOVA Graduate Students: Koichi HAYASHI, Takuma TOKI, Eiichi SUNAGAWA, Masataka TAKEUCHI, Yusuke TAKEUCHI, Yohei TANAKA, Shinya TARUMI Undergraduates: Yuichiro KONO, Hironobu JIMURA Support Staff: Naomi BANO Outlines

Information science has developed into knowledge science which is expected to play critical roles in the advanced information processing in this new century. In the real world, tiny computers of the higher performance have been used by ordinary people in their homes where they also enjoy access to vast amount of information sources scattered all over the world thanks to the internet. In academic society, on the other hand, the research on artificial intelligence is changing from building stand-alone machines which try to solve problems by themselves to building intelligent partners which augment human capability of problem solving. This division has been run under the philosophy that it contributes not only to the promotion of knowledge science but also to prosperity of the real world by the feedback of the research results to it in the information era. The major topic here is to investigate Ontological Engineering to establish basic theories and technologies for the next-generation knowledge science. The current research projects include: methodology for ontology development and its support environment based on basic theories of ontological engineering, creative design work bench and advanced diagnostic systems based on knowledge systematization, knowledge sharing and reuse, intelligent educational/training systems, and ontology-aware authoring systems. Current Research Programs

1. Ontology : Theoretical Foundation of Knowledge Engineering The research on knowledge-based systems aims at making computer systems more intelligent by mimicking intellectual capability of human. The key to achievement of this goal is the fluent knowledge-level communication between humans and computers. The current state of the art of knowledge engineering, however, has not been matured enough to realize it. Considerable amount of meaning of the concepts in human mind is lost in most of the existing knowledge-based systems. This is the major cause of the difficulty of knowledge reuse and sharing and the too strict behavior of the systems for users to feel comfortable. Thus, new theoretical foundation for knowledge engineering is badly needed in knowledge engineering fields. The research on ontology engineering is one of the most promising approaches to establishment of the foundation. We theorized about the fundamental issues on ontology from both scientific and

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engineering viewpoints. As a result, we published three enlightening papers which describe drawbacks of the current research, importance of ontological engineering, definitions of an ontology, its functions and roles, its classification and research topics. We further published some research results based on ontological engineering to show concrete examples of a new research direction. We have developed HOZO, an environment for ontology building/utilization based on our innovative theory on ontological engineering. HOZO has been augmented to make it a usable tool by revising its GUI and reimplementation of some functions. It has been extended to cope with distributed development of a large ontology. 2. Systematization of Functional Design Knowledge

In the engineering domain, the importance of knowledge sharing among designers has been widely recognized. Although advancement of computer technologies has enabled easy access to objective information such as structural information using CAD without designer’s intention, it is difficult to share conceptual engineering knowledge about functionality that can represent designer’s intention so-called design rationales, because there is neither rich common vocabulary for representing functionality of devices nor well-established ontological commitment for capturing such knowledge. The main goal of this research is to promote sharing of the conceptual engineering knowledge about functionality by providing a conceptual framework enabling systematic description of the functional knowledge. We have developed an ontological framework for its modeling including layered ontologies, which provides rich concepts for describing consistent and reusable knowledge. The framework has been deployed successfully in a production company. In 2003, we established a users’ group of the software based on our methodology, which promotes deployment in other companies. A knowledge modeling schema which integrates several conventional knowledge forms has been investigated as well.

3. Task Ontology for Intelligent Tutoring System

The goal of research on intelligent educational systems is to implement the intellectual capability of human teachers on computer systems. Huge efforts have been devoted to the research for the last two decades. However, the research field has not been growing methodologically because of lack of theoretical foundation. Ontology is expected to be a firm basis for knowledge engineering, on top of which we can accumulate our knowledge about the principled methodologies to build sharable and reusable knowledge bases. Especially, task ontology, which captures the inherent conceptual structure of problem solving, works as a bridge to fill the conceptual gap between humans and computers when building and using knowledge-based systems. It keeps up the correspondence between the conceptual structure in human mind and the functional structure of knowledge-based systems. In this research project, we have investigated the essential structure of a variety of educational tasks in detail and built educational task ontology. Furthermore, with the aid of the task ontology built, we have developed a sophisticated authoring tool (intelligent educational system development environment) for substation operator training. The latest results include a proposal of Ontology-Awareness aiming at marriage of learning and educational theories and technology. Based on the proposal, we have realized an ontology-aware authoring environment. In this year, we developed authoring task ontology and an

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architecture of an evolving authoring tool based on the task ontology. We also developed an analysis system for the interactions done in a collaborative learning and an innovative model of meta-cognitive skills. 4. Model-based Knowledge Management Support Environment

We continue to learn during our lifetimes. As researchers, for example, we learn basic knowledge through ‘book learning’, acquire up-to-date knowledge from the literature, develop original knowledge for ourselves, and then disseminate it to society. In this sense, we can share the idea that “life is a continuous process of learning.” “Learning” in a wide sense includes various forms of learning: for example, workplace learning, life-long learning, organizational learning, and so on. Along a similar line of thought, this research aims to develop a model of learning in a wide sense. Needless to say, we are all vaguely conscious of a similar model in our own minds which we apply to increase awareness of social relations among organization members; however, that model is implicit and not systemic in most cases. We propose a model called a “dual loop model”, which shows how intellect is formed in individual life in organizations and works as a fundamental component of a learning support platform. The dual loop model indicates an ideal relation between individual activity and organizational activity and clarifies roles of individuals, activities, and documents as a vehicle for intellectual communication in organizational learning. In this research project, we have been developing an IT platform, Kfarm, to develop users’ pro-found social intellectual awareness in organization. In this year, we developed a producing system of a collaboration field optimized for both of learning and practicing together with an explanation system of the design rationale of a collaboration field and a knowledge management system oriented toward learning. 5. Consensus Formation Support System In this research project, we propose a system to support the nebulous communication between the users who do not clearly express the concepts intended. When people have difficulty in understanding each other, using Talkabout to build an ontology of the common target world is helpful. By helping their inputting and showing some examples of concepts or ontologies from World Wide Web, the system enables users to discover the opinions of others on the use of the data. Then it facilitates discussion. This, in turn, should lead to a consensus or, at least, to a better understanding of why participants cannot come to an agreement. In this year, we have developed proposed system and verified the system. Publications Original Papers Ontology-based Description of Functional Design Knowledge and Its Use in a Functional Way Server,Y. Kitamura and R. Mizoguchi : Expert Systems with Application, 24[2] (2003) 153-166. Kfarm: An Ontology-aware Support Environment for Learning-Oriented Knowledge Management, Y. Hayashi, H. Tsumoto, M. Ikeda and R. Mizoguchi : The Journal of

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Information and Systems in Education, 1[1] (2003). 80-89. An Ontology-aware Design Environment for Learning Contents, Y. Hayashi, R. Yamasaki, M. Ikeda and R. Mizoguchi : Journal of Information Processing Society of Japan 44[1] (2003) 195-208. An Interaction Analysis Support System for CSCL, A. Inaba, R. Ohkubo, M. Ikeda and R. Mizoguchi : Journal of IPSJ, 44[11] (2003) 2617-2627. Communication Support System Adapted to a User's Background Knowledge and the Topic Context, K. Sumi and T. Nishida : Systems and Computers in Japan, 34[7] (2003) 87-98. Cell Signaling Networks Ontology, T. Takai-Igarashi and R. Mizoguchi, In Silico Biol. 4, 0008 (2003) Review Papers Knowledge Representation from the Modeling Point of View,R. Mizoguchi, M. Ikeda and Y. Kitamura, J. of JSAI 18[2] (2003) 183-192. Tutorial on Ontological Engineering - Part 1: Introduction to Ontological Engineering, R. Mizoguchi, New Generation Computing 21[4] (2003) 365-384. Books Ontology Engineering Environments, R. Mizoguchi, In Handbook on Ontologies, S. Staab and R. Studer (editors), Springer, (2003) 275-295. International Conferences Management of Dependency between Two or More Ontologies in an Environment for Distributed Development, E. Sunagawa, *K. Kozaki, Y. Kitamura and R. Mizoguchi, International Workshop on Semantic Web Foundations and Application Technologies (SWAFT), Nara, Japan, March 12, 2003 An Ontological Schema for Sharing Conceptual Engineering Knowledge (Poster), *Y. Kitamura and R. Mizoguchi, The International Workshop on Semantic Web Foundations and Application Technologies, Nara, Japan, March 12, 2003. Learning Goals and Design Rationales in Collaborative Learning - An Ontological Approach to Support Design of Collaborative Learning, *A. Inaba, M. Ikeda and R. Mizoguchi, The International Symposium of the Institute of Scientific and Industrial Research (ISIR Symposium), Osaka, Japan, March 10-11, 2003 Modeling Learner-To-Learner Interaction Process in Collaborative Learning - An Ontological Approach to Interaction Analysis, *A. Inaba, R. Ohkubo, M. Ikeda and R.

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Mizoguchi, The International Conference on Computer Support for Collaborative Learning (CSCL2003), Bergen, Norway, June 14-18 , 2003 How do Computers help a Learner to Master Self-regulation Skill?, *M. Kayashima and A. Inaba, The International Conference on Computer Support for Collaborative Learning (CSCL2003), Bergen, Norway, June 14-18, 2003. Process-aware Authoring of Web-based Educational Systems, *L. Aroyo and R. Mizoguchi, The First International Workshop of Semantic Web for Web-based Learning (SW-WL03), Velden, Austria, June 16, 2003 The Proposal of an Expression of the Instructional Model of Information Education based on Ontology Theory, *T. Kasai, H. Yamaguchi and R. Mizoguchi, World Conference on Educational Multimedia and Hypermedia (ED-MEDIA'03), Honolulu, Hawaii, June 23-28, 2003. Ontology of Tests, *L. Soldatova and R. Mizoguchi, Computers and Advanced Technology in Education, Rhodes, Greece, June 30 - July 2, 2003 Who is a Person of High Intellectual Reputation in an Organization?, *Y. Hayashi, M. Ikeda and R. Mizoguchi, The International Conference on Artificial Intelligence in Education (AIED2003), Sydney, Australia, July 20-24 ,2003. What Learning Patterns are Effective for a Learner's Growth? - An ontological support for designing collaborative learning, *A. Inaba, M. Ikeda and R. Mizoguchi, The International Conference on Artificial Intelligence in Education (AIED2003), Sydney, Australia, July 20-24 ,2003. Towards Helping Learners Master Self-Regulation Skills, *M. Kayashima and A. Inaba, The International Conference on Artificial Intelligence in Education (AIED2003), Sydney, Australia, July 20-24, 2003. Difficulties in Mastering Self-Regulation Skill and Supporting Methodologies, *M. Kayashima and A. Inaba, The International Conference on Artificial Intelligence in Education (AIED2003), Sydney, Australia, July 20-24 , 2003. An Ontological Approach for Supporting the Instructional Design Process of Information Education, *T. Kasai, H. Yamaguchi and R. Mizoguchi, The International Conference on Artificial Intelligence in Education (AIED'03), Sydney, Australia, July 20-24 , 2003. Authoring Support Framework for Intelligent Educational Systems, *L. Aroyo and R. Mizoguchi, The International Conference on Artificial Intelligence in Education

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(AIED2003), Sydney, Australia, July 20-24, 2003. Ontology Development at the Conceptual Level for Theory-Aware ITS Authoring Systems, *V. Psyché, R. Mizoguchi and J. Bourdeau, The International Conference on Artificial Intelligence in Education (AIED03), Sydney, Australia, July 20-24, 2003. Organizing Knowledge about Functional Decomposition, *Y. Kitamura and R. Mizoguchi, The 14th International Conference on Engineering Design (ICED 03), Stockholm, Sweden, August 19-21, 2003. Testing of Understanding by Use of an Ontology Methodology, *L. Soldatova and R. Mizoguchi, Joint Workshop of Cognition and Learning, Berlin, Germany, September 8-9, 2003. Document Exchange Model for Augmenting Added Value of B2B Collaboration, *K. Hayashi and R. Mizoguchi, Fifth International Conference on Electric Commerce, Pittsburgh, U.S.A., Sep 30 - Oct 3, 2003. An Environment for Distributed Ontology Development Based on Dependency Management, *E. Sunagawa, K. Kozaki, Y. Kitamura and R. Mizoguchi, The Second International Semantic Web Conference (ISWC2003), Sanibel Island, FL, USA, Oct. 2003. A Collaborative Learning Design Environment to Harmonize Sense of Participation, *M. Takeuchi, R. Odawara, Y. Hayashi, M. Ikeda, and R. Mizoguchi, The International Conference on Computers in Education (ICCE2003), Wanchai, HongKong, December 2-5, 2003. Models and Vocabulary to Represent Learner-to-Learner Interaction Process in Collaborative Learning, *A. Inaba, R. Ohkubo, M. Ikeda and R. Mizoguchi, Proceedings of the International Conference on Computers in Education (ICCE2003), Wanchai, HongKong, December 2-5, 2003. The Model of Metacognitive Skill and How to Facilitate Development of the Skill, *M. Kayashima, and A. Inaba, The International Conference on Computers in Education (ICCE03), Wanchai, Hong Kong, December 2-5, 2003. Development of a System that Support Teachers of IT Education in the Instructional Design Process based on Ontology, *T. Kasai, H. Yamaguchi and R. Mizoguchi, International Conference on Computers in Education (ICCE2003), Wanchai, Hong Kong, December 2-5, 2003. OntoAIMS: Ontological Approach to Courseware Authoring, *L. Aroyo, R. Mizoguchi

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and C. Tzolov, The International Conference on Computers in Education (ICCE2003), Wanchai, Hong Kong, December 2-5, 2003. Generation of Test Based on Test Ontology, *L. Soldatova and R. Mizoguchi, The International Conference on Computers in Education (ICCE2003), Wanchai, Hong Kong, December 2-5, 2003. Contributions to International Conferences and Journals Riichiro Mizoguchi International Conference on Computers in Education

2003(ICCE2003)(Conference Chair) Riichiro Mizoguchi International Conference on Artificial Intelligence in

Education 2003(AIED2003)(Conference Chair) Riichiro Mizoguchi International Conference on Computers and Advanced

Technology in Education 2003 (CATE-2003)(PC member) Riichiro Mizoguchi The 8th Ibero-American Conference on Artificial Intelligence

IBERAMIA'03(PC member) Riichiro Mizoguchi The Second International Semantic Web Conference 2003

(ISWC2003)(PC member) Riichiro Mizoguchi The 9th International Conference on User Modeling (UM03)

(PC member) Riichiro Mizoguchi IEEE International Conference on Advanced Learning

Technologies (ICALT 2003) (PC member) Riichiro Mizoguchi La Conferencia de la Asociación Española para la Inteligencia

Artificial (CAEPIA2003)(PC member) Riichiro Mizoguchi International Conference on the Convergence of Knowledge, Culture,

Language and Information Technologies (Convergences03) (PC member)

Riichiro Mizoguchi The 1st European Semantic Web Symposium (ESWS2004) (PC member)

Riichiro Mizoguchi IEEE International Workshop on Wireless and Mobile Technologies in Education (WMTE2003)(PC member)

Riichiro Mizoguchi President of Asia-Pacific Chapter of AACE Riichiro Mizoguchi President of International Artificial Intelligence in Education

Society Riichiro Mizoguchi International Journal of Artificial Intelligence in Education

(Editorial board) Riichiro Mizoguchi International Journal of Advanced Engineering Informatics

(Editorial board) Riichiro Mizoguchi International Journal of Web Semantics(Editorial board) Riichiro Mizoguchi International Journal of Computer and Engineering

Management(Editorial board)

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Riichiro Mizoguchi International Journal of Web Engineering and Technology (Editorial board)

Publications in Domestic Meetings Japanese Society for Artificial Intelligence 11 papers Japanese Society for Information and Systems in Education 3 papers Academic Degrees Master Degree of Engineering

Eiiichi SUNAGAWA An Environment for Distributed Ontology Development Based on Dependency Management

Masataka TAKEUCHI Design support system of collaboration fields optimized both for learning and practice in knowledge management

Yusuke KOJI Ontology-based Design Rationale Model about Supplementary Functions and its Transformation

Doctor Degree of Engineering Koichi HAYASHI Collaboration support by the integrated management of documents and

business processes Sponsorship Grant-in-Aid for Scientific Research on Priority Areas (2) R. Mizoguchi Management and Utilization of Knowledge Contents of

Design and Manufacturing based on Function ¥5,100,000

A. Inaba Constructing repositories of how we design effective collaborative learning to support instructional design process

¥3,200,000

Grant-in-Aid for Scientific Research (A) (2) R. Mizoguchi Development of a Theory-Aware Authoring Workbench ¥9,600,000

Grant-in-Aid for Encouragement of Young Scientists (B) Y. Kitamura Research on functional ontologies for sharing functional

design knowledge ¥1,300,000

A. Inaba Modeling learner-to-learner interaction process in collaborative learning

¥1,700,000

Other Allocations R. Mizoguchi Human-Centered Semantic Web ¥2,820,000

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Entrusted Research

R. Mizoguchi

Galaxy Express Corporation

MEXT IT Program e-Science Project Building a support system for operating a large-scale system using advanced IT

¥2,100,000

Cooperative Research R. Mizoguchi The Society of

Chemical Engineers, Japan

New Energy and Industrial Technology Development Organization Nanotechnology Materials Program "Structuralization of Materials Technology Know-How" Nanotechnology ontology studies and development of an ontology server

¥5,250,000

R. Mizoguchi Japan Aerospace Exploration Agency

Research on Application of Ontology Engineering to Satellite Design Support

¥4,300,000

R. Mizoguchi Sumitomo Electric Industries, Ltd.

Development of a tool for technical knowledge systematization

¥2,520,000

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Department of Intelligent Media Professor: Yasushi YAGI Visiting Professor: Tomio ECHIGO Research Associate: Ryusuke SAGAWA Graduate Students: Yuu OHARA, Takuji MAEDA, Kazuhiro

NAKAMINAMI, Yoshihiko FUJIMOTO, Tomoyuki YAO, Naoki KURITA

Research Students: Yasuhiro HAMANO, Yasuhiro YAMAGAMI, Seiji YAMAGUCHI

Support Staff: Chikako IWATA, Masako KAMURA, Noriko YASUI, Saiko ONISHI

Outlines

The studies in this laboratory focus on theory and applications related to computer vision and media processing. Some of the major research projects undertaken in the laboratory involve the creation of novel vision sensors, including the omni-directional vision system, and the development of algorithms for modeling real environments. Our research projects are motivated by applications in the fields of digital archiving, surveillance, intelligent robots, human interfaces and visualization. Current Research Programs

1. Seamless Integration of Real World and the Web Space using Contents Description Language "NWCDL" Mobile services using positional information have been in the limelight over the last few years. How the information on the real world is expressed influences the quality of the services. We suppose that the information in the real world has three axes, which are the temporal axis, the positional axis, and the qualitative axis. Based on the features of those three axes, we propose the contents description schema "NWCDL(Navigation and Web Contents Description Language)" which describes the information in the real world. From the middle of 1990s, Web sites have spread rapidly in the internet. By including the contents of Web sites into NWCDL, it is possible to materialize the environment where the real world and the Web space are integrated seamlessly. In this research, we choose an amusement park as the application of NWCDL. We made a prototype system which guided users in the amusement park. In order to verify the effectiveness of the positional axis in NWCDL, we compared the time required for our system with for the existing Web. Using questionnaires, we considered the effectiveness and the improvement of this system. As having obtained a favorable result, we have confirmed that NWCDL is effective. 2. Behavioral Analysis of Customers in a Store with an Omnidirectional Sensor As the demand for a behavioral analysis system is increasing, various systems have been proposed and put into practical use so far. We propose a system of analyzing

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customers’ behaviors by the real-time person feature extraction. The proposed system estimates customers' positions and their moving speed from a video, and shows their behaviors in the form which matches time and place. Here, customers' behaviors indicate how customers move in a store or what kind of goods they show an interest in. 3. Recognizing Actions for Automatically Acquiring Personal Preferences from TV Viewer’s Behaviors The importance of information services considering personal preferences is increasing. We proposed a system for automatically acquiring personal preferences from TV viewer’s behaviors. In this paper, we examine TV viewer’s behaviors based on psychological theory, and classify them into eight categories. We then describe recognition methods of the behaviors considered to be effective for acquiring personal preferences among classified behaviors through image and audio processing. Publications Original Papers Rolling and Swaying Motion Estimation for Mobile Robot by using Omnidirectional Optical Flows, Y. Yagi, W. Nishi, N. Benson, M. Yachida, International Journal of Machine Vision and Applications, 14[2] (2003) 112-120. Superresolution Modeling Using an Omnidirectional Image Sensor, H. Nagahara, Y. Yagi, M. Yachida, IEEE Transactions on Systems, Man, and Cybernetics, Part B: Cybernetics, 33[4] (2003) 607-615 International Conferences Contents Description Language ``NWCDL'' for Integrating Web Contents with Navigation, *K. Nakaminami, F. Shibata, N. Babaguchi, the 6th SANKEN(ISIR) International Symposium, Osaka, Japan, 2003.3.10-11. Wide Field of View Head Mounted Display for Tele-presence with An Omnidirectional Image Sensor, *H. Nagahara, Y. Yagi, M. Yachida, Workshop on Omnidirectional Vision and Camera Networks, Madison Wisconsin, USA, June 21, 2003. Parallel Alignment of a Large Number of Range Images, *T. Oishi, R. Sagawa, A. Nakazawa, R. Kurazume, K. Ikeuchi, 3DIM 2003, Banff, Alberta, Canada, October 6-10, 2003. Iconic Memory-based Omnidirectional Route Panorama Navigation, *Y. Yagi, K. Imai, M. Yachida, IEEE International Conference on Robotics and Automation, pp.564-570, Taipei, Taiwan, Sep. 16-18, 2003. Wide Field of View Catadioptrical Head-Mounted Display, *H. Nagahara, Y. Yagi, M. Yachida, In IEEE/RSJ International Conference on Intelligent Robots and Systems, Las Vegas,Nevada,U.S.A., October 27-31, 2003.

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Super Wide View Tele-operation System, *H. Nagahara, Y. Yagi, H. Kitamura, M. Yachida, IEEE Conference on Multisensor Fusion and Integration for Intelligent Systems, Tokyo, Japan, July 30- August 1, 2003. Super-resolution Modeling, *H. Nagahara, Y. Yagi, M. Yachida, IEEE Conference on Multisensor Fusion and Integration for Intelligent Systems, Tokyo, Japan, July 30- August 1, 2003 Walking Person Identification Dealing With Resolution and Appearance Changes, *Y. Ohara, R. Sagawa, T. Echigo, Y. Yagi, SANKEN International Workshop on Inteligent Systems, December 17, 2003. Super Wide Viewer Using Catadioptrical Optics, *H. Nagahara, Y. Yagi, M. Yachida, 10th ACM Symposium on Virtual Reality Software and Technology, Osaka, Japan, October 1-3, 2003. Real-time Human Feature Acquisition and Human Tracking by Omnidirectional Image Sensor, T. Mituyosi, *Y. Yagi, M. Yachida, IEEE Conference on Multisensor Fusion and Integration for Intelligent Systems, Tokyo, Japan, July 30- August 1, 2003. Taking Consensus of Signed Distance Field for Complementing Unobservable Surface, *R. Sagawa, K. Ikeuchi, 3DIM 2003, Banff, Alberta, Canada, October 6-10, 2003. Effective Nearest Neighbor Search for Aligning and Merging Range Images, *R. Sagawa, T. Masuda, K. Ikeuchi, 3DIM 2003, Banff, Alberta, Canada, October 6-10, 2003. Contributions to International Conferences and Journals Y. YAGI OMNIVIS'04 The fifth Workshop on Omnidirectional Vision, Camera

Networks and Non-classical cameras (Program Committee Members) Y. YAGI 10th ACM Symposium on Virtual Reality Software and Technology

(Program Committee Members) Y. YAGI Omnivis 2003: Omnidirectional Vision and Camera Networks 2003

(Workshop Co-chair) Y. YAGI the International Journal of Automation and Computing (Editorial Board)

Publications in Domestic Meetings Information Processing Society of Japan 1 paper The Institute of Electronics, Information and Communication Engineers 1 paper Academic Degrees Master Degree of Engineering Kazuhiro Nakaminami

Seamless Integration of Real World and the Web Space using Contents Description Language "NWCDL"

Yoshihiko Fujimoto Behavioral Analysis of Customers in a Store with an

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Omnidirectional Sensor Tomoyuki Yao A Proposal of a System for Automatically Acquiring Personal

Preferences from TV Viewer's Behaviors Sponsorship Grant-in-Aid for Scientific Research (B) Y. Yagi Basic research on task oriented ominidirectional image

sensor ¥4,800,000

Grant-in-Aid for Scientific Research on Priority Area Y. Yagi Sensing system for human behavior analysis ¥5,100,000

Other Research Funds Y. Yagi Handai Frontier Research Center (FRC)

Development of omni-directional surveillance system ¥6,400,000

Y. Yagi Japan Science and Technology Agency (JST) Development of medical technology using omnidirectional vision

¥29,000,000

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Department of Architecture for Intelligence Professor: Masayuki NUMAO Associate Professor: Akihiro KASHIHARA (Until Nov. 30) Research Associate: Akiko INABA (Until Sep. 30) COE Researcher: Sukree SINTHUPINYO (From Aug. 1) Graduate Students: Roberto LEGASPI, Nobuhiro KONISHI, Kenji SHIMIZU Special Research Students: Cholwich NATTEE, Atsushi SHIRO, Tetsuo TAKATA Research Student: Kenichi FUKUI Outlines

The main research objective is to explore basic technology for computer systems,

which support human learning and understanding, beyond conventional artificial intelligence. We particularly focus on the process of human-computer interaction to discover and create architecture of intelligence for such systems. We try to produce highly original research with findings from cognitive science, psychology, education, and computer science. Principal issues addressed are as follows: 1. Constructive Adaptive User Interfaces, 2. Web-based Learning Environments, and 3. Instructional Design Support for Collaborative Learning.

Current Research Programs

1. Constructive Adaptive User Interfaces This department is developing a computer with learning ability, for which it researches efficient learning algorithms, acquisition of background knowledge for learning, application to Intelligent Tutoring Systems. These are applied to adaptive user interfaces. The conventional adaptive user interfaces only select a good response out of some previously given ones. Although this helps to use interfaces, such as a navigation system, it is not sufficient to stimulate human intelligence or creativity. The department has developed a method to compose a new content adaptively. This technology enables automatic acquisition of human feelings, and automatic music composition system adapted to personality and emotion of its user. 2. Web-based Learning Environments Web can be viewed as a promising learning platform that facilitates self-directed learning with hypermedia/hypertext-based learning resources. In particular, learners can deeply learn about a certain topic by navigating a number of learning resources dealing with the topic, and can navigate the Web pages to construct their own knowledge from the contents of the navigated pages. However, it is not so easy to learn web-based learning resources in a self-directed way. It is particularly difficult for learners to navigate hyperspace, which is a learning space provided by the learning resources, in a constructive way. In order to overcome these problems, we address an issue of how to support meta-cognition in hyperspace. (1) Adaptive Navigation Previewing

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Web-based learning resources provide learners with hyperspace where they can navigate domain concepts/knowledge in a self-directed and a constructive way. However, learners often fail in making the navigation path since they reach an impasse due to a cognitive overload, which is caused by the complexity of hyperspace. In order to resolve this problem, we have developed an adaptive previewer, which is composed of hyperspace map, page previewer, and path previewer. The page previewer generates an overview of each WWW page in the map by extracting information from the HTML file according to the learning contexts. The path previewer helps learners make a sequence of the pages previewed as navigation path plan. These facilities help learners decide which page to visit and plan a navigation path without visiting hyperspace. (2) Adaptive Reflection Support for Learning in Hyperspace

The main problem addressed here is how to help learners reflect on knowledge that they have constructed in navigating existing hypermedia/hypertext based learning resources on the Web. In order to resolve this problem, we have developed an adaptive postviewer that can identify and display the contents learners have learned in each page navigated. We have also developed history comparator and knowledge externalization environment for motivating learners to reflect their knowledge constructed in hyperspace. 2. Instructional Design Support for Collaborative Learning Collaborative learning, which is one of the typical learning styles, on computer networks has been gathering many researchers' interests. It is important how computer systems can support the collaborative learning at some phases; design, implementation, analysis, and evaluation. Many of software designers of computer supported collaborative learning (CSCL) environment have experiences of being suffered with complex and subtle educational requirements offered by clients. One of major causes of the problem they face is the lack of shared understanding of collaborative learning. We do not know what design rationale of CSCL environment is and even do not have common vocabulary to describe what the collaborative learning is. In this research we are aiming at supporting such complex instructional design (ID) process of CSCL environment. To fulfill the aim we have been constructing an ontology to represent CSCL session. The ontology will work as both vocabulary to describe the session and design pattern referred to during the instructional design process. With the ontology, we can represent many kinds of CSCL sessions in terms of common vocabulary. It will facilitate users' shared understandings and reuse a learning scenario of a session. It is important to store and provide effective learning scenarios as design patterns. We adopt learning theories as foundation to analyze, design, and develop the learning sessions. The design patterns inspired with the theories provide design rationale for CSCL design. We have been constructing some ID support tools for CSCL, and an instructional design support environment which enables users to design learning scenarios easily and to arrange some tools for CSCL in the scenarios.

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Publications Original Papers Supporting Reflection on Self-Directed Learning Process in Hyperspace, A. Kashihara, M. Sakamoto, S. Hasegawa, and J. Toyoda: Journal of Japanese Society for Artificial Intelligence, 18 [5](2003), 245-256. A Knowledge Externalization Support for Constructive Learning in Hyperspace, S. Hasegawa, A. Kashihara, R. Suzuki, and J. Toyoda: Transactions of Japanese Society for Information and Systems in Education, 20 [2](2003), 106-118. e-Learning Library with Local Indexing and Adaptive Navigation Support for Web-based Learning, S. Hasegawa, A. Kashihara, and J. Toyoda: Journal of Educational Multimedia and Hypermedia, AACE 12 [1] (2003), 91-111. A Local Indexing for Learning Resources on WWW, S. Hasegawa, A. Kashihara, and J. Toyoda: Systems and Computers in Japan, 34 [3] (2003), 1-9. An Interaction Analysis Support System for CSCL, A. Inaba, R. Ohkubo, M. Ikeda and R. Mizoguchi : Journal of IPSJ, 44[11] (2003) 2617-2627. International Conferences Self-evaluated Learning Agent in Multiple State Games, * K. Moriyama, and M. Numao, European Conference on Machine Learning 2003, Cavtat-Dubrovnik, Croatia, September 22-26, 2003. Mining Chemical Compound Structure Data Using Inductive Logic Programming, *C. Nattee, S. Sinthupinyo, M. Numao, and T. Okada, Second International Workshop on Active Mining, Maebashi, Japan, October 28, 2003. Relational Mining for Temporal Medical Data, *R. Ichise and M. Numao, The Second IASTED International Conference on Information and Knowledge Sharing (IKS2003), Scottsdale, AZ, USA, November 17-19, 2003. Discovery of Temporal Relationships using Graph Structures, *R. Ichise and M. Numao, The Second International Workshop on Active Mining, Maebashi, Japan, October 28, 2003. Towards Designing Meta-Navigation Space for Self-directed Learning on the Web, *N. Konishi, A. Kashihara, and M. Numao, International Conference on Computers in Education 2003, Hong Kong, December 2-5, 2003. Designing Intelligent Self-Directed Learning Platform on the Web, *A. Kashihara, and S. Hasegawa, 11th International Conference on Artificial Intelligence in Education, Sydney, Australia, July 20-24, 2003.

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LearningBench: A Self-Directed Learning Environment on the Web, *A. Kashihara, and S. Hasegawa, World Conference on Educational Multimedia, Hypermedia & Telecommunications 2003, Honolulu, Hawaii, USA, June 23-28, 2003. A Digital Repository of Navigational Learning Histories on the Web, *A. Kashihara, S. Yoshimoto, S. Hasegawa, and J. Toyoda, Telecommunications+Education Workshop in 10th International Conference on Telecommunications, Papeete, Tahiti, French Polynesia, March 1, 2003. Learning Goals and Design Rationales in Collaborative Learning - An Ontological Approach to Support Design of Collaborative Learning, *A. Inaba, M. Ikeda and R. Mizoguchi, Proceedings of the International Symposium of the Institute of Scientific and Industrial Research (ISIR Symposium), pp.81-84, Osaka, Japan, March 10-11, 2003 Modeling Learner-To-Learner Interaction Process in Collaborative Learning - An Ontological Approach to Interaction Analysis,: *A. Inaba, R. Ohkubo, M. Ikeda and R. Mizoguchi, Supplementary Proceedings of the International Conference on Computer Support for Collaborative Learning (CSCL2003), pp.4-6, Bergen, Norway, June 14-18 , 2003 How Do Computers Help a Learner to Master Self-regulation Skill?, *M. Kayashima and A. Inaba: Supplementary Proceedings of the International Conference on Computer Support for Collaborative Learning (CSCL2003), pp.123-125, Bergen, Norway, June 14-18, 2003. What Learning Patterns Are Effective for a Learner's Growth? - An ontological support for designing collaborative learning, *A. Inaba, M. Ikeda and R. Mizoguchi, Proceedings of the International Conference on Artificial Intelligence in Education (AIED2003), pp. 219-226, Sydney, Australia, July 20-24 ,2003. Towards Helping Learners Master Self-Regulation Skills, *M. Kayashima and A. Inaba : Supplementary Proceedings of the International Conference on Artificial Intelligence in Education (AIED2003), pp.602-614, Sydney, Australia, July 20-24, 2003. Difficulties in Mastering Self-Regulation Skill and Supporting Methodologies, *M. Kayashima and A. Inaba, Proceedings of the International Conference on Artificial Intelligence in Education (AIED2003), pp.443-445, Sydney, Australia, July 20-24 , 2003. Models and Vocabulary to Represent Learner-to-Learner Interaction Process in Collaborative Learning, *A. Inaba, R. Ohkubo, M. Ikeda and R. Mizoguchi, Proceedings of the International Conference on Computers in Education (ICCE2003), pp.1088-1096, Wanchai, Hong Kong, December 2-5, 2003.

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The Model of Metacognitive Skill and How to Facilitate Development of the Skill, *M. Kayashima, and A. Inaba : Proceedings of the International Conference on Computers in Education (ICCE03), pp.277-285, Wanchai, Hong Kong, December 2-5, 2003. Contributions to International Conferences and Journals M. Numao New Generation Computing (Area Editor) M. Numao 6th Annual Symposium on Japanese-American Frontiers of Science

(Planning Group Member) M. Numao The 3rd International Joint Conference on Autonomous Agents and

Multi Agent Systems (Program Committee) M. Numao 14th International Symposium on Methodologies for Intelligent

Systems (Program Committee) M. Numao The 8th Pacific Rim International Conference on Artificial

Intelligence (Program Committee) M. Numao The IEEE/WIC/ACM International Conference on Web

Intelligence/Intelligent Agent Technology (Program Committee) A. Kashihara Journal of International Forum of Educational Technology & Society

(Editorial Board) A. Kashihara World Conference on Educational Multimedia, Hypermedia

&Telecommunications (Program Committee) A. Kashihara e-Society 2003 IADIS (International Association for Development of

the Information Society) International Conference (Program Committee)

Publications in Domestic Meetings Japanese Society for Artificial Intelligence: 9 papers Japanese Society for Information and Systems in Education: 3 papers The Institute of Electronics, Information and Communication Engineers 6 papers Information Processing Society of Japan 5 papers Academic Degrees Doctor Degree of Engineering

C. Nattee Learning First-order Rules from Multiple-part Data

Master Degree of Engineering

N. Konishi Designing Meta-Space for Scaffolding Meta-Cognition in Learning Web Contents

A. Shiro Preprocessing Planning for Data Mining T. Takata A Sampling Method for Acquiring Human Feelings

Sponsorship Grant-in-Aid for Scientific Research on Priority Area (2) M. Numao Automatic Information Gathering and Preprocessing by

using Multistage Learning Method ¥8,400,000

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A. Inaba Constructing Repositories of How We Design Effective Collaborative Learning to Support Instructional Design Process

¥3,200,000

Grant-in-Aid for Scientific Research (B)(2) M. Numao Data-gathering Apprentice for Data Mining ¥3,100,000 Grant-in-Aid for Scientific Research (C)(2) A. Kashihara How to Scaffold Self-Monitoring of Learning Processes

in Hyperspace ¥1,700,000

Grant-in-Aid for Encouragement of Young Scientists (B) A. Inaba Modeling Learner-to-Learner Interaction Process in

Collaborative Learning ¥1,700,000

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Department of Advanced Reasoning Professor: Hiroshi MOTODA Associate Professor: Takashi WASHIO Research Associates: Tetsuya YOSHIDA, Kouzou OHARA Post Doctoral Fellow: Chien Phu NGUYEN Graduate Students: Akihiro INOKUCHI, Fuminori ADACHI, Warodom GEAMSAKUL, Atsushi FUJIMOTO Research Students: Yuki MITSUNAGA, Akira MOGI Support Staff: Kana KOYAGI Outlines

Being able to reason is fundamental to the intelligent activities of human beings. We humans create new ideas and entities based on our internal knowledge resource acquired by both external facts and past experiences. However, there is a cognitive and psychological limit in our information processing capability. Humans are very good at reasoning and interpreting a small amount of data be it semantically or syntactically, but are very poor at extracting useful/meaningful information in a short period of time from a huge amount of data. Our laboratory's research focus is on exploring various methods of mining/discovering informative knowledge from massive data using mathematical constraints, heuristic and statistical search techniques. During this year, we have worked on 1) knowledge acquisition from human experts and data, 2) knowledge discovery from graph structured data, 3) information retrieval under various data format, 4) discovery of time dependent law equations from data, and 5) derivation of association rules for data with numeric attributes. Current Research Programs 1. Knowledge acquisition from human experts and data Human experts can justify a given example case when put in a right context, whereas they are not good at explicitly stating the knowledge used in the problem solving for the case. We have investigated the performance of ripple down rules (RDR) technique, which efficiently acquires and utilizes expertise cultivated by experienced users in real fields. This approach always ensures the integrity of the accumulated knowledge after every addition of new piece of knowledge. The main results obtained up to this year include the followings. 1. We found that which knowledge to use as the default strongly affects the efficiency

of knowledge acquisition and the compactness of the final knowledge base, and proposed a measure that can select the best default knowledge. The measure is to select the knowledge whose minimum description length is maximum. We have tested this against 15 different datasets from UCI data repository and confirmed the usefulness of this measure.

2. We further investigated how to delete existing knowledge from the knowledge base

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that is no more valid due to environment change. This ensures that RDR is a useful technique of knowledge acquisition even in a dynamic changing environment.

3. We have extended the RDR approach to incorporate knowledge acquisition from

existing data. The new method can construct an RDR tree using the minimum description length principle from data alone. Thus, it is now possible to acquire knowledge and build a single RDR tree from two different sources of knowledge, i.e., human experts and accumulated labeled data. Switching of knowledge acquisition from human expert to data and vive versa can be made at any time point of knowledge base development.

4. We investigated a method to accelerate the knowledge acquisition not only by

waiting for a new piece of data coming but also by actively asking a human expert from RDR, and proposed a promising method that allows an expert to answer only the class labels when the prediction of RDR is not correct and yet yields a knowledge base which is as good as the one built by a standard RDR method in which an expert has to refine the knowledge base.

5. We integrated the mechanisms: extension to an environment change and knowledge

acquisition from a human expert and data. The analysis confirmed that these two can work as expected in an integrated environment.

6. We added a function to prune the acquired knowledge in addition to the function to

delete useless knowledge in order to enhance the generalization capability, and demonstrated its effectiveness by a large number of datasets.

This year we did an extensive study of performance evaluation for various

combination of knowledge source and environment change comparing the case where we trust human expert decision and the case where we modify the expert’s decision using the information available from data when both kinds of knowledge are available, and verified that the latter results in a better performance in general. We think that the major objectives of this research subject are accomplished. 2. Knowledge discovery from graph structured data There have recently been many attempts on data mining but most of them are targeted to data in the standard transaction format or the relational database format. It appears that there are no effective methods that allow us to mine a dataset that has a more complex structure. Noting that most of the knowledge and concepts we handle can be represented in a graph structure, we have been working for the knowledge discovery from graph-structured data from various perspectives over the last several years. The task of finding frequently appearing subgraphs (subgraph isomorphism) is known to be computationally hard and this is a very difficult problem to solve. The main results obtained up to this year include the followings. 1. We have developed a learning mechanism called “graph-based induction (GBI)”

that discovers characteristic patterns in a graph based on a simple idea of repeated

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chunking of linked two nodes in the graph. We also have expanded the method to discover classification rules that can predict the root node of a tree-structured data, and applied this to command prediction which is one of the functions needed for friendly user interface and to browsing pattern discovery from WWW log data. This method has a pruning function to suppress the overfitting.

2. We have developed a framework of the conventional basket analysis to derive

association rules among sub-graphs by appropriately pre-processing the graph-structured data to a standard transaction of the conventional basket analysis. This approach allows to use the well-known Apriori algorithm without any modification to a graph-structured data but it is limited to a graph where each node has a unique label.

3. We have succeeded in dropping the requirement of the uniqueness of each node by

rebuilding a completely different method called “Apriori-based Graph Mining (AGM)” that allows to handle topological structure. Graph structure is represented by adjacency matrix and isomorphic structure is efficiently disambiguated by introducing a notion of canonical form. Unlike GBI which is very fast but can only obtain approximate solutions, AGM’s search is complete and derives all frequent induced subgraphs. AGM can handle the most general class of graphs, which includes both connected/unconnected, directed/undirected graphs with colored/un-colored nodes and labeled/unlabeled links. Self-looped link is also allowed.

4. We have extended GBI to handle multi-inputs/outputs, directed/undirected graph

with/without node and link labels and loop structure (including a self-loop). It is not capable of handling non-connected graph. The method was verified to work as expected using artificially generated data. The repeated pairwise chunking does not by any means ensure the optimal solutions. It only extracts frequently appearing patterns in an approximate manner. However, its time complexity is shown to be almost linear to the size of graph.

5. In order to make AGM more efficient, further improvement was made to the data

structure and the algorithm, i.e., extension of code expression representing a graph, change of the definition of the canonical form and the improvement of the search method. This accelerated the execution speed by two order of magnitude. In fact, the past AGM needed much computation time to analyze the subgraph co-occurrence in the molecular substructures of chemical compounds having mutagenesis and carcinogenesis. With this improvement, it is now possible to solve this problem within a tractable time.

6. Extensive improvement was also made on GBI without loosing its merit of greedy

approach. Two separate criteria were introduced one for generating chunks and the other for extracting chunks. Repeated chunking is based on frequency measure but a different measure such as class separability measure can now be used to select good set of chunks. Further, canonical labelling was introduced to identify whether two subgraphs that are generated by different chunking history are indeed isomorphic. With this enhancement, both directed and undirected graphs are now uniformly

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treated. The most important improvement was to adopt a beam search to expand the search space, which is quite effective in reducing the omitted important patterns.

7. We applied GBI to a real world medical dataset of hepatitis B and C, and went

through all the phases of data mining: data preprocessing, conversion to graphs, extraction of typical subgraphs, evaluation of medical expert, and repeated this cycle four times. During the course of analysis, we made an improvement such as biasing the chunking direction, the need that really came from actual practice.

8. We proposed a new method of building a classifier DT-GBI for a graph structured

data using GBI recursively at each node of a decision tree and applied it to a preliminary study of hepatitis data analysis.

9. We extended the adjacency matrix elements which are basic graph representation in

AGM to explicitly represent edge labels in a graph. By this extension, generic, efficient and complete mining of frequent subgraphs which include edges having various labels has been enabled.

10. AcGM has been developed which can mine frequent generic subgraphs and frequent

connected subgraphs not limited to frequent induced subgraphs. This has been achieved by introducing biases to constrain join operation to generate candidate frequent subgraphs in AGM’s search. Especially, the connected subgraph mining is very efficient, and highly practical result in application to Bioactive Compounds Analysis has been obtained.

11. B-AGM has been developed which can mine frequent sub-ordered trees, frequent

sub-unordered trees, frequent subpathes and frequent subsequences not limited to frequent subgraphs. The application fields of AGM have been significantly extended by this development.

12. We extended AGM to do a complete search reflecting the 3 dimensional sub-graph

structure taking into account the 3 dimensional coordinates of vertices in the graph. This year, we performed an extensive analysis of hepatitis data using DT-GBI. Our

aim was to investigate whether it is possible to predict the fibrosis level of liver, type of hepatitis B or C and effectiveness of interferon therapy using the safe and inexpensive blood test without going through an expensive and painful biopsy. The analysis is still underway. During this study, we proposed an approximate method of solving subgraph isomorphism problem. On the other hand, the algorithms of the aforementioned AcGM and B-AGM have been further improved to enable very fast data mining of the structures. With this improvement, AcGM and B-AGM are now one of the fastest complete graph mining tools. Moreover, AcGM was made to be a public software to return the benefit resulted in our research to the public society. Another significant work in our graph mining research is the proposal of a standard of PMML (Predictive

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Model Markup Language) to represent graph structured data. PMML is a subset of XML. The current graph mining tools in public support a graph representation only dedicated to each tool. This is the significant difficulty in sharing the graph data and their mined results. However, with our proposal, a powerful environment becomes available for flexibly combining and using many tools and system in graph mining. 3. Information retrieval under various data format Massive data having various formats such as text, movie, sound, coded data and data specific to each application are being accumulated in computers and their networks. However, information retrieval systems such as search engines remain within the keyword based text search approach. Though some new retrieval methods specific to each data format such as movies and sounds have been proposed, these new retrieval methods can hardly handle many data formats newly borne year by year. We have started developing a new generic retrieval approach that is independent of data format since last year and the following result is obtained last year. 1. A framework has been developed that enables the generic retrieval of various data

format under a single principle.

2. The principle is based on the use of the fast Fourier transform having a mathematical nature of transformation invariance which enables the robust retrieval against the various similar byte sequences to be retrieved.

3. The retrieval algorithm based on this principle has been applied to the keyword based retrieval on text data files and the binary data based retrieval on binary data files of a word processor. In both cases, good performance of the proposed approach has been confirmed.

4. The performance evaluation has been conducted on many more different kinds of binary document data sets, and the efficiency of the retrieval program has been improved. By removing redundant retrieval in the algorithm, the speed of the retrieval has been increased more than 10 times.

5. The program has been extended to enable binary data having two dimensional structure such as picture image data. Only slight extension was required for this purpose because of the essential generality of this approach in nature.

This year, a collaborative research has been done with an industrial company to

remove spam mails from a massive set of e-mail data by retrieving only spam mails which have a large variety of unformatted documents based on the aforementioned techniques. 4. Discovery of time dependent law equations from data

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Just like physicists have tried for many years to find the truth that is hidden in the experimental data by the deep insight and understood the phenomena, computer can assist in analysing a huge amount of data that are beyond the capability of human cognition and derive equations that explain the phenomena. Being able to reproduce the experimental data does not necessarily mean that the derived equations represent the first principle. We are developing a method that ensures to derive the first principle. The main results obtained up to this year include the followings. 1. We have developed a theory of first principle discovery and implemented it to a

working system that can discover multiple simultaneous equations under experimental setting. Notion of scales of the experimental data and an interesting property that is deduced by dimensional analysis are the basis of the method. These two together with simple mathematics can constrain the form of admissible relations among the variables.

2. We have extended the above approach to derive equations from observed data

where no active experimentation is allowed. This extension expands the scope of the application areas of our approach to various practical domains. The manipulation of quantities is not possible, under the environment of passive observation, to obtain numeric data from which to extract the relations among quantities. We introduced a technique to emulate virtual experiments to identify the relations among quantities within a given set of observed data. The final system works for passively observed phenomena for which nothing is known about the equation formulae that are needed to describe them and no knowledge of dimensions of the variables involved is available. It can handle a system that is described by several equations and many variables. The simulation results indicate that the method is noise resistant.

3. We have developed a method that can enhance the reliability of the obtained

equations using two different sets of quantities for the same phenomenon and the information of scale-types of the quantities.

4. An approach to discover a complex law equation model consisting of simultaneous

equations was developed when only the passive observation is available. This work investigated the mathematical properties of invariance, symmetry and lattice structure of a simultaneous equation, and established a principle to figure out the number of equations governing the observed data simultaneously and the configuration of quantities in the equations. Based on the principle, an algorithm to derive law based simultaneous equations from data is developed and implemented. Its high ability to discover the complex models for the data obtained from a process plant and a social phenomenon has been confirmed.

The above work is to discover law equations representing static relations holding

among quantities associated with objects independent to time. In contrast, this year we investigated some principles to discover time dependent law equations which are differential equations reflecting the dynamics of the objects. The equations are discovered based on the observed time series data of quantities associated with the

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objects. 5. Derivation of association rules for data with numerical attributes

Basket Analysis is to derive frequently co-occurred symbolic features and the relations among them, i.e., association rules. However, its applicability is limited to some narrow field since most of practical data are mixtures of symbolic and numerical features. In this regard, the extension of Basket Analysis to make it applicable to the data containing numerical features is expected to highly widen the application area of data mining. We have worked on this issue in our following past work. 1) An approach to discretize numerical feature data into symbolic feature data was

developed. The data are preprocessed by this approach and applied to Basket Analysis. This approach enables to apply Basket Analysis to the data containing numerical features under a certain rough discretization, i.e., approximation, of numerical data.

A drawback of this approach is to lose some detailed information contained in the

original numerical feature data though the discretization, and this induces the loss of accuracy and the miss of the associations rules. In this regards, this year, we investigated some principles and algorithms to search association rules in a more rigorous manner without introducing numerical discretization in the framework of Basket Analysis. Publications Original Papers Application of Data Mining to Biomedical Engineering, T. Washio, J. Kim and M. Kitakaze: Japanese journal of medical electronics and biological engineering, 41[Supp1.1] (2003) 32. Application of a New Data Analysis Method to Medical Informatics, J. Kim, T. Isomura, T. Washio and M. Kitakaze: Japanese journal of medical electronics and biological engineering, 41[Supp1.1] (2003) 35. Complete Mining of Frequent Patterns from Graphs: Mining Graph Data , A. Inokuchi, T. Washio and H. Motoda: Machine Learning, 50 [3] (2003) 321-354. Performance Improvement of AGM ALgorithm and APplication to 3D Structure Analysis, Y. Nishimura, T. Washio, T. Yoshida, H. Motoda, A. Inokuchi and T. Okada: Journal of JSAI, 18[5C] (2003) 257-268. Review Papers State of the Art of Graph-based Data Mining, T. Washio and H. Motoda: SIGKDD

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Explorations, 5 [1] (2003) 59-68. Books Knowledge Management (Y. Osawa Ed.), T. Washio, Ohmsha, (2003) 77-84, 117-125. International Conferences Active Feature Selection Using Classes, H. Liu, L. Yu, D. Manoranjan and *H. Motoda, The 7th Pacific-Asia Conference on Knowledge Discovery and Data Mining (PAKDD2003), Seoul, Korea, Apr. 30-May 2, 2003. Classifier Construction by Graph-Based Induction for Graph-Structured Data, *W. Geamsakul, T. Matsuda, T. Yoshida, H. Motoda and T. Washio, The 7th Pacific-Asia Conference on Knowledge Discovery and Data Mining (PAKDD2003), Seoul, Korea, Apr. 30-May 2, 2003. On Personalizing Video Portal System with Metadata, *K. Ohara, T. Ogura and N. Babaguchi, The 7th International Conference on Knowledge-Based Intelligent Information and Engineering Systems (KES2003), Oxford, UK, Sep. 3-5, 2003. Constructing a Decision Tree for Graph Structured Data, W. Geamsakul, T. Matsuda, T. Yoshida, *H. Motoda and T. Washio, The First International Workshop on Mining Graphs, Trees and Sequences (MGTS-2003) in the 14th European Conference on Machine Learning (ECML'03) and the 7th European Conference on Principles and Practice of Knowledge Discovery in Databases (PKDD'03), Cavtat-Dubrovnik, Croatia, Sep. 23, 2003. Specific Biases for Mining Frequent Substructures, A. Inokuchi, *T. Washio and H. Motoda, The First International Workshop on Mining Graphs, Trees and Sequences (MGTS-2003) in the 14th European Conference on Machine Learning (ECML'03) and the 7th European Conference on Principles and Practice of Knowledge Discovery in Databases (PKDD'03), Cavtat-Dubrovnik, Croatia, Sep. 23, 2003. Performance Evaluation of Decision Tree Graph-Based Induction, *W. Geamsakul, T. Matsuda, T. Yoshida, H. Motoda and T. Washio, The 6th International Conference on Discovery Science (DS2003), Sapporo, Japan, Oct. 17-19, 2003. Development of Generic Search Method Based on Transformation Invariance, *F. Adachi, T. Washio, H. Motoda, A. Fujimoto and H. Hanafusa, The 14th International Symposium on Methodologies for Intelligent Systems (ISMIS03), Maebashi, Japan, Oct. 28-31, 2003. Extracting Diagnostic Knowledge from Hepatitis Dataset by Decision Tree Graph-Based Induction, *W. Geamsakul, T. Yoshida, K. Ohara, H. Motoda and T. Washio,

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The 2nd International Workshop on Active Mining (AM2003), Maebashi, Japan, Oct. 28, 2003. Data Mining Oriented CRM Systems Based on MUSASHI: C-MUSASHI, *K. Yada, Y. Hamuro, N. Katoh, T. Washio, I. Fusamoto, D. Fujishima and T. Ikeda, The 2nd

International Workshop on Active Mining(AM2003), Maebashi, Japan, Oct. 28, 2003. Effect of Personalization on Retrieval and Summarization of Sports Video, *N. Babaguchi, K. Ohara and T. Ogura, The 4th International Conference on Information, Communications & Signal Processing/4th IEEE Pacific-Rim Conference On Multimedia (ICICS-PCM03), Singapore, Dec. 15-18, 2003. Contributions to International Conferences and Journals H. Motoda Intelligent Data Analysis: An International Journal(Editorial Board) H. Motoda Advanced Engineering Informatics (Editorial Board) H. Motoda International Journal of Human-Computer Studies (Editorial Board) H. Motoda Knowledge and Information Systems: An International Journal

(Editorial Board) H. Motoda Discovery Science Conference (Steering Committee, Chair) H. Motoda Pacific-Asia Conference on Knowledge Discovery & Data Mining

(Steering Committee, Chair) H. Motoda Pacific Rim International Conference on Artificial Intelligence

(Steering Committee) H. Motoda First International Workshop on Data Mining Lessons Learned (Co-

organizer) H. Motoda Fourth Pacific Rim Knowledge Acquisition for Knowledge-Based

Systems Workshop: PKAW04 (Honorary chair) H. Motoda International Workshop on Active Mining: AM-2003 (Co-organizer) H. Motoda The 6th IFIP International Conference on Information Technology

for BALANCED AUTOMATION SYSTEMS in Manufacturing and Services, Track D: Machine learning and data mining in industry (Program Committee)

H. Motoda The 14th International Conference on Knowledge Engineering and Management - EKAW 2004 (Program Committee)

H. Motoda The 15th European Conference on Machine Learning ECML (Program Committee)

H. Motoda The 8th European Conference on Principles and Practice of Knowledge Discovery in Databases PKDD (Program Committee)

H. Motoda The 16th European Conference on Artificial Intelligence, ECAI2004 (Program Committee)

H. Motoda The 5th Pacific Rim Knowledge Acquisition for Knowledge-Based Systems Workshop: PKAW04, 2004 (Program Committee)

H. Motoda The 8th Pacific-Asia Conference on Knowledge Discovery & Data Mining: PAKDD04 (Program Committee)

H. Motoda The First International Workshop on Mining Graphs, Trees and Sequences (MGTS-2003) (Program Committee)

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H. Motoda The 2nd International Workshop on Multi Relational Data Mining (MRDM-2003) (Program Committee)

H. Motoda The 2003 International Workshop on Data Mining for Software Engineering and Knowledge Engineering (DMSK'03) (Program Committee)

H. Motoda The International Workshop on Foundation of Data Mining and Discovery (Program Committee)

H. Motoda The 7th Pacific-Asia Conference on Knowledge Discovery & Data Mining (Program Committee)

H. Motoda The 2003 IEEE International Conference on Data Mining (Program Committee)

H. Motoda The 14th European Conference on Machine Learning (Program Committee)

H. Motoda The 7th European Conference on Principles and Practice of Knowledge Discovery in Databases (Program Committee)

H. Motoda The 14th International Symposium for Methodology of Intelligent Systems (Program Committee)

T. Washio New Generation Computing (Editorial Board) T. Washio The 2003 IEEE International Conference on Data Mining (ICDM03)

(Program Committee) T. Washio Thirteenth International Workshop on Principles of Diagnosis

(DX'03) (Program Committee) T. Washio Tenth International Conference on Machine Learning (ICML-2003)

(Program Committee) T. Washio Web Intelligence Research and Development (Proc. of First Asia

Pacific Conf., WI2003) (Program Committee) T. Washio Fifth International Conference on Data Warehousing and Knowledge

Discovery (DaWaK 2003) (Program Committee) T. Washio First International Workshop on Mining Graphs, Trees and

Sequences (MGTS-2003) In conjunction with 14th European Conference on Machine Learning (ECML'03) and 7th European Conference on Principles and Practice of Knowledge Discovery in Databases (PKDD'03) (Workshop Chair)

T. Yoshida International Workshop on Active Mining (AM-2002) (Program Committee)

T. Yoshida 2003 IEEE/WIC International Conference on Web Intelligence (WI2003) (Program Committee)

T. Yoshida 2003 International Conference on Active Media Technology (ICAMT2003)(Program Committee)

T. Yoshida International Symposium for Methodology of Intelligent Systems (ISMIS2003) (Program Committee)

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Publications in Domestic Meetings

Japanese Society for Artificial Intelligence 7 papers The Institute of Electronics, Information and Communication Engineers 4 papers Japanese Society for Medical and Biological Engineering 2 papers Information Processing Society of Japan 1 paper

Academic Degrees Doctor Degree of Engineering A. Inokuchi Study on Mining General Structure Patterns Master Degree of Engineering W. Geamsakul Classifier construction for Graph Structured Data by using

Decision Tree Graph-Based Induction Sponsorship Grant-in-Aid for Scientific Research on Priority Area (1) H. Motoda Implementation of Active Mining in the Era of

Information Flood ¥7,900,000

H. Motoda Active Mining from Structured Data ¥16,400,000

Grant-in-Aid for Scientific Research (B)(2) H. Motoda Development of Knowledge Acquisition System that

Can Cope with Environment Changes ¥3,100,000

Grant-in-Aid for Exploratory Research T. Washio Development of Generic Retrieval Method Based on Feature

Extraction from Various Format Data ¥900,000

Grant-in-Aid for Encouragement of Young Scientists (2) T. Yoshida Development of Co-Training System that can utilize

both Labeled and Unlabeled Data ¥1,600,000

K. Ohara Research on Learning Biases from Interaction between Learning System and User

¥1,600,000

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Division of Biological Sciences Outline

The Division of Biological Sciences is composed of three departments: Dept. of Molecular Cell Biology, Dept. of Cell Membrane Biology, and Dept. of Structural Molecular Biology. These departments are engaged in researches in various fields of biological sciences including molecular enzymology, signal transduction, energy transformation, membrane transport, and mechanism of gene expression. The research projects covered by this division are as follows: 1. The mechanism of energy coupling in ATP synthesis/hydrolysis 2. The mechanism and regulation of formations of cytoplasmic single membrane

(endomembrane) organelles with varying acidic pH 3. The molecular structures and the molecular mechanisms of xenobiotic extruding pumps

functioning as a host-defense mechanism in cellular level 4. Comprehensive studies on bacterial xenobiotic exporter genes and the regulation of the

expression by two-component signal transduction systems 5. Physiological roles of efflux transporters in signal transduction and mammalian

development 6. The mechanisms of biogenesis of the topa quinone cofactor in copper amine oxidase and

other novel “built-in” cofactors in quinohemoproteins 7. Identification of novel protein kinase C-interacting proteins and elucidation of their roles

in signal transduction 8. Development of a new method of the gene delivery system using hepatitis B virus

surface antigen particles Achievements • Rotational catalysis of F- and V-type H+ ATPases • Subunit structure of V-ATPase: Isoforms of extrinsic membrane subunits • Vacuolar type H+ ATPase specific for osteoclasts • Regulation of acidic organeller function coupled with cellular signal transduction • Biogenesis of organelles with acidic pH. • Determination of the crystal structure of bacterial major multidrug exporter AcrB • Site-directed mutagenesis studies based on the crystal structure of AcrB • Construction of the expression library of E. coli response regulator

genes of two-component systems, and analysis of their roles in multidrug resistance • Analysis of regulation network on bacterial multidrug exporters • Analysis of ABCA5 knock-out mice, a novel ABCA subfamily transporter • Studies on the sphingosine-1-phosphate export mechanism from platelet • Identification of novel mammalian RND-type transporters • Chemical and kinetic reaction mechanisms of quinohemoprotein amine dehydrogenase from Paracoccus denitrificans • Stereochemistry of 2-phenylethylamine oxidation catalyzed by bacterial copper

amine oxidase • Identification of a tissue-non-specific homologue of axonal fasciculation and

elongation protein zeta-1 • Novel nanoparticles for the delivery of genes and drugs to human hepatocytes • Chemical rescue of a site-specific mutant of bacterial copper amine oxidase for generation

of the topa quinone cofactor

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Department of Structural Molecular Biology Professor: Katsuyuki TANIZAWA Associate Professor: Shun’ichi KURODA Research Associate: Kenji TATEMATSU Post Doctoral Fellows: Andrés D. MATURANA, Kenji SUZUKI,

Tomoko YAMASAKI, Yen-Chen CHIU (2003.4–2003.6) Research Assistants: Mana IDEI, Setsuko NAGAO Graduate Students: Daisuke KITAGUCHI, Toshitsugu FUJITA,

Miki IWATA, Kazutoshi ONO, Nobuo YOSHIMOTO, Takeshi MURAKAWA, Nobuyuki BOKUI, Junko IKUTA, Ken KISHIGAMI, Masayuki USUI

Support Staff: Mayumi MURATA Outlines

The primary research of this department continues to focus on the biochemical and molecular biological studies on various functional proteins, with particular emphasis on the amino acid-metabolizing enzymes. The active-site structures and catalytic functions of amino acid residues in several interesting enzymes are being investigated by means of affinity labeling, site-directed mutagenesis, various spectroscopies, and X-ray crystallography. One of the recent conspicuous findings is the copper ion-dependent, post-translational modification mechanism for the biogenesis of the topa quinone cofactor in copper amine oxidase. In addition, this department started to investigate the intracellular mechanisms involving protein kinase C family, which play important roles in the cell proliferation, differentiation, oncogenesis, and apoptosis by cross talking with other molecules. Recently, we have succeeded to identify several protein kinase C-interacting proteins and characterized them as regulatory proteins for the protein kinase activities and/or their subcellular localization and also as effectors of kinase signaling. In addition, we have developed bio-nanoparticles displaying various biorecognition molecules, which are expected to be an ideal vector for the tissue- and cell type-specific gene and drug delivery system. Current Research Programs 1. Chemical and Kinetic Reaction Mechanisms of Quinohemoprotein Amine Dehydrogenase from Paracoccus denitrificans.

Quinohemoprotein amine dehydrogenase (QHNDH) possesses a cysteine tryptophylquinone (CTQ) prosthetic group which catalyzes the oxidative deamination of primary amines. In addition to CTQ, two heme c cofactors are present in QHNDH that mediate the transfer of the substrate-derived electrons from CTQ to an external electron acceptor. Steady-state kinetic assays yielded relatively small kcat values (< 6 s–

1) and the rate-limiting step appears to be the interprotein electron transfer from heme in QHNDH to the external electron acceptor. Transient kinetic studies of the CTQ-dependent reduction of heme in QHNDH by amine substrates yielded different rate constants for different substrates (72 s–1, 190 s–1, and 162 s–1 for methylamine,

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butylamine, and benzylamine, respectively). Deuterium kinetic isotope effect (KIE) values of 5.3, 3.9 and 8.5 were observed, respectively, for the reactions of methylamine, butylamine, and benzylamine. These results suggest that the abstraction of a proton from the α-methylene group of the substrate, which occurs concomitant with CTQ reduction, is the rate-limiting step in the CTQ-dependent reduction of hemes in QHNDH by these amine substrates. In contrast, the reaction of 2-phenylethylamine with QHNDH does not exhibit a significant KIE (Hk3/Dk3 = 1.05) and exhibits a much smaller rate constant of 16 s–1. This suggests that for 2-phenylethylamine the rate-limiting step is either hydrolysis of the imine reaction intermediate from CTQ or product release prior to intraprotein electron transfer. Analysis of the products of the reactions of QHNDH with chiral deuterated 2-phenylethylamines demonstrated that the enzyme abstracts the pro-S proton of substrate in a highly stereospecific manner. Inspection of crystal structure of phenylhydrazine-inhibited QHNDH suggests that Asp33γ is the residue that performs the proton abstraction. On the basis of these results, kinetic and chemical reaction mechanisms for QHNDH are proposed and discussed in the context of the crystal structure of the enzyme. 2. Stereochemistry of 2-Phenylethylamine Oxidation Catalyzed by Bacterial Copper Amine Oxidase.

Stereochemical course of the reaction catalyzed by copper amine oxidase from Arthrobacter globiformis has been investigated using 2-phenylethylamine stereospecifically deuterium-labeled at the C1 position. Measurements of deuterium content in the product phenylacetaldehyde by gas chromatography-mass spectrometry revealed stereospecific abstraction of the pro-S hydrogen during the enzymatic oxidation, as predicted from the structure modeling for the enzyme-bound substrate. 3. Identification of a Tissue-non-specific Homologue of Axonal Fasciculation and Elongation Protein Zeta-1.

Fasciculation and elongation protein zeta-1 (FEZ1) is a mammalian orthologue of the Caenorhabditis elegans UNC-76 protein involved in the axonal outgrowth and fasciculation and promotes neurite extension of PC12 cells through interaction with protein kinase C zeta (PKCζ). The gene coding for FEZ2, a homologue of FEZ1, has also been reported in rat and human. In this study, we compared mRNA expression of FEZ1 and FEZ2 in adult rat tissues and mouse embryos by Northern blot and in situ hybridization analyses. In contrast to FEZ1 whose mRNA is expressed almost exclusively in rat brain and temporarily around the neurogenesis stage of mouse embryos, the message for FEZ2 is detected weakly in most tissues and abundantly throughout the mouse embryonic stages. Similar to FEZ1, FEZ2 interacted with PKCζ and induced neurite extension of PC12 cells when coexpressed with a constitutively active mutant of PKCζ. These results suggest that FEZ2 plays an important role in the morphological changes of various cells by associating with PKCζ in a tissue-non-specific manner. 4. Novel Nanoparticles for the Delivery of Genes and Drugs to Human Hepatocytes.

Hepatitis B virus envelope L particles overproduced by yeast are hollow nanoparticles displaying a peptide indispensable for human liver-specific infection. We

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here demonstrate that L particles are applicable for efficient and specific transfer of a gene or drug into human liver-derived cultured cells. In a mouse xenograft model injected intravenously with L particles carrying the gene for green fluorescence protein or a fluorescent dye, fluorescence was observed only in human hepatocellular carcinomas, neither in other human carcinomas nor in mouse tissues. When the human clotting factor IX gene was transferred into the xenograft model using L particles, factor IX was produced in a therapeutically significant level for hemophilia B. The yeast-derived L particle is free of viral genomes, highly specific to human liver cells, and able to accommodate not only genes but also drugs. These advantages should facilitate the gene and drug delivery targeted to human liver. 5. Chemical Rescue of a Site-specific Mutant of Bacterial Copper Amine Oxidase for Generation of the Topa Quinone Cofactor.

The topa quinone (TPQ) cofactor of copper amine oxidase is produced by posttranslational modification of a specific tyrosine residue through the copper-dependent, self-catalytic process. We have site-specifically mutated three histidine residues (His431, His433, and His592) involved in binding of the copper ion in the recombinant phenylethylamine oxidase from Arthrobacter globiformis. The mutant enzymes, in which each His was replaced by Ala, were purified in the Cu/TPQ-free, precursor form and analyzed for their Cu-binding and TPQ-generating activities by UV–visible absorption, resonance Raman, and electron paramagnetic resonance spectroscopies. Among the three His-to-Ala mutants, only H592A was found to show a weak activity to form TPQ upon aerobic incubation with Cu2+ ions. Also for H592A, exogenous imidazole rescued binding of copper and markedly promoted the TPQ formation. Accommodation of a free imidazole molecule within the cavity created in the active site of H592A was suggested by X-ray crystallography. Although the TPQ cofactor in H592A mutant was readily reduced with substrate, its catalytic activity was very low even in the presence of imidazole. Combined with the crystal structures of the mutant enzymes, these results demonstrate the importance of the three copper-binding histidine residues for both TPQ biogenesis and catalytic activity, fine-tuning the position of the essential metal. Publications Original Papers Identification of a Tissue-non-specific Homologue of Axonal Fasciculation and Elongation Protein Zeta-1, T. Fujita, J. Ikuta, J. Hamada, T. Okajima, K. Tatematsu, K. Tanizawa, and S. Kuroda: Biochem. Biophys. Res. Commun., 313 (2003) 738–744. Stereochemistry of 2-Phenylethylamine Oxidation Catalyzed by Bacterial Copper Amine Oxidase, M. Uchida, A. Ohtani, N. Kohyama, T. Okajima, K. Tanizawa, and Y. Yamamoto: Biosci. Biotechnol. Biochem., 67 (2003) 2664–2667. Overexpression of Nell-1, a Craniosynostosis-Associated Gene, Induces Apoptosis in Osteoblasts During Craniofacial Development, X. Zhang, D. Carpenter, N. Bokui, C. Soo, S. Miao, T. Truong, B. Wu, I. Chen, H. Vastardis, K. Tanizawa, S. Kuroda, and K. Ting: J. Bone and Mineral Res., 18 (2003) 2126–2134.

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Phospholipase D from Streptoverticillium cinnamoneum: Protein Engineering and Application for Phospholipid Production, C. Ogino, S. Kuroda, S. Tokuyama, A. Kondo, N. Shimizu, K. Tanizawa, and H. Fukuda: J. Mol. Cat. B, 23 (2003) 107–115. Alteration of Substrate Specificity of Leucine Dehydrogenase by Site-directed Mutagenesis, K. Kataoka, and K. Tanizawa: J. Mol. Cat. B, 23 (2003) 299–309. Chemical and Kinetic Reaction Mechanisms of Quinohemoprotein Amine Dehydrogenase from Paracoccus denitrificans, D. Sun, K. Ono, T. Okajima, K. Tanizawa, M. Uchida, Y. Yamamoto, F. S. Mathews, and V. L. Davidson: Biochemistry, 42 (2003) 10896–10903. A Neuron-specific EGF Family Protein, NELL2, Promotes Survival of Neurons through Mitogen-activated Protein Kinases, K. Aihara, S. Kuroda, N. Kanayama, S. Matsuyama, K. Tanizawa, and M. Horie: Molecular Brain Research, 116 (2003) 86–93. Disrupted-in-Schizophrenia 1, a Candidate Gene for Schizophrenia, Participates in Axonal Outgrowth, K. Miyoshi, A. Honda, K. Baba, M. Taniguchi, K. Oono, T. Fujita, S. Kuroda, T. Katayama, and M. Tohyama: Mol. Psychiatry, 8 (2003) 685–694. Nanoparticles for the Delivery of Genes and Drugs to Human Hepatocytes, T. Yamada, Y. Iwasaki, H. Tada, H. Iwabuki, M. K. L. Chuah, T. VandenDriessche, H. Fukuda, A. Kondo, M. Ueda, M. Seno, K. Tanizawa, and S. Kuroda: Nature Biotechnol., 21 (2003) 885–890. Detection of Protein-Protein Interactions on SiO2/Si Surfaces by Spectroscopic Ellipsometry, S. Kodera, T. Okajima, H. Iwabuki, D. Kitaguchi, S. Kuroda, T. Yoshinobu, K. Tanizawa, M. Futai, and H. Iwasaki: Anal. Biochem., 321 (2003) 65–70. The Active Site Structure of Quinohemoprotein Amine Dehydrogenase Inhibited by p-Nitrophenylhydrazine, A. Satoh, O. Adachi, K. Tanizawa, and K. Hirotsu: Biochim. Biophys. Acta, 1647 (2003) 272–277. A PKCε-ENH-channel Complex Modulates N-type Ca2+ Channels, Y. Maeno-Hikichi, S. Chang, K. Matsumura, M. Lai, H. Lin, N. Nakagawa, S. Kuroda, and J. F. Zhang: Nature Neuroscience, 6 (2003) 468–475. Role of Copper Ion in Bacterial Copper Amine Oxidase: Spectroscopic and Crystallographic Studies of Metal-substituted Enzymes, S. Kishishita, T. Okajima, M. Kim, H. Yamaguchi, S. Hirota, S. Suzuki, S. Kuroda, K. Tanizawa, and M. Mure: J. Am. Chem. Soc., 125 (2003) 1041–1055. Review Papers Pinpoint Drug Delivery System Using Hollow Nanoparticles (in Japanese), A. Kondo, S. Kuroda, K. Tanizawa, M. Seno, and M. Ueda: Chemical Engineering, 67 (2003) 686–

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688. Novel Peptide Built-in Quinone Cofactors: Their Structures, Catalytic Functions, and Mechanism of Biosynthesis, K. Tanizawa: Vitamin, 77 (2003) 275–283. New Progress in Researches of Peptidyl Built-in Cofactors, T. Okajima and K. Tanizawa: Protein, Nucleic Acid, and Enzyme, 48 (2003) 740–746. Pinpoint Delivery System for Genes and Drugs with Bio-Nanoparticles, M. Seno, S. Kuroda, A. Kondo, H. Tada, K. Tanizawa, and M. Ueda: BIO INDUSTRY, (2003), No. 4, 54–62. Nanoparticle-directed Tissue-specific Delivery System for Genes and Drugs, S. Kuroda, T. Yamada, and K. Tanizawa: Discovery Medicine, 3 (2003), No. 18, 56–57. Books New Technology in Nanobiotechnology (A. Ueda, Ed.) (in Japanese), S. Kuroda, A. Kondo, M. Seno, M. Ueda, and K. Tanizawa: CMC Publishers, (2003) 295–304. Nanoparticle Technology (M. Hosokawa and K. Nogi, Eds.) (in Japanese), S. Kuroda, A. Kondo, M. Seno, M. Ueda, and K. Tanizawa: Nikkan Kogyo News Papers, (2003) 122–126. Nanoparticle Technology (M. Hosokawa and K. Nogi, Eds.) (in Japanese), S. Kuroda, A. Kondo, M. Seno, M. Ueda, and K. Tanizawa: Nikkan Kogyo News Papers, (2003) 171–178. Patents “Therapeutic Agents for Hemophilia and Method of Treatment” M. Ueda, S. Kuroda, K. Tanizawa, M. Seno, A. Kondo, T. VandenDriessche, M. K. L. Chuah: JP2003-071788. “Comprehensive Analysis Method for Protein Kinase Activities Using Surface Plasmon Resonance” K. Inamori, M. Kyo, K. Tanizawa, S. Kuroda, K. Tatematsu, Y. Katayama, Y. Kita: JP2003-080645. “Screening Method for Receptor Ligands” A. Kondo, S. Kuroda, A. Ueda, J. Ishii, H. Fukuda, K. Tatematsu: JP2003-417482. “Therapeutic Agents for Treatments of Cardiac Hypertrophy and Related Heart Disease” K. Tanizawa, M. Iwata, S. Kuroda: USP60/496935. International Conferences Conformation of Substrate Schiff-Base in the Active Site of Copper Amine Oxidase Defines the Stereospecificity of Proton Abstraction from Substrate (Poster), *T. Okajima, Y.-C. Chiu, M. Uchida, Y. Yamamoto, H. Hayashi, and K. Tanizawa, Protein Society, Boston, MA, USA, July 26–30, 2003.

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Stereospecificity of α-Proton Abstraction by Copper Amine Oxidase Is Defined by Conformation of Substrate Schiff-Base Intermediate Formed in the Active Site (Invited), Y.-C. Chiu, T. Okajima, S. Kuroda, and *K. Tanizawa, 8th International Congress on Amino Acids and Proteins, Rome, Italy, September 5–9, 2003. Mechanistic Studies of Topaquinone-dependent Copper Amine Oxidase (Invited), *K. Tanizawa, Dutch-Japanese Workshop on Biocatalysis, Noordwijk, Netherlands, September 24–27, 2003. Mechanism of Reductive Half-reaction of Bacterial Copper/TPQ-dependent Amine Oxidase (Invited), *K. Tanizawa, Y.-C. Chiu, T. Murakawa, and T. Okajima, Gordon Research Conferences on Protein Derived Cofactors, Radicals and Quinones, Ventura, CA, USA, January 11–16, 2004. Involvement of a Hypothetical [Fe-S]-binding Protein in the Biogenesis of Quinohemoprotein Amine Dehydrogenase (Poster), *K. Ono, T. Okajima, and K. Tanizawa, Gordon Research Conferences on Protein Derived Cofactors, Radicals and Quinones, Ventura, CA, USA, January 11–16, 2004. Mechanism of Reductive Half-reaction of Bacterial Copper/TPQ-dependent Amine Oxidase (Poster), *T. Murakawa, Y.-C. Chiu, T. Okajima, and K. Tanizawa, Gordon Research Conferences on Protein Derived Cofactors, Radicals and Quinones, Ventura, CA, USA, January 11–16, 2004. Publications in Domestic Meetings Japanese Biochemical Society 7 papers Japanese Society for Molecular Biology 2 papers Japan Society for Bioscience, Biotechnology, and Agrochemistry 1 papers Japanese Protein Science Society 1 papers Bimonthly Meeting of Vitamin B Committee 2 papers Academic Degrees Master Degree of Science J. Ikuta Structural and Functional Characterization of FEZ2 protein, a homolog

of an axonal guidance protein FEZ1 Doctor Degree of Science T. Fujita Molecular and Cell Biological Studies on Fasciculation and Elongation

Proteins Zeta (FEZ) Sponsorship

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Grant-in-Aid for Scientific Research on Priority Areas (B) (2) K. Tanizawa Molecular Design of Composite Catalyst Containing

Quinone-type Built-in Cofactors and Metal Ions. ¥8,100,000

Grant-in-Aid for Scientific Research on Priority Areas (C) (2) S. Kuroda Development of New Pinpoint Gene Delivery System

Using Nanoparticles Fused with Bio-recognition Molecule.

¥5,900,000

Grant-in-Aid for Scientific Research (B) (2) S. Kuroda Analysis of Signal Transduction Mechanism Involving

Two NELL Proteins for the Differentiation of Neural Crest-Derived Cells.

¥10,300,000

Grant-in-Aid for Scientific Research for Young Scientist Andrés D. Maturana

Role of Molecular Complex Containing PDZ-3LIM Protein ENH1 in Cardiac Hypertrophy Signaling Cascade.

¥1,200,000

K. Suzuki Stabilization of Lipid Bilayer and Purification of Membrane Protein Using Surface Microarchitecture.

¥1,100,000

Grant-in-Aid for Scientific Research (21st Century COE) K. Tanizawa Development of Drug Delivery System with

Bionanoparticles and Molecular Design of Functional Proteins Based on Structures

¥13,000,000

T. Fujita Analysis of Mitochondrial Transport Mechanism Involving Axonal Guidance-Related Protein FEZ1 in Neuronal Cells

¥400,000

N. Yoshimoto Development of Targeted Removal System for Intracellular Disease-Related Protein with Bio-missile

¥800,000

K. Ono Analysis of Nano-scale Regulatory Mechanism by Radical SAM Protein

¥400,000

T. Murakawa Nanostructure-Based Catalytic Mechanism of Topaquinone-Containing Copper Amine Oxidase

¥400,000

Cooperative Research K. Tanizawa

Osaka University COE Fund

Atom Scale Processing for the Creation of Highly Harmonized Functional Materials

¥3,000,000

Entrusted Research K. Tanizawa

Agriculture, Forestry, and Fisheries Research Council

De Novo Design, and Analysis of Structure and Function of Quinone-Containing Built-in Enzymes

¥3,554,000

K. Tanizawa Mitsubishi Electric Company, Ltd.

Analysis of Intracellular Signal Networks for Industrial

¥4,200,000

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(NEDO) Application of Genomics K. Tanizawa Japan Science and

Technology Agency (CREST)

Creation of Functional Materials/ System that Utilize Nano Biotechnology for Realizing a Noninvasive Medical Treatment System: Novel Cell-selective Gene Delivery System Using Intracellular Signal-responsive Molecular System

¥1,157,000

S. Kuroda

Ministry of Education, Culture, Sports, Science, and Technology

Protein 3000 Project ¥5,000,000

S. Kuroda Osaka Science and Technology Center (Ministry of Economy, Trade and Technology)

Development of Proteome-based High Throughput Screening System Using Combinatorial Biochemistry.

¥2,100,000

S. Kuroda Japan Science and Technology Agency (Innovation Plaza Osaka)

Development of Hollow Nanoparticles for Pinpoint Gene/Protein/Drug Delivery to Various Tissues and Cells in Animals.

¥0

Other Research Funds K. Tanizawa Vitamin B Committee Research on Built-in Cofactors ¥350,000

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Department of Molecular Cell Biology Professor: Masamitsu FUTAI Associate Professor: Yoh WADA Research Associate: Ge-Hong SUN-WADA Post Doctoral Fellows: Takao TOYOMURA, Kazuaki NISHIO Graduate Students: Hideaki MURAKAMI, Yuya KUNISADA,

Yoshiaki NICYU, Hiroyuki HOSOKAWA, Shigeru KAGATA

Under Graduate Students: Hiroyuki SHIMIZU, Kei INOUE Supporting Staffs: Mikako NAKASHIMA, Sachiko

SHIMAMURA Researchers: Yoshiko MURATA, Minako AOYAMA Research Supporting Staff: Akinori FUKUYAMA Outlines Our research is focusing on solving basic questions in biological membranes including: (1) The mechanism of energy coupling between ATP synthesis/hydrolysis and ion transport: (2) Biogenesis of organelles with varying acidic pH: (3) Sensing mechanism of ions and protons. We have shown that mechanism of F-ATPase (ATP synthase) includes subunit rotation in planar membranes: γεc10 complex, rotor: α3β3δab2 complex, stator. The rotor and stator are interchangeable and energy conversion between chemical reaction (ATP hydrolysis) and rotation are very efficient, almost 100 %. We have also demonstrated that vacuolar-type proton-ATPase (V-ATPase, proton pump found in membranes of acidic organelles) also carries out rotational catalysis. The exciting finding of this year is that V-ATPase subunits have isoforms including those found in specific cells: the subunit C contained isoform C2 specifically expressed in type II alveolar cells. Subunit a has four isoforms found in endomembranes and plasma membrane. In addition, the tissue-specific isoforms assembled preferentially to form tissue-specific enzymes. V-ATPase with a3 isoform is localized to lysosomes of the progenitor, whereas the same enzyme is found in the plasma membranes in mature osteoclasts. This result suggests that the plasma membrane is formed from lysosomal membranes. Current Research Projects 1. Energy Coupling in Rotational Catalysis by F-type H+ ATP Synthase. ATP synthase FoF1 (α3β3δab2γεc10) couples an electrochemical proton gradient and a chemical reaction through the rotation of its subunit assembly. Thus, this enzyme can be considered as a nano-scale biological motor. We established that the γεc10 and α3β3δab2 complexes are mechanical units of the membrane-embedded enzyme involved in rotational catalysis.

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2.

3.

4.

Diversity of Subunit Structure of Vacuole type H+ ATPase The vacuolar ATPase (V-ATPase) is located to the endomembrane compartments along with secretory and vacuolar systems, and acidifies lumen of organelles by transporting protons across the membranes. It is also localized to the plasma membrane of differentiated cells including osteoclast or renal and bladder epithelia cells and acidifies the extracellular space. We have identified four subunit a isoforms (a1, a2, a3, and a4) of V-ATPase in mouse. a1 is predominantly localized to secretory vesicles, and a2 is associated with Golgi, whereas a3 is a late endosomal/lysosomal resident. a4 is specifically expressed in renal intercalated cells and localized to the plasma membranes.

Subunit Structure of V-ATPase: Isoforms of Extrinsic Membrane Subunits. As well as the Vo, the membrane peripheral V1 sector also exhibits structural divergence. V-ATPase with a novel E1 isoform is expressed specifically in the acrosomal membrane of sperm with a2 isoform, whereas the ubiquitously expressed E2 is the component in other tissues. Brain expresses a unique G2 isoforms as well as a ubiquitous isoform G1. Thus, the divergent physiological functions of V-ATPase in various acidic compartments are established, in part, by utilizing distinctive subunit isoforms.

Biogenesis of Organelles with Acidic pH. Mammals contain various cells differentiated in both morphology and function, which play vital roles in tissue-specific functions. Late endosome/lysosome and lysosomal-related organelles are involved in these specialized functions including antigen presentation, bone remodeling and hormone regulation. The luminal acidification of these organelles is closely correlated with their functions. We have identified multiple molecules that may function as machinery for biogenesis of late endosomes and lysosomes. The physiological role of each molecule is examined using its gene knockout mice. Publications Original Papers Subunit Rotation of Vacuolar-Type Proton Pumping ATPase: Relative Rotation of the G as to c Subunit, T. Hirata, A. Iwamoto-Kihara, G.-H. Sun-Wada, T. Okajima, Y. Wada, and M. Futai: J. Biol. Chem., 278 (2003) 23714-23719. Detection of Protein-Protein Interactions on SiO2/Si Surfaces by Spectroscopic Ellipsometry, S. Kodera, T. Okajima, H. Iwabuki, D. Kitaguchi, S. Kuroda, T. Yoshinobu, K. Tanizawa, M. Futai, and H. Iwasaki: Anal. Biochem., 321 (2003) 65-70. Specific Recognition of Leishmania major Poly- β-galactosyl Epitopes by Galectin-9: Possible Implication of Galectin-9 in Interaction between L. major and Host Cells, I. Pelletier, T. Hashidate, T. Urashima, N. Nishi, T. Nakamura, M. Futai, Y. Arata, K. Kasai, M. Hirashima, J. Hirabayashi, and S. Sato: J. Biol. Chem., 278 (2003) 22223-22230.

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Revised Nomenclature for Mammalian Vacuolar-type H+-ATPase Subunit Genes, A.N. Smith, R.C. Lovering, M. Futai, J. Takeda, D. Brown, F.E. Karet: Mol. Cell, 12 (2003) 801-803. Diversity of Mouse Proton-Translocating ATPase: Presence of Multiple Isoforms of the C, d and G Subunits, G.-H. Sun-Wada, T. Yoshimizu, Y. Imai-Senga, Y. Wada, and M. Futai: Gene, 302 (2003) 147-153. Mouse Proton Pump ATPase C Subunit Isoforms (C2-a and C2-b) Specifically Expressed in Kidney and Lung, Sun-Wada, G.-H., Y. Murata, M. Namba, A. Yamamoto, Y. Wada, and M. Futai: J. Biol. Chem., 278 (2003) 44843-44851. Involvement of Syntaxin 7 in Human Gastric Epithelial Cell Vacuolation Induced by the Helicobacter pylori-Produced Cytotoxin VacA, J. Suzuki, H. Ohnishi, A. Wada, T. Hirayama, H. Ohno, N. Ueda, H. Yasuda, T. Iiri, Y. Wada, M. Futai, and H. Mashima: J. Biol. Chem., 278 (2003) 25585-25590. From Lysosomes to Plasma Membrane: Localization of Vacuolar Type H+-ATPase with the a3 Isoform during Osteoclast Differentiation, T. Toyomura, Y. Murata, A. Yamamoto, T. Oka, G.-H. Sun-Wada, Y. Wada, and M. Futai: J. Biol. Chem., 278 (2003) 22023-22030. Review Papers Lysosome and Lysosome-Related Organelles Responsible for Specialized Functions in Higher Organisms, G.-H. Sun-Wada, Y. Wada, and M. Futai: Cell Struct. Func., 28 (2003) 455-463. Vacuolar H+ Pumping ATPases in Luminal Acidic Organelles and Extracellular Compartments: Common Rotational Mechanism and Diverse Physiological Roles, G.-H. Sun-Wada, Y. Wada, and M. Futai: J. Bioenerg. Biomembr., 35 (2003) 347-358. Lysosome-Related Organelles Responsible for Specialized Functions in Higher Organisms, G.-H. Sun-Wada, Y. Wada, and M. Futai: Experimental Medicine, 21 (2003) 162-167. Books Methods in Post Genome Protein Science, G.-H. Sun-Wada, M. Maeda, and M. Futai: Tokyo Kagakudojin, (2003) 139-155. International Conferences Subunit Isoforms of Proton Pump V-ATPase for Diverse Endomembrane Organelles, *G.-H. Sun-Wada, Y. Wada, and M. Futai, Experimental Biology 2003, San Diego, CA, USA, Apr. 19-24, 2003. Subunit Rotation of ATP Synthase Embedded in Membranes: α or β Subunit Rotation Relative to the c Subunit Ring (invited), *M. Futai, K. Nishio, A. Iwamoto-Kihara, A. Yamamoto, and Y. Wada, Experimental Biology 2003, San Diego, CA, USA, Apr. 19-24,

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2003. a2-Subunit of V-ATPase Localizes in Endosomes and Interacts with ARNO in Kidney Proximal Tubule Epithelial Cells, *A. Hurtado-Lorenzo, J. El-Annan, S. Bechoua, M. Futai, S. Bourgoin, J.E. Casanova, D. Brown, D.A. Ausiello, and V. Marshansky, American Society of Nephrology Renal Week, San Diego, CA, USA, Nov. 12-17, 2003. V-ATPase: Rotational Catalysis and Diverse Isoforms (invited), *M. Futai, Gordon Research Conference on Molecular & Cellular Bioenergetics, Meriden, NH, USA, Jun. 22-27, 2003. Vo and V1 Subunit Isoforms of Mouse Vacuolar Proton ATPase V1Vo, *G.-H. Sun-Wada, T. Yoshimizu, Y. Murata, T. Oka, Y. Wada, and M. Futai, Gordon Research Conference on Molecular & Cellular Bioenergetics, Meriden, NH, USA, Jun. 22-27, 2003. Rotation Mechanisms in the ATP synthase (invited), *M. Futai, FASEB Conference in transport ATPase, Vermont, NH, USA, Jul. 12-17, 2003. Subunit Isoforms of Proton Pump V-ATPase for Diverse Endomembrane Organelles, *Y. Wada. FASEB Conference in Transport ATPase, Vermont, NH, USA, Jul. 12-17, 2003. Subunit Rotation of ATP Synthase in Membranes, *M. Futai (invited) The Human Proteome Organization (HUPO) 2nd Annual and the International Union of Biochemistry and Molecular Biology (IUBMB) XIX Joint World Congress, Montreal, Canada, Oct. 8-11, 2003. Mouse Proton Pump ATPase C Subunit Isoforms Specifically Expressed in Kidney and Lung, * G.-H. Sun-Wada, Y. Wada, and M. Futai, The American Society for Cell Biology, 43nd Annual Meeting, San Francisco, CA, USA, Dec. 14-17, 2003. Contributions to International Journals M. Futai Arch. Biochem. Biophys. (USA, Editorial Board) M. Futai J. Bioener. Biomembr. (USA, Editorial Board) M. Futai J. Biol. Chem. (USA, Editorial Board) M. Futai Biological Chemistry (USA, Editorial Board) Publications in Domestic Meetings Japanese Biochemical Society Japanese Molecular Biology Society Japan Society for Cell Biology Japanese Bioenergetics Group

5 papers 3 papers 1 paper 1 paper

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Academic Degrees Awarded Master Degree of Engineering Y. Kunisada Establishment of a novel method for construction of

knock-in/knock-out vectors Sponsorship Grants-in-Aid for Scientific Research on Priority Areas Y. Wada Membrane Dynamics during Mammalian Development ¥23,800,000 M. Futai Mechanism of Biological Nanomotors ¥17,900,000

Grants-in-Aid for Scientific Research M. Futai ATP Synthase: Mechanism with Subunit Rotation ¥11,100,000 G.-H Sun-Wada Genetic Diseases and V-ATPase ¥8,580,000 T. Toyomura Studies on V-ATPase a Subunit Isoforms ¥1,200,000 K. Nishio Rotation of F-ATPase ¥1,100,000 Grants-in-Aid for Exploratory Scientific Research

Y. Wada Highly Efficient Gene Manipulation by Homologous Recombination in E. coli. ¥2,000,000

Entrusted Research M. Futai Japan Science and Technology Corporation

(CREST) Function and Biogenesis of Acidic Organelles

¥2,860,000

Y. Wada Applied Enzyme Corporation ¥1,000,000 Y. Wada Noda Foundation of Scientific Research ¥2,000,000 G.-H Sun-Wada Hayashi Foundation of Scientific Research of

Women ¥150,000

G.-H Sun-Wada Foundation of Scientific and Medical Research ¥500,000 G.-H Sun-Wada Nagase Foundation of Scientific Research ¥300,000 M. Futai Japan Science and Technology Corporation

(CREST) Function and Biogenesis of Acidic Organelles

¥27,700,000

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Department of Cell Membrane Biology Professor: Akihito YAMAGUCHI Research Associates: Satoshi MURAKAMI, Takahiro HIRATA Post Doctoral Fellows: Ryosuke NAKASHIMA, Takashi MATSUMOTO Yoshiyuki KUBO Graduate Students: Norihisa TAMURA, Nobuyoshi KOBAYASHI, Hidetada

HIRAKAWA, Yuko OKAWA, Keisuke SAITO, Sayaka SEKIYA, Junko YAMADA, Fumiaki ISHIBASHI, Yoshihiko INAZUMI, Naoki KOBAYASHI, Satofumi HASHIMOTO

Research Students: Takeshi MASAKI, Shinya YAMAMOTO Support Staff: Mari NISHIDA, Chikako MURAKAMI, Kyoko

TAMURA, Masako TOTSUKA, Chiemi TAKENAKA, Ayumi IWATA

Outlines Xenobiotic extruding pumps have recently been known to be widely distributed in living organisms from mammalian to bacteria as a host-defence mechanism in cellular level. These pumps not only confer multidrug resistance of cancer cells and pathogenic bacteria but also cause hereditary diseases through the mutation. The purposes of our laboratory are to elucidate the molecular structures and the molecular mechanisms of these xenobiotic exporters and the roles of these exporters in cell functions. In addition, the exporters having xenobiotic exporter-like molecular structures are identified in brain and platelets in order to elucidate the possible roles of exporters in intercellular signal transduction. We previously reported the high resolution crystalline structure of the xenobiotic exporter AcrB, that is a trimer having jellyfish like shape. The structure well explains TolC-docking, dual entrance model and possible proton penetrating pathways. This is the first case for the crystal structure determination of multidrug transporters as well as proton coupling one and gives a structural basis for understanding the membrane transport mechanism. This structural information enable us to be in outstanding position to elucidate the molecular mechanism of transport process combining with molecular biological information such as mutation studies, which is now on-going. Current Research Programs 1. Crystallographic and protein engineering analysis of xenobiotic exporters. We have succeeded in determining the first crystalline structure of bacterial multidrug efflux transporter AcrB published in Nature 407, 971-977 (2002). We are trying to solve the structure of co-crystals of AcrB and its substrates. We are also performing the mutagenesis studies based on the crystal structure. AcrB trimer has a central pore in the periplasmic head piece. Cysteine-scanning mutagenesis studies on the pore helix revealed the importance of the inner wall of the pore for the substrate translocation. In addition, the site-directed mutagenesis of the conserved charged

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residues in AcrB revealed that the essential charged residues form ion pairs in the transmembrane region probably making proton pathway. We are also performing random approach and isolated about 80 mutants form regions such as TolC-docking domain, pore domain and transmembrane regions and characterized the amino acid residues in each domain. Furthermore, we could successfully detect the spontaneous disulfide cross-linking between Cys-introduced AcrB and TolC. This clearly reveals AcrB interact directly with TolC. We hope that these studies help understanding how the structure acts as a drug exporter. 2. Studies on the regulatory networks of xenobiotic exporters in E. coli.

We previously constructed the set of E. coli 37 putative drug exporter gene library. Among them, 20 genes actually encode drug exporters. Although E. coli has intrinsic 20 drug exporter genes, most of them are hardly expressed under the normal growth conditions. However, the signals that induce the expression of these genes are unknown. We found that indole and AI-2 induces some drug exporter genes via both two-component systems and two-component system-independent pathway. We also found that N-acetyl glucosamine induced a MdtEF drug transporter. In addition, we found that some nucleiod proteins such as H-NS or Hfq control the expression of drug exporter genes.

3. Identification of novel exporter genes in brain and platelets, database mining and cloning of eukaryotic RND-type transporters to study the physiological roles of these transporters using cultured cells and knockout mice. We constructed the knockout mice of a novel ABCA-type gene, ABCA5, which is mainly expressed in brain and testis. The knockout mice die at about 10-12 weeks after birth by dilated cardiomyopathy. We are now studying the cause of the phenotype and the biochemical characterization of the ABCA5 protein using specific monoclonal antibody. In addition, we found that sphingosine-1-phosphate is exported from platelet probably by ABC-type transporters. We are now making an effort to identify the transporter. We also found and cloned the novel three mouse RND-type transporters containing Sterol-sensing domains (SSD) and their expressions in various tissues were determined by RT-PCR analysis.

Publications Original Papers Comprehensive Studies of Drug Resistance Mediated by Overexpression of Response Regulators of Two-Component Signal Transduction Systems in Escherichia coli, H. Hirakawa, K. Nishino, T. Hirata, and A. Yamaguchi : J. Bacteriol., 185, (2003) 1851-1856. Global Analysis of Genes Regulated by EvgA of the Two-Component Regulatory System in Escherichia coli, K. Nishino, Y. Inazumi, and A. Yamaguchi : J. Bacteriol., 185, (2003) 2667-2672. Cloning of Rat ABCA7 and Its Preferential Expression in Platelets, M. Sasaki, A. Shoji,

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Y. Kubo, S. Nada, and A. Yamaguchi: Biochem. Biophys. Res. Commun., 304, (2003) 777-782. Membrane Topology of ABC-type Macrolide Antibiotic Exporter MacB in Escherichia coli, N. Kobayashi, K. Nishino, T. Hirata, and A. Yamaguchi: FEBS Lett., 546, (2003) 241-246. Roles of TolC-dependent Mmultidrug Transporters of Escherichia coli in Rresistance to β-lactams, K. Nishino, J. Yamada, H. Hirakawa, T. Hirata, and A. Yamaguchi: Antimicrob. Agents Chemother., 47, (2003) 3030-3033. β-lactam Resistance Modulated by the Overexpression of Response Regulators of Two-Component Signal Transduction Systems in Escherichia coli, H. Hirakawa, K. Nishino, J. Yamada, T. Hirata, and A. Yamaguchi: J. Antimicrob. Chemother., 52, (2003) 576-582. Crystal Structure of Bacterial Multidrug Efflux Transporter AcrB, A. Yamaguchi, S. Murakami, R. Nakashima and E. Yamashita: FASEB J. 17, (2003) A1185( part2) suppl. S. Mechanisms of Drug/H+ Antiport: Complete Cysteine-Scanning Mutagenesis and the Protein Engineering Approach, N. Tamura, S. Konishi, and A. Yamaguchi: Curr. Opin. Chem. Biol., 7 (2003) 570-579. Multidrug-Exporting Secondary Transporters, S. Murakami, and A. Yamaguchi: Curr. Opin. Struct. Biol., 13 (2003) 443-452.

Review papers Crystal Structure of Bacterial Multidrug Efflux Transporter AcrB: S. Murakami and A. Yamaguchi, PNE (Tanpakusitu Kakusan Kouso) 48:26-32 (2003) Review, Japanese

[Crystal Structure of Bacterial Multi-Drug Efflux Transporter AcrB.] S. Murakami, R. Nakashima, E. Yamashita and A. Yamaguchi, (Review) J. Crystallographic Soc. Jpn 45, 45:256-261 (2003) [Crystal Structure of Bacterial Multi-Drug Efflux Transporter AcrB.] S. Murakami, R. Nakashima, E. Yamashita and A. Yamaguchi, (Review) Houshakou 16, 204 (2003) [Crystallographic Analysis of Multi-Drug Efflux Transporter AcrB.]. S. Murakami, R. Nakashima, E. Yamashita and A. Yamaguchi, (Review) Seibutsu-Kogaku 81, 155-160 (2003) Whole Genome Approach of Drug Exporter Genes and Their Regulatory Networks: K. Nishino, Nippon Saikingaku Zasshi, 58 (2003)581-594. the Review for the Prof.

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Kuroya’s Award, Japanese International Conferences Crystal Structure of Bacterial Multidrug Efflux Transporter AcrB (Invited), *A. Yamaguchi, S. Murakami, R. Nakashima and E. Yamashita ASBMB Annual Meeting 2003 San Diego Convention Center, USA, April 12-16, 2003. Comprehensive Analysis of Two-component Signal Transduction System Induced Multidrug Resistance in Escherichia coli. (Poster) *H. Hirakawa, K. Nishino, J. Yamada, Y. Inazumi, T. Hirata, A. Yamaguchi, American Society for Microbiology 103rd General Meeting, Wshington DC Convention Center, USA , May 18-22, 2003. Histone-like Protein H-NS Controls the Expression of AcrEF and YhiUV Multidrug Transporters in Escherichia coli. (Poster) *K. Nishino, T. Hirata, T. Honda and A. Yamaguchi, American Society for Microbiology 103rd General Meeting, Wshington DC Convention Center, USA, May 18-22, 2003. Identification of Functional Amino Acids in AcrB Multidrug Transporter of Escherichia coli. (Poster) A. Saito, *T. Hirata, S. Murakami and A. Yamaguchi, American Society for Microbiology 103rd General Meeting, Wshington DC Convention Center, USA May 18-22, 2003. Crystal Structure of Bacterial Multidrug Efflux Transporter AcrB (Invited), *S. Murakami, R. Nakashima, T. Matsumoto, E. Yamashita and A. Yamaguchi: International Symposium on Diffraction Structural Biology, Tsukuba, Japan, May 28-31, 2003. Crystal Structure of Multidrug Efflux Transporter AcrB and Its Functional Implications (Invited) *A. Yamaguchi, S. Murakami, R. Nakashima and E. Yamashita: Gordon Research Conferences (Molecular & Cellular Bioenergetics) Kimball Union Academy, USA, June 22-29, 2003. X-ray Crystallographic Analysis of Multidrug Efflux Transporter AcrB (Invited): *S. Murakami, RIKEN/BBSRC Joint Symposium, Japan-UK Membrane Protein Structure Biology -Towards high-throughput membrane protein crystallography and related technology- SPring-8 Public Relation Hall, Harima, Himeji, Japan, Sep. 11, 2003. Structure and Function of the Xenobiotic Efflux Transporter, *A. Yamaguchi: International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), ISIR, Osaka Univ, Osaka, Japan, Dec. 8-9, 2003. Research Developments in the Nano-Bioscience Group, *A. Yamaguchi, M. Futai, K. Tanizawa, H. Sasai, T. Majima, H. Iwasaki and N. Kato: Second 21st Century COE

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"Towards Creating New Industries Based on Inter-Nanoscience", 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Icho-Kaikan, Osaka Univ. Osaka, Japan, Jan. 13-14, 2004. Comprehensive Analysis of Two-component Signal Transduction System Induced Multidrug Resistance in Escherichia coli, (Poster) *H. Hirakawa, J. Yamada, Y. Inazumi, T. Masaki, T. Hirata and A. Yamaguchi: Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience", 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Icho-Kaikan, Osaka Univ. Osaka, Japan, Jan. 13-14, 2004. Structure and Function of Multi-drug Efflux Transporter (Poster), *S. Murakami and A. Yamaguchi: Second 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience", 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science - Perspectives in Nanoscience -, Icho-Kaikan, Osaka Univ. Osaka, Japan, Jan. 13-14, 2004. Structure and Function of Multi-drug efflux transporter (Invited), *S. Murakami and A. Yamaguchi, ISCNN'04: International Symposium on the Creation of Novel Nanomaterials, Icho-Kaikan, Osaka Univ. Osaka, Japan, Jan. 20-22, 2004. Publications in Domestic Meetings

Pharmaceutical Society of Japan 7 papers Japanese Society for Bacteriology 6 papers Japanese Biochemical Society 10 papers Membrane-Drug Interaction Symposium 3 papers Japanese Biochemical Society (Kinki-branch) 5 papers Symposium on Microbial Drug Resistance 1 paper Japanese Society for Chemotherapy (Higashi-Nippon branch) 1 paper Japanese Bioenergetics Group 3 papers The Molecular Biology Society of Japan 4 papers Academic Degrees Master’s Degree of Pharmaceutical Sciences Yuko Ookawa Functional Analysis of E.coli Major Xenobiotics Exporters, AcrB

by the Random Mutagenesis. Keisuke Saito Cloning and Investigation of a Novel ABCG Subfamily

Transporter. Sayaka Sekiya Analysis of Knockout Mice for ABCA5, a Novel ABCA subfamily

Transporter. Junko Yamada β-lactam Resistance Mediated by Xenobiotic Exporters and the

Regulation Mechanism of Efflux Transporters in Escherichia coli.

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Bachelor's Degree of Pharmaceutical Sciences Takeshi Masaki Screening of Regulators that Repress acrD and mdtABC,

Xenobiotic Exporter Genes in Escherichia coli. Shinya Yamamoto Topology Analysis of EmrB, a Xenobiotic Exporter of Escherichia

coli. Sponsorship Grant-in-Aid for Scientific Research on the Priority Area (B) A. Yamaguchi Studies on the Nano-structure and Transport Mechanism of

Antiport-type Efflux Transporter for Organic Compounds. ¥29,700,000

Grant-in-Aid for Scientific Research on the Foundation Area (S) A. Yamaguchi Post-genome Analysis of Bacterial Xenobiotic Exporter

and Studies on the Novel Resistance Mechanism. ¥20,000,000

Grant-in-Aid for 21st Century COE program A. Yamaguchi Towards Creating New Industries Based on Inter-

Nanoscience. ¥6,941,000

S. Murakami Development of Novel Artificial Enzyme ¥1,000,000 N. Tamura Formation of the Complex between AcrB and TolC in

Escherichia coli ¥400,000

N. Kobayashi Identification of Sphingosine-1-phosphate Exporter in Platelet

¥400,000

H. Hirakawa Studies on the Regulatory Networks of Xenobiotic Exporter Nanomachine Induced by the Bacterial Signal Transduction

¥400,000

Grant-in-Aid for JSPS Research Fellows R. Nakashima X-ray Structural Analysis of Xenobiotic Exporter. ¥1,200,000

N. Tamura Principles for Topology Formation of Polytopic Membrane Proteins.

¥1,000,000

N. Kobayashi Structure and Functional Analysis of the first ABC-type Drug-Exporter of Gram-nagative bacteria, MacB

¥900,000

Entrusted Research T. Hirata AstraZeneca Co. Ltd. Establishment of the high throughput

AcrB assay system and binding assay system to find roles of functional amino acids for understanding the molecular efflux mechanism

¥2,000,000

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Other Research Fund A. Yamaguchi Japan Science and

Technology Corporation (CREST)

Investigation of the Structure and Function for Xenobiotics Transporters and Clarification of Multidrug Resistance Mechanism

¥43,200,000

A. Yamaguchi Japan Science and Technology Corporation (CREST), entrusted

As above ¥4,550,000

S. Murakami Japan Science and Technology Corporation (Sakigake 21)

Structural Analysis of Drug Recognition Mechanism in Multidrug Efflux Transporter for Drug Resistance.

¥9,480,000

S. Murakami Japan Science and Technology Corporation (Sakigake 21), entrusted

As above ¥650,000

T. Hirata National Agriculture and Bio-oriented Research Organization, entrusted

Molecular Mechanism and Regulation of Acquisition of Drug Resistance in Escherichia coli

¥3,000,000

(Other Allocations) A. Yamaguchi COE fund Atomic Scale Processing for

the Creation of Highly Harmonised Functional Materials.

¥3,000,000

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Division of Quantum Beam Science & Technology Outline The quantum beam is the general term for all kinds of radiation beams producing quantum mechanical effects on materials. It includes photon beams and charged particle beams such as lasers, X-rays, synchrotron radiation, γ-rays and free electron lasers, electrons, positrons, muons and ions, as well as neutron beams. Quantum beam science has developed from radiation science and its research fields are classified into two groups. One of them is study on production, control and measurement of new high-brightness and high quality quantum beams, which are remarkably developing recently. The other is study on processes induced by quantum beams in materials, as well as on applications to materials science based on accurate understanding of these phenomena induced by a quantum beam.

The division of Quantum Beam Science and Technology is composed of the department of Accelerator Science and the department of Beam Materials Science. In the department of Accelerator Science, studies are conducted on accelerators, which are main apparatuses for producing quantum beams, and on production, control and measurement of quantum beams using accelerators. In the department of Beam Materials Science, basic studies are conducted to investigate phenomena induced by quantum beams and to apply them to materials science; that is, production and application of new materials such as functional materials and materials working under extreme conditions. Both departments closely work together with different points of view; generation of new quantum beams and applications of them to materials science. This division also cooperates with the Radiation Laboratory, attached to the Institute, in order to promote advanced studies conducted at a university with a different point of view from that of national laboratories. Furthermore we plan to actively promote researches to develop and use high-performance accelerators suitable for producing new kinds of high-brilliant and high-quality beams and for applying to materials science, which are being developed or under construction in this country as well as abroad. Achievements • Remodeling of the L-band linac in progress to improve stability and reproducibility

of operation drastically. • Measurement of angular distributions of Self-Amplified Spontaneous Emission

(SASE) for the fundamental peak and higher harmonic peaks due to non-linear harmonic generation.

• Development of a new type of wiggler with strong focusing force, called the edge focusing wiggler, for SASE and FEL

• Study on stability of the L-band linac with the autoregressive model • Improvement of performance of the Siam Photon Source in Thailand and design

study of the first undulator for it.

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194

• First comprehensive and quantitative studies on charge carriers and reactive intermediates of conjugated polymer molecules by pulse radiaolysis technique.

• Drastic improvements in the S/N ratio of the subpico-, pico-, and nano-second pulse radiolysis system.

• Success in analysis of reaction mechanisms of high sensitive resists for nanoelectronics.

• Formation of size-controlled nano-wires along particle trajectories in polymeric materials.

• Pulse radiolysis studies on biological systems including DNA, active oxygen, and NO

• Application of slow positron beams to polymer science and technology as the probes for nano-sized space in the materials.

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Activity of Facilities

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Department of Accelerator Science Professor: Goro ISOYAMA Associate Professor: Ryukou KATO Research Associates: Toshiji IKEDA, Shigeru KASHIWAGI Graduate Students: Tetsuya IGO, Akihito MIHARA, Chikara OKAMOTO, Takanori NODA Research Student: Kenji KOBAYASHI Outlines Particle accelerators are widely used from basic science to industrial applications. In this department, we conduct research on accelerators and quantum beams such as a free electron laser (FEL). Although accelerators are artificial things, fundamental aspects of physics such as non-linearity and the collective effect become apparent when extreme performance is pursued. Because new kinds of quantum beams extend the world we can see with, they are expected to be used in a large variety of fields extending from basic research to applications. To put it concretely, we conduct researches on production of a highly brilliant electron beam with a linear accelerator and related beam dynamics, development of an infrared FEL for user experiments and SASE (Self-Amplified Spontaneous Emission) in the infrared region. In addition to these, we collaborate with the National Synchrotron Research Center (NSRC) in Thailand for development of a synchrotron radiation source. Current Research Programs

1. Remodeling of the L-band linac All instruments ordered for remodeling of the linac had been delivered by the end of

March 2003 and their performance was tested at site in April. All the old wirings for control, input, and output were taken away in May and a computer control system was newly constructed in Jun and July. The initial operational test of the accelerator system was conducted and software bugs was got out of the control system in August and September. The earnest operational test began in October. The database for logged data by the control system was available from December and it has been used for finding errors of instruments.

One of the most crucial instruments newly made is the klystron modulator for the klystron. The pulse-to-pulse fluctuation of the output pulse voltage is reduced to less than the specified value of 0.1 % by changing the monitor circuit for charging voltage. The specification for the pulse-top flatness of 0.1 % is fulfilled, for the moment, in the latter 5.5 µs part of the pulse out of the total length of 8 µs. A serious problem we had is discharge or spark in the wave-guide system for high power RF. Sparks were found in two 90° twist wave guides, a power divider in the pre-buncher line and a phase shifter in the buncher line. The twist wave-guides and the power divider in the pre-buncher were modified, so that sparks ceased. The phase shifter will be replaced with a new one. The last remaining problem is small and random power fluctuations of the RF power observed in the output of the klystron. We are now clearing up the cause.

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2. Development of a High Performance Wiggler for SASE We are developing a new type of wiggler to be used for Self-Amplified Spontaneous Emission (SASE), which squeezes the electron beam small so that gain of SASE is enhanced. It is a Halbach type wiggler with an edge angle for focusing and named the edge-focus wiggler. We have made a model wiggler with 5 periods and measured the magnetic field to evaluate its performance. The main parameters of the wiggler are the period length of 6 cm and the maximum magnetic field of 0.43 T at the magnet gap of 30 mm, which are same as those of the wiggler presently used for development of FEL and SASE in the far-infrared region. Since the natural focusing force in the vertical direction is strong in the energy region 10-20 MeV, the edge angle is chosen as 2°, which gives simultaneous and equal focusing in the horizontal and the vertical directions by means of the week focusing scheme. We have also proposed a new method to make a wiggler with small magnetic errors without adjustment, which we call the ideal wiggler, by automatic cancellation of magnitude and angle errors of magnetization, and applied it in the model wiggler for test. The magnetic field measurement and its analysis are in progress. 3. Development of the Synchrotron Radiation Source We are conducting study on the accelerator system for the synchrotron radiation source, called the Siam Photon Source, in collaboration with the National Synchrotron Research Center in Thailand. The maximum beam current stored in the storage ring exceeded 150 mA during the commissioning period and we were working for improvement of performance last year. The beam lifetime, however, did not become longer than expected and unforeseen affairs happened, such that the beam injection to the storage ring sometimes became impossible. We, therefore, measured betatron functions around the storage ring and found that the four-fold symmetry, which the storage ring should intrinsically have, was largely broken and that betatron functions went over 50 m at a few locations. As malfunction of the quadrupole magnets was suspected, the voltage drop through each coil of the quarupoles was measured and internal short circuits were found in many coils. Among them, short circuits with three coils were found to occur time to time and these were causes of poor reproducibility of operation and sudden beam losses. We changed four most problematic coils with temporary coils made urgently, so that the injection efficiency, the stored beam current, and the beam lifetime were considerably improved; the beam current is higher than 200 mA and the beam lifetime longer than 7 hours at 100 mA. We have decided to change all the 64 coils of 16 quadrupole magnets donated by SORTEC and we are getting ready for it now. Publications Original Papers Proposal for the Edge-Focusing Wiggler for SASE, G. Isoyama, M. Fujimoto, R. Kato, S. Yamamoto, K. Tsuchiya, Nucl. Instr. and Meth. A507 (2003) 234-237. Characteristic Measurements of Higher Harmonics Generated in the SASE-FEL, R. Kato, M. Fujimoto, T. Igo, S. Isaka, T. Onishi, S. Furukawa, S. Okuda, S. Suemine, G.

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Isoyama, Nucl. Instr. and Meth. A507 (2003) 409-412. Control System for Siam Photon Source, R. Apiwatwaja, G. Hoyes, G. Isoyama, T. Ishii and W. Pairsuwan, Nucl. Instr. Meth. B199 (2003) 517-519. International Conferences Development of the Edge-Focusing Wiggler for SASE, (Poster) *S. Kashiwagi, A. Mihara, R. Kato, G. Isoyama, S. Yamamoto and K. Tsuchiya, The 25th International Free electron Laser Conference, Tsukuba, Ibaraki, Japan, September 8-12, 2003, Mo-P-14. Stability Analysis of the RF Linac Based on an AR Model, (Poster) *R. Kato, S. Isaka, H. Sakaki, S. Kashiwagi and G. Isoyama, The 25th International Free electron Laser Conference, Tsukuba, Ibaraki, Japan, September 8-12, 2003, Tu-P-63. Upgrade of the L-Band Linac at ISIR, Osaka University for Highly Stable Operation, (Poster) *R. Kato, G. Isoyama, S. Kashiwagi, T. Yamamoto, S. Suemine, Y. Yoshida, Y. Honda, T. Kozawa, S. Seki and S. Tagawa, The 25th International Free electron Laser Conference, Tsukuba, Ibaraki, Japan, September 8-12, 2003, Tu-P-64. Measurement of the Longitudinal Wake Field in the L-band Linac at ISIR, (Poster) *T. Igo, R. Kato, S. Kashiwagi, A. Mihara, C. Okamoto, T. Noda, K. Kobayashi and G. Isoyama, The 25th International Free electron Laser Conference, Tsukuba, Ibaraki, Japan, September 8-12, 2003, Tu-P-68. Development of the Far-Infrared FEL and SASE at ISIR, Osaka University, (Poster) *G. Isoyama, R. Kato, S. Kashiwagi, S. Suemine, T. Igo, A. Mihara, C. Okamoto, T. Noda and K. Kobayashi, The 25th International Free electron Laser Conference, Tsukuba, Ibaraki, Japan, September 8-12, 2003, We-P-47. Oxidative Degradation of CR-39 Track Detector in the Surface Region during Gamma-Radiation, (Poster) *T. Yamauchi, Y. Somaki, H. Nakai, K. Oda, T. Ikeda, H. Honda and S. Tagawa, The 5th International Symposium on Ionizing Radiation and Polymers, Sainte-Adele, Quebec, Canada, September, 2003. Publications in Domestic Meetings The 28th Linear Accelerator Meeting in Japan, July 30-August 1, 2003, Tokai, Japan

7 papers

The 14th Symposium on Accelerator Science and Technology, November 11-13, 2003, KEK, Tsukuba, Japan

4 papers

The 2nd Scientific Meeting of Japanese Society of Radiation Safety and Management, December 3-5, 2003, Tsukuba, Japan

1 paper

The 17th Annual Meeting of the Japanese Society of Synchrotron Radiation 2 papers

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Research and Joint Symposium of the Synchrotron Radiation Facilities, January 8-10, 2004, Tsukuba, Japan Academic Degrees Master Degree of Science A. Mihara Research and Development of the Edge-Focus Wiggler. Sponsorship Grant-in Aid for Scientific Research on Exploratory Research G. Isoyama Development of a Novel Method for Reducing the

Electron Beam Emittance of the Synchrotron Light Source.

¥2,600,000

Cooperative Research G. Isoyama KEK Cooperative

R&D Basic study of SASE in the Long Wavelength Region for Realizing X-Ray SASE.

¥1,000,000

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Department of Beam Materials Science Professor: Seiichi TAGAWA Associate Professor: Yukio YAMAMOTO Research Associates: Kazuo KOBAYASHI, Akinori SAEKI Graduate Students: Yoshitake TERASHIMA, Satoshi TSUKUDA,

Atsuro NAKANO, Koji MIYAMOTO, Motoyuki TODO, Hiroki YAMAMOTO, Yoshiko KOIZUMI

Under Graduate Students: Yusuke DOI, Ryuhei YAMAGAMI Post Doctoral Fellow: Mutsumi TASHIRO, Anjali ACHARYA Support Staff: Minori KITO Outlines Main subjects of the present department are utilization of quantum beams for molecular science, research on mechanisms of phenomena induced by quantum beams, and analysis of microscopic structure of materials. Quantum beams mean both beams such as photons and beams inducing interactions with materials in the microscopic level of quantum mechanics. The beams cause completely different physico-chemical reactions in condensed matters from conventional chemical reactions. Features of beams are highly developed for electrons, ions, positrons, as well as photons (synchrotron radiation, γ-rays, and lasers). Current Research Programs 1. Analysis of Primary Process in Interactions between Beams and Molecular Materials Physico-chemical reactions, which occur within nano- and pico- second region, are considered to dominate followed reactions and products in molecular materials. The direct observation of reactive intermediates is carried out to elucidate the mechanisms and to control the reaction by using next measurement techniques in the program. 2. Research on Ultrafast Measurement System Using Electron and Photon Pulses The measurement system was developed to trace ultrafast phenomena by ultra short pulses of electrons and photons in the current program. Transient spectroscopy is done within 3 psec approaching to shorter time region. Excited state dynamics have been already observed for several molecular materials. 3. Electronic Structure and Physical Properties of σ-and π-Conjugated Polymers Polysilanes and polygermanes containing only silicon and germanium in the backbone are attached considerable attention because of their interesting electro-optical properties which are due to conjugated bondings in the main chain. The electronic structure of conjugated skeleton is investigated in the present program, which leads to improve the physical properties of the conjugated polymers. 4. Reaction Mechanisms in Polymeric Materials for Microelectronics

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Chemically amplified resist system is one of the most practical candidates in the future technology in semiconductor fabrication. Reaction mechanisms in the system are analyzed upon exposure to electron beams, X rays, and laser beams to design newly developed lithography technique in the present program. 5. Radiation-Induced Reactions in Aromatics Aromatics have high radiation resistance. The characteristic has been used in electron beam lithography. Especially, the radiation–induced reaction of aromatics is important to improve and understand the resist materials. Primary process of irradiated aromatics from nano- to picosecond time scale is investigated by electron beam pulse radiolysis. 6. Pulse Radiolysis Studies in Biological Systems Pulse radiolysis technique has been employed for the study of the mechanism action of the oxidation-reduction proteins, the molecular mechanisms of the oxidation stress, the molecular mechanisms of radiation-induced DNA oxidation damage. Publications Original Papers Subpicosecond Pulse Radiolysis Study of Geminate Ion Recombination in Liquid Benzene, K. Okamoto, A. Saeki, T. Kozawa, Y. Yoshida, and S. Tagawa: Chem. Lett. 32 (2003) 834. Direct Observation of Guanine Radical Cation Deprotonation in Duplex DNA Using Pulse Radiolysis, K. Kobayashi and S. Tagawa: J. Am. Chem. Soc. 125 (2003) 10214. The Interaction between Polymer Thin Films and Positron from Slow Positron Beam, K. Miyamoto, Y. Terashima, M. Tashiro, Y. Honda, S. Tagawa: J. Photopolym. Sci. Technol. 16 (2003) 411. Relation between spatial resolution and reaction mechanism of chemically amplified resists for electron beam lithography, T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida, and S. Tagawa: J. Vac. Sci. Technol. 21 (2003) B3149. Dependence of Outgassing Characters at a 157 nm Exposure on Resist Structures, Y. Matsui, S. Umeda, S. Seki, S. Tagawa, S. Ishikawa T. Itani: Jpn. J. Appl. Phys. 43 (2003) 3894. Pulse Radiolysis Study of Radical Cations of Polysilanes, T. Kawaguchi, S. Seki, K. Okamoto, A. Saeki, Y. Yoshida, S. Tagawa: Chem. Phys. Lett. 374 (2003) 353. Transient Absorption Spectroscopy of Radical Ions of Rigid Anti- and Syn-tetrasilane, S. Seki, Y. Matsui, S. Tagawa, H. Tsuji, A. Toshimitsu, K. Tamao: Chem. Phys. Lett. 380 (2003) 141.

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Nonisothermal Crystallization Kinetics of Biodegradable Random Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)and Block one, S. Chanprateep, K. Kikuya, H. Shimizu, S. Seki, S. Tagawa, S. Shioya: J. Chem. Eng. Jpn. 36 (2003) 639. Nano-wire Formation and Selective Adhesion on Substrates by Single Ion Track Reaction in Polysilanes, S. Seki, S. Tsukuda, Y. Yoshida, T. Kozawa, S. Tagawa, M. Sugimoto, S. Tanaka: Jpn. J. Appl. Phys. 43 (2003) 4159. The Effects of Free Volumes on Charge Carrier Transport in Polysilanes Probed by Positron Annihilation, S. Seki, Y. Terashima, K. Kunimi, T. Kawamori, M. Tashiro, Y. Honda, S. Tagawa: Radiat. Phys. Chem. 68 (2003) 501.

Influence of Radiation-induced Species on Positronium Formation in Poly(methylmethacrylate) at Low Temperature, M. Tashiro, C.Y. Tseng, S. Seki, Y. Honda, S. Tagawa: Radiat. Phys. Chem. 68 (2003) 475. Study of Nano-Space in Au-Polysilane Interfaces by Slow Positron Beam, Y. Terashima, S. Seki, M. Tashiro, Y. Honda, S. Tagawa: J. Photopolym. Sci .Technol. 16 (2003) 445. The Study of Nano-space in Polyhydroxystyrene/Polystyrene Bilayer by Slow Positron Beam, Y. Terashima, M. Tashiro, K. Miyamoto, Y. Honda and S. Tagawa: Radiat. Phys. Chem. 68 (2003) 589. Cross-linked Polymer Nanowires with Controlled Shape and Orientation by High Energy Single Ion Hitting, S. Tsukuda, S. Seki, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka: J. Photopolym. Sci .Technol. 16 (2003) 433. Promotion of Thermal Dehydration of Poly(vinyl alcohol) Film by Diphenyliodonium Salt, Y. Yamamoto and S. Tagawa: Chem. Lett. 31 (2003) 572. Effect of Poly(vinyl alcohol) on Radiation-induced Acid-generation of Diphenyliodonium Salt, K. Sakai, Y. Yamamoto, and S. Tagawa : J. Photopolym. Sci .Technol. 16 (2003) 19. Behavior of positronium in polystyrene and its derivatives, Y. Honda, M. Watanabe, M. Tashiro, Y. Terashima, K. Miyamoto, N. Kimura and S. Tagawa: Radiat. Phys. Chem.68 (2003) 463. Dependence of Outgassing Characters and Total Amount of Outgassed Species at 157 nm Exposure on the Structures of Resist Base Polymer, Y. Matsui, S. Umeda, S. Matsui, S. Seki, S. Tagawa, S. Ishikawa, T. Itani: Proc. SPIE 5039 (2003) 121. Review Papers

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Study of Organic Polymer Thin Film Etching by Plasma Beam Irradiation", A. Egami, K. Kurihara, T. Yagishita, Y. Yamaoka, M. Nakamura, T. Kawachi, S. Seki, and S. Tagawa, Proc. DPS 55, 2003

International Conferences Cross-linked Polymer Nanowires with Controlled Shape and Orientation by High Energy Single Ion Hitting, *S. Tsukuda, S. Seki, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka: The 20th Conference of Photopolymer Science and Technology, Chiba, Japan, June 24-27, 2003. The Interaction between Polymer Thin Films and Positron from Slow Positron Beam, *K. Miyamoto, Y. Terashima, M. Tashiro, Y. Honda, S. Tagawa: The 20th Conference of Photopolymer Science and Technology, Chiba, Japan, June 24-27, 2003. Study of Nano-Space in Au-Polysilane Interfaces by Slow Positron Beam, *Y. Terashima, S. Seki, M. Tashiro, Y. Honda, S. Tagawa: The 20th Conference of Photopolymer Science and Technology, Chiba, Japan, June 24-27, 2003. Outgassed Species from Various Triphenylsulfonium Salts during 157 nm, *Y. Matsui, S. Seki, S. Tagawa, S. Irie, T. Itani: 4th International Symposium on 157 nm Lithography, Tokyo, Japan, Aug. 25-28, 2003. Study of Interfaces in Polymer bilayers by Slow Positron Beam, *Y. Terashima, S. Seki, K. Miyamoto, M. Tashiro, Y. Honda, S. Tagawa: The 13th International Conference on Positron Annihilation, Kyoto, Japan, Sept. 7-12, 2003. Effects of Ester Groups on Proton Generation and Diffusion in Polymethacrylate Matrices, *A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Polymer Screening Method for Chemically Amplified Electron Beam and X-Ray Resists, *H.Yamamoto, A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Outgassed Species from 157-nm-Irradiated Triphenylsulfonium Salts, *Y. Matsui, S. Seki, S. Tagawa, S. Irie, T. Itani: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Applications of Polysilanes for a Negative-Tone Resist in Ion Beam Lithography, *Y. Matsui, S. Seki, S. Tsukuda, T. Kozawa, and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003.

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Fabrication of Molecular Photoelectronic Devise Using Polysilane Nanowires, *S. Tsukuda, S. Seki, A. Saeki, T. Kozawa, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Pulse Radiolysis Study on Proton and Charge Transfer Reactions in Poly (Methyl Methacrylate),* A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Adjacent Effect on Positive Charge Transfer from Radical Cation of n-Dodecane to Scavenger Studied by Supbicosecond Pulse Radiolysis, Statistical and Monte Carlo Approach, *A. Saeki, T. Kozawa, Y. Yoshida and S. Tagawa: 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Oriented Nano-Wire Formation by Single Ion Track Reaction in Polysilanes *S. Seki, S. Tsukuda, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka and A. Oshima, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003.

Subpicosecond Pulse Radiolysis Study of Solvated Electron in Alcohols *T. Kozawa, Y. Numata, A. Saeki, K. Okamoto, Y. Yoshida, S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Modeling of Nano-Wires by Single Ion Hitting for Si-Based Polymers *S. Tsukuda, S. Seki, S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003.

The Relation between Spatial Resolution and Reaction Mechanism of Chemically Amplified Resists for Electron Beam Lithography *T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida and S. Tagawa The 47th International Conference on Electron, Ion and Photon Beam Technology and Nanofabrication, Florida, USA, May 27-30, 2003. Contributions to International Conferences and Journals

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S. Tagawa 13th Microprocess and Nanotechnology Conference (Organizing Committee)

S. Tagawa International Nuclear Conference ’02 (Organizing Committee) Publications in Domestic Meetings The Japan Society of Radiation Chemistry 14 papers Chemical Society of Japan 2 papers Atomic Energy Society of Japan 1 paper The Japan Society of Applied Physics: 3 papers Society of Polymer Science, Japan 1 paper The Japanese Biochemical Society 1 paper Academic Degrees Docter Degree of Engineering Y. Terashima

Interface Structures of Polymer Bilayer Using Slow Positron Beam

Master Degree of Engineering S. Tsukuda

Formation and Control of Polymer Nano-structure by High-energy Ion Beam

M. Todo

Study on Dynamics of Aromatic Radical Cations Formed by Radiation Induced Reaction in Condensed Phase

K. Miyamoto

Studies on Dependence of Nano-space and Ps Formation on Polymer Structure by Positron Annihilation Lifetime Spectroscopy

Sponsorship Grant-in-Aid for Scientific Research on Priority Areas K. Kobayashi Structure-Function of the Sensor Protein for Short-Lived

Intermediates ¥6,000,000

Grant-in-Aid for Scientific Research S. Tagawa Femtosecond Pulse Radiolysis Study on

Radiation-Induced Reactions in Nanoscopic Region ¥13,800,000

K. Kobayashi Molecular Mechanism of Redox-driven Proton Pumping by Respiratory Terminal Oxidase Revealed by Pulse Radiolysis

¥4,300,000

Y. Terashima

Microstructural Characterization for Polymer Films by Slow Positron Beams

¥ 900,000

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Entrusted Research S. Tagawa,

Advanced Semiconductor Engineering and Technology

Mechanisms of Polymer Etching Processes by Ultra Low Energy Ion Beams

¥5,250,000

S. Tagawa Advanced Semiconductor Engineering and Technology

Reaction Mechanism in Chemically Amplified Resist Materials

¥1,575,000

S. Tagawa,

Semiconductor Leading Edge Technology Inc.

Outgassing Characters from F2 Laser Resist Materials

¥4,000,000

Cooperative Research S. Tagawa,

Japan Atomic Energy Research Institute

Ion Beam Pulse Radiolysis in Condensed Matter

S. Tagawa,

Japan Atomic Energy Research Institute

Nanostructure Formation along Charged Particle Trajectory

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Nanoscience and Nanotechnology Center Director Professor: Tomoji KAWAI Support Staff: Umi SUENAGA Outlines

Nanoscience and Nanotechnology Center was founded in April 2002 for developing Bottom-up Nanotechnology, Top-down Nanotechnology, and their Industrial Application. This center consists of three divisions, (1) Nanomaterial and Nanodevices, (2) Beam Science for Nanotechnology, (3) Nanoscience and Nanotechnology for Industrial Applications.

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Division of Nanomaterials and Nanodevices Outlines

The main purpose of this department is to construct function harmonized nano-materials which can mimic flexible data processing like human body. By using typical “Bottom-up Nanotechnology” of artificial lattice technique, we combine metal, inorganic and organic(bio) materials at atomic/molecular level to new nano-materials.

The object of this department is to research molecular-scale devices based on the function of single molecule. We are developing new techniques for the measurement of physical and chemical properties of single or several molecules.

Design and syntheses of supramolecules such as artificial DNA, proteins, photosynthetic molecules, and nanoparticles having more efficient and selective functions than those of single molecules have been investigated towards constructions of organized supramolecular systems such as artificial living cells and nanodevices indicating multifunctions, complex properties, and conjugated functions

Proteins and their complex with other biomolecules are regarded as nano bio devices. The research of our group is focused on structural and functional studies on such devices. We are also interested in developing highly sensitive biosensors and nano machines. Achievements

Construction of functional nano-materials, which can mimic flexible date processing like human body.

• • • • • • • •

• • • •

• • •

Investigation of relationship with structure and material properties at nano-scale. Control of nano-sacle interface among organic, inorganic, metal materials. Development of bottom up nano technology system. Creation of super-five senses sensor and brain type memory. Programmed self-assembly and self-organization for molecular device. Selective nano-fabrication by chemical surface modifications. Electronic properties of single molecule connected to metals or semiconductors. Novel techniques on scanning probe microscopy and scanning electron microscopy for molecular devices. Molecular design of DNA wires by synthesis and assembly of molecule-conjugated DNA. Synthesis and assembly of photochemical probe molecules for bioimaging. Photochemical control of functionalized artificial proteins. Preparation of nanoparticles by self-assembly. Preparation of molecular devices by synthesis and assembly of functionalized polymers. Structural and functional studies of nano bio devices. Development of highly sensitive biosensors. Construction of nano machines driven by a molecular motor.

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Department of Artificial Nanomaterials for Bio-Information Systems Professor: Hitoshi TABATA Research Associate: Hiromasa SAEKI Research Fellow: Hiroaki MATSUI Support Staff: Megumi IKEDA Outlines

The main purpose of this department is to create function harmonized nano-materials

which can mimic flexible data processing like human body. By using typical “Bottom-up Nanotechnology” of artificial lattice technique and

programmed self organizing function, we combine metal, inorganic and organic (bio) materials at atomic/molecular level to new nano-materials. Current Research Programs

1. Construction of Functional Nano-materials, which can Mimic Flexible Date Processing like Human Body. Programmed self assembly is a unique technique for fabrication new materials. In case of artificial superlattice formation, we supply atoms and molecules followed by our own sequences. These fabrication techniques can be called programmed assembly which is well known in the bio-materials. We have successively formed hetero-structural bio mimetic materials with a sequence of CuPc (mimetic for eye) and PZT and BaTiO3/(La,Sr)MnO3 (mimetic for brain). 2. Investigation of Relationship Between Structure and Material Properties at Nano-meter Scale. An artificial lattice of a spinel type RuAlFe2O4 and ZnNiFe2O4 have been prepared for the first time by a laser MBE. Especially, charge disproportionate elements such as Ti etc. are essential for creating the photo-induced magnetization. They show spin glass behaviours above room temperature and light irradiated magnetism. Spin-glass property is expected to mimetic brain (synaptic) type memory. 3. Development of Bottom up Nano Technology System for Bio-electronics.

Self-assemble properties of DNA and bio based molecules were studied by use of SPM with Si as a substrate. By use of an ethanol, DNA network was successfully stabilized on a mica substrate. Formation of DNA networks are confirmed also on various substrate other than mica, i.e. silicon wafer, pyrolytic carbon etc. Conditions to control size of meshes were also found. This scaffold is a candidate for bio-nano electronics and bio-chips. New type non-fluorescent molecules labelled DNA-chips have been constructed by using IS-FET devices. For creating nano-patterns, we have developed bottom-up nano-fabricating apparatus such as nano-imprinting and nano-inkjet.

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4. Spin Electronics by Wide Gap Oxide Semiconductors The main purpose of this department is to construct function harmonized nano-materials which have spin and charge at the same time. One of the candidate materials for them is spin-electronic material. We have successively fabricated the magnetic oxide-semiconductors of Co and V-doped ZnO by a pulsed laser deposition technique. It shows ferromagnetic property above room temperature and transparent character. The ferromagnetic properties have been confirmed by not only SQUID measurements but also MCD, XMCD and NMR in experimentally and theoretically. Publications Original Papers Electrical Conducting Properties of DNA Molecules in a Metal (tip)/DNA/Highly Oriented Pyrolytic Graphite Configuration, S.Tanaka, L.T.Cai, H.Tabata and T. Kawai:Jpn. J. Appl. Phys. 42 (2003) 2818-2823. Toward the DNA Electronics, H.Tabata, L.T.Cai, J.-H.Gu, S.Tanaka, Y.Otsuka, Y.Sacho, M.Taniguchi and T.Kawai:Synthetic Metals 133-134 (2003) 469-472. Transparent Thin Films Transistors Using ZnO as an Active Channel Layer and their Electrical Properties, S.Masuda, K.Kitamura, Y.Okumura, S.Miyatake, H.Tabata and T.Kawai:J. Appl. Phys. 93 (2003) 1624-1630. Influence of Co-Doping with Ga on the Electrical and Optical Properties of N-doped ZnO Films, H.Matsui, H.Saeki, H.Tabata and T.Kawai:J. Electrochem. Soc. 150 (2003) G508-G512. Role of Ga for Co-Doping of Ga with N in ZnO Films, H.Matsui, H.Saeki, H.Tabata and T.Kawai:Jpn. J. Appl. Phys. 42 (2003) 5494-5499. Artificial Control of Order Degree State of B-Site Ions in Ba(Zr,Ti)O3 by a Superlattice Technique, Y.Hotta, G.W.J.Hassink, T.Kawai and H.Tabata:Jpn. J. Appl. Phys. 42 (2003) 5908-5912. Humidity Dependence of Electrical Resistivity in Poly(dG)・Poly(dC) DNA Thin Film, M.Taniguchi, Y.Otsuka, H.Tabata and T.Kawai:Jpn. J. Appl. Phys. 42 (2003) 6629-6630. Review Papers DNA Electronics,H. Tabata, M. Taniguchi, H. Tanaka, Y. Otsuka, S. Tanaka, T. Kawai:Hyoumenkagaku 24 [11] (2003) 677-683. DNA as Nano-Wires,H. Tabata:Koubunshi 52 [3] (2003) 126-129.

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Bottom up Type Semiconducting Processes using DNA, H. Tabata:M&E 12 (2003) 168-175. DNA Semiconductor, H. Tabata:Nikkei Biobusiness 6 (2003) 78-79. Books Hakumaku, H. Tabata,MARUZEN Co., Ltd., (2003) 231-243. Hand Book for Ion Technology, H. Tabata:Ion Engineering Laboratory Co., Ltd., (2003) 944-948. Patents The Production Technique of Electrically Conducting Material, Electroconductive Thin Films, Composite Film and Electrically Conducting Material, H. Tabata, T. Kawai, Mathew Joseph, Patent number:3472791 Ferroelectrics Memories and the Production Technique for Them, T. Kawai, H. Kobayashi, H. Tabata, E. Rokuta, Tokkai2003-060167 International Conferences DNA Nano- electronics: Physical and Electrical Properties of DNA(Invited), *H. Tabata, T. Kawai, The 7th World Multi-Conference on Systemics, Cybernetics and Informatics (SCI2003), Florida, U.S.A., Jul. 27-30, 2003. Grain Size Dependence of Electrical and Magnetic Properties of Polycrystalline NiFe2O4 Spinel, A. A.K.M. Hossain, M. Seki, T. Kawai, *H. Tabata, 10th International Workshop on Oxide Electoronics, Augsburg, Germany, Sep. 11-13, 2003. Magnetism of Vanadium-doped ZnO Thin Films (Poster), *H. Saeki, H. Tabata, 10th International Workshop on Oxide Electronics, Augsburg, Germany, Sep. 11-13, 2003. Polarity Effect of ZnO Homoepitaxial Films Grown Using Laser Molecular Beam Epitaxy (Poster), H. Matsui, H. Saeki, A. Sasaki, M. Yoshimoto and *H. Tabata, 10th International Workshop on Oxide Electronics, Augsburg, Germany, Sep. 11-13, 2003. Correlation between Relaxor Behaviour and Ordered-Disordered State in Ba(ZrxTi1-x)O3 : a Study Using Monte-Carlo Simulations and Artificial Superlattices (Poster), *Y. Hotta, G.W.J. Hassink, D.H.A. Blank, T. Kawai and H. Tabata, 10th International Workshop on Oxide Electronics, Augsburg, Germany, Sep. 11-13, 2003. Spin (Cluster) Glass State and Photo-Induced Magnetization on Spinel and Garnet Ferrites Thin Films (Poster), *M. Seki, A.K.M. Akther Hossain, K. Tanimura, T. Kawai and H. Tabata, 10th International Workshop on Oxide Electronics, Augsburg, Germany, Sep. 11-13, 2003.

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Synthesis of Long Strand DNA with Specific Sequences Using Enzymatic Reaction, Poly(dA)-Ploy(dT) (Poster), *S. Tanaka, H. Tanaka, M. Taniguchi, H. Tabata, S. Fujiwara, S. Uchiyama, K. Fukui and T. Kawai, Materials Chemistry Forum・Materials Discussion 6 -Controlled Polymer Architectures from Micro to Meso Scale-, Durham, UK, Sep. 12-14, 2003. Synthesis of Long Poly(dG)-Ploy(dC) without Structural Defects Using Enzymatic Reaction (Poster), *S. Tanaka, M. Taniguchi, H. Tabata, S. Fujiwara, S. Uchiyama, K. Fukui and T. Kawai, Materials Chemistry Forum・Materials Discussion 6 -Controlled Polymer Architectures from Micro to Meso Scale-, Durham, UK, Sep. 12-14, 2003. Ferroelectric Relaxor Behaviors in BaTiO3/BaZrO3 Superlattices Depending on Ordered-Disordered State of the B-site Cations, *H. Tabata and Y. Hotta, The 5th International Meeting of Pacific Rim Ceramic Societies (PacRim5), Nagoya, Japan, Sep. 29-Oct. 2, 2003. Relaxor-Ttype Ferroelectric Superlattices. -Ordered/Disordered Control of B-Site Ions-(Invited), *H. Tabata and Y. Hotta, The 8th IUMRS International Conference on Advanced Materials (IUMRS-ICAM2003), Yokohama, Japan, Oct. 11-13, 2003. Ordered- Disordered Control of B-Site Ions in the BaTiO3-BaZrO3 Relaxor Superlattices (Invited), *H. Tabata and Y. Hotta, 204th Meeting of The Electrochemical Society (ECS), Florida, U.S.A., Oct. 12-17, 2003. Electric and Magnetic Properties of Hetero and Homo Epitaxial Thin Films of ZnO on Sapphire and Polarity Controlled ZnO Single Crystals, *H. Tabata, H. Matsui, H.Saeki, S.Choopun and T. Kawai, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec. 8-9, 2003. Homoepitaxy in ZnO: Zn-Polar Growth (Poster), *H. Matsui, H. Saeki, A. Sasaki M. Yoshimoto, M.Tsubaki and H.Tabata, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec.8-9, 2003. Immobilization of Probe DNA on Ta2O5 Thin Film and Detection of Hybridized Helix DNA by Using IS-FET (Poster), *T. Ohtake, C. Hamai, T. Uno, H. Tabata and T. Kawai, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec.8-9, 2003. Fabrication of Nano-Gap Electrode without Lithography Technique and Electrical Characteristics of Nano structured Molecules (Poster), *Y.Otsuka、Y. Naitoh, W. Mizutani, T. Matsumoto, H. Tabata, T. Kawai, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, Dec.8-9, 2003.

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Measuring Electrical Conductivity of Molecules with Nano-Gap Electrode (Poster), *Y.Otsuka、Y. Naitoh, W. Mizutani, T. Matsumoto, H. Tabata, T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, Dec. 11-13, 2003 Nanoscale Electrical Characterization Techniques for Molecular Nanoelectronics, *Y.Otsuka、Y. Naitoh, W. Mizutani, T. Matsumoto, H. Tabata, T. Kawai, 21st Century COE Nanomaterial Group Student Seminar 2003, Finland, Jan. 7-10, 2004. Characteristics of Zn-Plar ZnO and ZnMgO Films Grown Using Homo-Epitaxy Technique Towards Quantum Atructures (Poster), *H. Matsui, H. Saeki and H. Tabata, 2nd 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium, Osaka, Japan, Jan. 13-14, 2004. DNA Nano-Patterning with Self-Organization by Using Nanoimprint (Poster), *T.Ohtake, K.Nakamatsu, S.Matsui, H.Tabata and T.Kawai, 2nd 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium, Osaka, Japan, Jan. 13-14, 2004. Large Negative Magnetoresistance in Spinel Type Zn1-xNixFe2O4 and Zn1-xCoxFe2O4 Ferrites (Poster), *A. K. M. Akther Hossain, M. Seki, T. Kawai, H. Tabata, 2nd 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium, Osaka, Japan, Jan. 13-14, 2004. Direct Detection of DNA Using ISFET Based on PNA (Poster), *T. Uno, T. Ohtake, H. Tabata and T. Kawai, 2nd 21st Century COE "Towards Creating New Industries Based on Inter-Nanoscience" 7th SANKEN International Symposium, Osaka, Japan, Jan. 13-14, 2004. Interdisciplinary Nano-Technology of Bottom-Up and Top-Down for DNA and Bio-Electronics (Invited), *H. Tabata, T. Ohtake, T. Uno, Y. Otsuka and T. Kawai, International Workshop on Plasma Nano-Technology and Its Future Vision, Takayama, Japan, Feb. 5-6, 2004. Interdisciplinary Nano-Technology of Bottom-Up and Top-Down for DNA and Bio-Electronics (Poster), H. Tabata, *T. Ohtake, T. Uno, Y. Ohtsuka and T. Kawai, International Workshop on Plasma Nano-Technology and Its Future Vision, Takayama, Japan, Feb. 5-6, 2004. Large Negative Magnetoresistance in Spinel type Ni and Co doped Zinc Ferrites, *A. K. M. Akther Hossain, M. Seki, T. Kawai, H. Tabata, Annual APS March Meeting 2004, Montreal, Canada, Mar. 22-26, 2004. Fabrication of Nano-gap Electrodes Without Lithography Technique and Electrical Characteristics of Nano Structured Molecules, *Y. Otsuka, Y. Naitoh, T. Matsumoto, W.

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Mizutani, H. Tabata, T. Kawai, Annual APS March Meeting 2004, Montreal, Canada, Mar. 22-26, 2004. Contributions to International Conferences and Journals H. Tabata International Conference on Solid State Devices and Materials 2003

(SSDM2003)(Program Committee/Subcommittee)

H. Tabata The Seventh International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures(Publication Committee)

H. Tabata International Conference on Solid Films and Surfaces (ICSFS-12)(Program Committee)

H. Tabata The fifth Japan-Korean Conference on Ferroelectrics(Publication Committee)

Publications in Domestic Meetings The Japan Society of Applied Physics 19 papers The Physical Society of Japan 1 paper The Society of Polymer Science, Japan 1 paper Others 13papers Sponsorship Grant-in-Aid for Scientific Research on Priority Areas (2) H. Tabata Functional Harmonized Materials Made by Perfect Interface

Control ¥14,000,000

Grant-in-Aid for Scientific Research (B) H. Tabata Creation of New Ferroelectric Thin Films ¥2,900,000 Grant-in-Aid for Basic Research (C)(2) H. Tabata Sensors of Super Five Sense and Brain Mimetic Devices

Formed by Organic/Inorganic Hetero Structures ¥1,400,000

Other Research Fund H. Tabata PRESTO21 Creation of Noble Dielectric Properties

by Ordered-Disordered Artificial Super Lattices

¥4,800,000

H. Tabata Special Coordination Funds for Promoting Science and Technology

Spin-Electronics Formed with Oxide Semiconductors

¥25,645,000

H. Tabata Sumitomo-seika Chemicals Company

Research on Nitrogen Oxide Gases ¥1,050,000

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215

H. Tabata KONICA MINOLTA Holdings,Inc.

The Research of the Photocharacterization in a Functional Oxide Thin Films

¥500,000

H. Tabata dept Corporation Developing of the Nanotechnology Using the Self-Organized Metals

¥600,000

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Department of Single-Molecular Integrated Devices Professor: Tomoji KAWAI Associate Professor: Takuya MATSUMOTO Research Associate: Masateru TANIGUCHI Researcher: Akihiko TAKAGI Outlines

The object of this department is to research molecular-scale devices based on the function of single molecule. We are developing new techniques for the measurement of physical and chemical properties of single or several molecules. Current Research Programs and Achievements Programmed self-assembly and self-organization for molecular-scale devices. DNA is a key material in the fabrication of nanostructures by the “bottom-up” process, which incorporates highly selective chemical recognition and self-assembly. In particular, DNA-templated assembly of nanoparticles has been studied intensively in the hope of building nanoscale circuits where nanoparticles might play roles such as conductive nanowire, quantum dot, anchor sites for molecules, and so on. We demonstrated DNA-templated assembly of gold-nanoparticles (AuNP) via step-by-step binding reaction. The control of hydrophilicity for the substrate surface makes it possible to preserve the structure of AuNP-combined DNA network with resistance to Au-thiolate reaction in ethanol solvent. This method realizes the formation of a continuous AuNP array with uniform height and small width. Novel techniques on scanning probe microscopy for molecular-scale electronics. Molecular-scale electronics has attracted much attention in the last quarter-century. In the past several years, scanning tunneling microscopy has provided fascinating results for the tunneling conductivity of single molecule on metal substrates. However, such investigations have not directly led to actual molecular-scale devices due to the inadequacy for insulating surface. Because the electronic devices should be formed on insulating substrate as a necessity, effective methods for the study of single molecular structure and properties on insulating surfaces are much awaited. We proposed point-contact current-imaging AFM (PCI-AFM)—which combines tapping mode (for mapping topographic image) and point-contact operation (for measuring current-voltage characteristics)—has been developed. This new AFM technique can simultaneously map high-resolution topographic image and measure spatially resolved I-V characteristics of materials (placed on an insulative substrate and connected to a gold electrode) on the nanoscale. The high performance of the PCI-AFM system was evaluated in experiments on single-walled carbon nanotubes (SWNTs). Furthermore, we also propose charge transfer force microscopy / spectroscopy (CTFM/S) based on dynamic mode scanning force microscopy. It enable us to obtain a map of density of state (DOS) and DOS spectra in nanometer scale for the surface consisting of insulating and conductive regions. Such surface is typical from the

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viewpoint of electronic devices but inadequate for the sample of scanning tunneling microscopy/ spectroscopy. The CTFM/S is promising method to investigate local DOS of nanometer scale devices. Synthesis of Tailored DNA The clarification of the electronic conductive phenomenon of DNA molecules is presently one of the most important subjects in the fields of bio- and nano-science. However, the conductivity of DNA strongly depends on sequences and structural defects. We synthesized long Poly(dA)·Poly(dT) Poly(dG)·Poly(dC) without structural defects by using enzymatic reaction. The length of synthesized Poly(dA)·Poly(dT) and Poly(dG)·Poly(dC) were estimated to be 1000 and 500 base pairs, respectively, from agarose gel electrophoresis. The structure of synthesized Poly(dA)·Poly(dT) and Poly(dA)·Poly(dT) were characterized using scanning tunneling microscope (STM). The observed DNA was linear structure. The average width of this DNA is about 3.0 nm, which supports the absence of structural defects for the DNA molecule. Control of Electrical Conductivity of DNA Electrical resistivity of Poly(dA)·Poly(dT) and Poly(dG)·Poly(dC) DNA were measured in a vacuum on nano-gap electrodes separated by 30-50 nm. The DNAs showed very low conductivity of less than 0.1 pA at 1 V. On the other hand, I2-doped Poly(dA)·Poly(dT) and Poly(dG)·Poly(dC) DNA form conducting DNAs, the current of which increased with an increase in the doping time. Doped Poly(dG)·Poly(dC) DNA shows higher current than doped Poly(dA)·Poly(dT) DNA. Time dependence of resistivity of Poly(dG)·Poly(dC) DNA doped with iodine molecules exhibited that the total current composes of both hole current and ion current.

Publications Original Papers Point-Contact Current-Imaging Atomic Force Microscopy: Measurement of Contact Resistance between Single-walled Carbon Nanotubes, Y. Otsuka, Y. Naitoh, T. Matsumoto, and T. Kawai : Appl. Phys. Lett. 82 (2003) 1944-1946. Nanoscale Obserbation of Room-temperature Ferromagnetism on Ultrathin (La,Ba)MnO3 Films, T. Kanki, R.-W. Li, Y. Naitoh, H. Tanaka, T. Matsumoto, and T. Kawai : Appl. Phys. Lett. 83 (2003) 1184. Electronic Transport Properties of Free-base Tape-porphyrin Molecular Wires Studied by Self-consistent Tight-binding Calculations, K. Tagami, M. Tsukada, T. Matsumoto, and T. Kawai : Phys. Rev. B. 67 (2003) 245324. Theoretical Prescriptions for Improving Conductance of Short DNA Segments Sandwiched between Metal Electrode, K. Tagami, T. Matsumoto, T. Kawai, and T. Tsukada : Jpn. J. Appl. Phys. 42 (2003) 5887. Development of Point-Contact Current Imaging Atomic Force Microscopy, Y.

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Otsuka,Y. Naitoh, A. Terayaki, T. Matsumoto,and T. Kawai : Hyomen Kagaku 24 (2003) 573. STM Imaging of Individual Porphyrin Hexamers; meso-meso Slingly Linked Orthogonal Hexamer and meso-meso, β-β, β-β tiply-linked Planear Hexamer on Cu(100) Surface, A. Takagi, Y. Yanagawa, A. Tsuda, N. Aratani, T. Matsumoto, A. Osuka and T. Kawai : Chem. Commun. 24 (2003) 2986-2987. Toward the DNA Electronics, H. Tabata, L. T. Cai, J.–H. Gu, S. Tanaka, Y. Otsuka, Y. Sacho, M. Taniguchi, and T. Kawai: Synth. Met. 133-134 (2003) 469-472. Humidity Dependence of Electrical Conductivity in Poly(dG)・Poly(dC) DNA, M. Taniguchi, Y. Ohtsuka, H. Tabata, and T. Kawai : Jpn. J. Appl. Phys. 42 (2003) 6629-6630. Review Papers Nanotester: T. Matsumoto, and T. Kawai : Ohyoubuturi 72 (2003) 602-604. DNA Electronics, H. Tabata, M. Taniguchi, H. Tanaka, Y. Otsuka, S. Tanaka, and T. Kawai : Hyomen Kagaku 24 (2003) 677-683. International Conferences Charge Transfer Force Microscopy/ Spectroscopy, *Y. Naitoh, T. Matsumoto, and T. Kawai, 3rd International Symposium on Scanning Probe Spectroscopy and Related Methods, Poznam-Malta, Poland, July 16-19, 2003. Charge Transfer Force Microscopy/ Spectroscopy and Their Application for Molecular Systems, *Y. Naitoh, T. Matsumoto, and T. Kawai, 12th International Conference on Scanning Tunneling Microscopy/ Spectroscopy and Related Techniques, Eindhoven, the Netherlands, July 21-25, 2003. Superparamagnetisim of Fe Nanoclusters Observed by Non-contact Magnetic Force Microscopy, *T. Matsumoto, Y. Naitoh, K.Sato, Y. Hirotsu, and T.Kawai, 12th International Conference on Scanning Tunneling Microscopy/ Spectroscopy and Related Techniques, Eindhoven, the Netherlands, July 21-25, 2003. Structure and Electronic Properties of DNA-metal Nanoparticle Comples, *F. Yamada, H. Tanaka, T. Matsumoto, and T. kawai, 12th International Conference on Scanning Tunneling Microscopy/ Spectroscopy and Related Techniques, Eindhoven, the Netherlands, July 21-25, 2003. Structure and Electronic Properties of DNA-dye Complex, *C. Takatoh, T. Matsumoto, and T. Kawai, 12th International Conference on Scanning Tunneling Microscopy/ Spectroscopy and Related Techniques, Eindhoven, the Netherlands, July 21-25, 2003. Photo-coincident Time-resolved Force Detection by Non-contact Atomic Force

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Microscopy, *T. Matsumoto, and T. Kawai, Sixth International Conference on Noncontact Atomic Force Microscopy, Dingle, Ireland, August 31-September 3, 2003. Electronic Properties of Biomolecular Systems: Towards the Realization of Bottom-up Molecular-scale Electronics(Invited), *T. Matsumoto, and T. Kawai, The5th RIES-Hokudai Symposium on Advanced Nanoscience, Sapporo, Japan, December 1-2, 2003. Electrical Conductivity of Cytochrome c on a Promoter-modified Substrate, *T. matsumoto, M. Kataoka, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa Japan, December 11-13, 2003. DNA-templated Assembly of Gold Nanopaticles, *F. Yamada, Y. Otsuka, T. Matsumoto, H. Tanaka, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, December 11-13, 2003. Measuring Electrical Conductivity of Molecules with Nano-gap electrodes, *Y. Otsuka, Y. Naitoh, T. Matsumoto, W. Mizutani, H .Tabata, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, December 11-13, 2003. Discrimination of Escherichia Coli Ribosomal Subunits by Atomic Force Microscopy, *T. Matsuura, K. Kobayashi, H. Tanaka, T. Matsumoto, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, December 11-13, 2003. Alignment of Au Nano-particle on HOPG Surface, *K. Ojima, K. Adachi, K. Yamada, T. Matsumoto, and T. Kawai, The 11th International Colloquium on Scanning Probe Microscopy, Atagawa, Japan, December 11-13, 2003. Stracture and Electoronic Properties of DNA-metal Nanoparticle Complex, *F. Yamada, H. Tanaka, T. Matsumoto, and T. Kawai, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, December 8-9, 2003. Fabrication of Nano-gap Electrodes Without Lithography Technique and Electrical Characteristics of Nano Structurde Molecules, *Y. Otsuka, Y. Naitoh, T. Matsumoto, W. Mizutani, H. Tabata, and T.Kawai, International Symposium on Scientific and Industrial nanotechnology, Osaka, Japan, December 8-9, 2003. Synthesis of Long Strand DNA with Specific Sequences Using Enzymatic Reaction: Poly(dA)Poly(dT), *S. Tanaka, H. Tanaka, M. Taniguchi, H. Tabata, S. Fujiwara, S. Uchiyama, K. Fukui, and T. Kawai, Royal Society of Chemistry, U.K., September 12-14, 2003. Synthesis of Long Poly(dG)Poly(dC) without Structural Defects Using Enzymatic Reation, *S. Tanaka, M. Taniguchi, H. Tabata, S. Fujiwara, S. Uchiyama, K. Fukui, and T. Kawai, Royal Society of Chemistry, U.K., September 12-14, 2003. Electronic Structure of DNA Under the Chemical-doping Condition, M. Furukawa, M,

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Tanuguchi, H. S. Kato, T. Hatsui, N. Kosugi, T. Kawai, and M. Kawai, Suroconference of spin and charge transport in nanostructures, Spain, September 1-5, 2003. Complex Incorporation in DNA Duplexes, K. Adachi, M. Taniguchi, T. Kawai, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, December 8-9, 2003. Publications in Domestic Meetings The Physical Society of Japan 4 papers The Japan Society of Applied Physics 2 papers The Chemical Society of Japan 1 paper Others 8 papers Sponsorship Grant-in-Aid for Scientific Research (B) T. Matsumoto Conductivity Measurement of Single Molecule ¥3,800,000 Exploratory Research T. Matsumoto Photo-Induced Electron Transfer of Individual

Molecules ¥1,300,000

21st Century Center of Excellence Young Scientist A M. Taniguchi Electrical Characteristic Evaluation of Nanoparticles

Using Nanogap Electrdes ¥1,000,000

Entrusted research T. Matsumoto Japan Science and

Technology Corporation

Mesoscopic Devices of Huge Porphyrin Arrays

¥1,200,000

Other Research Funds T. Matsumoto Japan Science and

Technology Corporation

Mesoscopic Devices of Huge Porphyrin Arrays

¥11,000,000

M. Taniguchi Shin-Etsu Chemical Co., Ltd

Development of FET ¥1,000,000

M. Taniguchi Kansai Research Foundation from Technology Promotion

Development of high-mobility FET Based or Polymers Using Inkjet Process

¥1,000,000

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Department of Supramolecular Chemistry Professor: Tetsuro MAJIMA Research Associates: Masayuki ENDO, Shinobu TAKIZAWA Outlines

Design and syntheses of supramolecules such as artificial DNA, proteins, photosynthetic molecules, and nanoparticles having more efficient and selective functions than those of single molecules have been investigated towards constructions of organized supramolecular systems such as artificial living cells and nanodevices indicating multifunctions, complex properties, and conjugated functions. 1. Molecular design of DNA wires by synthesis and assembly of molecule-conjugated DNA 2. Synthesis and assembly of photochemical probe molecules for bioimaging 3. Photochemical control of functionalized artificial proteins 4. Design and syntheses of novel immobilized chiral catalysts for developing environmentally benign processes Current Research Programs 1. Creation of Nanostructures by DNA Supramolecular Structures

Molecular manipulation for creation of nanometer-scale materials by assembling functional molecules has attracted an attention in the field of nanotechomology. We investigate the novel strategy for building up nano-scale functional scaffolds based on the ability of self-assembly by employing novel DNA supramolecular units. For construction of wide variety of DNA supramolecular structures, we designed and synthesized cross-linked DNAs where two DNA strands are connected by disulfide linkage, bismaleimide linkers, and porphyrin derivatives. The DNA supramolecular units containing two cross-linked DNAs and complementary strands showed the stable complex formation. Using these DNA units, one-dimensional structures to be a micrometer-scale were prepared by molecular assembly and DNA ligation. The structures of the ligated products were examined by AFM, and the products were observed as rod-like straight structures. Also two dimensional sheet structures were created by using the DNA units, and the structures were confirmed by AFM. We demonstrated the novel strategy for assembling the DNA units into the one and two dimensional controlled structures, and controlling the arrangement of the functional molecules can be utilized for creation of novel functional nano-materials.

2. Metal-bridged Polymers as Enantioselective Catalysts Immobilization of catalysts facilitates environmentally benign processes by enabling

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their recovery and reuse. We have developed a movel approach for the effective immobilization of the multicomponent catalysts utilizing metal-bridged polymers which is formed by a metal-mediated self-organization of bis(bidentate) ligand. Recently we found that treatment of (R,R)-6,6’-bi(BINOL) with either LiAlH

4 or Ti(O-i-Pr)

4 generates a chiral

metal-bridged polymer which catalyzed Michael reaction and carbonyl-ene reaction respectively with high enantioselectivities. Publications Original Papers Formation of Pyrene Dimer Radical Cation in DNA Reflecting DNA Dynamics in the Time Range of 1 μs to 1 ms, K. Kawai, K. Miyamoto, S. Tojo, and T. Majima: J. Am. Chem. Soc., 125 [4] (2003) 912-915. A Two-Color Laser Photolysis Methods for Determining Reaction Rates of Short-Lived Intermediates by Product Analysis: Applictaion to the o-inodimethane Problem, A. Ouchi, Z. Li, M. Sakuragi, and T. Majima: J. Am. Chem. Soc., 125 [4] (2003) 1104-1108. Naphthalene in the Higher Triplet Excited State, X. Cai, M. Hara, K. Kawai, S. Tojo, and T. Majima: Chem. Commun., 2 (2003) 222-223. Sensitized Reactions of Benzophenone in the Higher Triplet Excited State, X. Cai, M. Hara, K. Kawai, S. Tojo, and T. Majima: Chem. Phys. Lett., 371 [1-2] (2003) 68-73. Hole Transfer in DNA: DNA as a Scaffold for Hole Transfer between Two Organic Molecules, T. Takada, K. Kawai, S. Tojo, and T. Majima: Tetrahedron Lett., 44 (2003) 3851-3854. Kinetics of Weak Distance Dependent Hole Transfer in DNA by Adenine Hopping Mechanism, K. Kawai, T. Takada, S. Tojo and, T. Majima: J. Am. Chem. Soc., 125 [23] (2003) 6842-6843. Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants, F. Takei, S. N, K. Onitsuka, A. Ishida, S. Tojo, T. Majima, and S.Takahashi: Chem. Lett., 32 [6] (2003) 06-507. Three-color Three-laser Photochemistry of Di(p-methoxyphenyl)methyl Chloride, M. Hara, S. Tojo, and T. Majima: J. Phys. Chem. A, 107 [24] (2003) 4778-4783. Ionization and Fragmentation of Some Chlorinated Compounds and Dibenzo-p-dioxin with an Intense Femtosecond Laser Pulse at 800 nm, H. Harada, M. Tanaka, M. Murakami, S. Shimizu, T. Yatsuhashi, N. Nakashima, S. Sakabe, Y. Izawa, S. Tojo, and T. Majima: J.

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Phys. Chem. A, 107 [34] (2003) 6580-6586. Transient Phenomena of Dibenz[a,h]anthracene in the Higher Triplet Excited States, X. Cai, M. Hara, K. Kawai, S. Tojo, M. Fujitsuka, and T. Majima: Tetrahedron Lett., 44 [32] (2003) 6117-6120. Photoisomerization of 2’-Deoxyribofuranosyl and Ribofuranosyl 2-Phenylazoimidazole, M. Endo, K. Nakayama, Y. Kaida, and T. Majima: Tetrahedron Lett., 44 [36] (2003) 6903-6906. Rapid cleavage of Naphthylmethyl-O bond in the Higher Triplet Excited States, X. Cai, M. Sakamoto, M. Hara, S. Tojo, M. Fujitsuka, A. Ouchi, and T. Majima: Chem. Commun., (2003) 2604-2605. Benzophenones in the Higher Triplet Excited States, X. Cai, M. Sakamoto, M. Hara, A. Sugimoto, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima: Photochem. Photobiol. Sci., 2 (2003) 1209-1214. Tandem Double Helix Nano-Structures Using Interstrand Crosslinked DNA with Maleimide Linkers, M. Endo and T. Majima: Angew. Chem. Int. Ed. Eng., (2003) 5744-5747. Control of A Double Helix Assembly by Use of Crosslinked Oligonucleotides, M. Endo and T. Majima, J. Am. Chem. Soc., 125 [45] (2003) 13654-13655. Long-lived Charge-Separated State Leading to DNA Damage through Hole Transfer, K. Kawai, T. Takada, T. Nagai, X. Cai, A.Sugimoto, M. Fujitsuka, and T. Majima: J. Am. Chem. Soc., 125 (2003) 16198-16199. Effects of Base Pairing on the One-electron Reduction Rate of Cytosine, K. Kawai, A.Yokoohji, S. Tojo, and T. Majima: Chem. Commun., (2003) 2840-2841. One-electron Oxidation of Aromatic Sulfides Adsorbed on the Surface of TiO

2 Particles

Studied by Time-resolved Diffuse Reflectance Spectroscopy, T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima: Chem. Phys. Lett., 382 (2003) 618-625. Excess Electron Transfer in DNA Studied by Pulse Radiolysis and γ-Radiolysis of Naphthalimide and Iodouridine Containing ODN, K. Kawai, T. Kimura, K. Kawabata, S. Tojo and T. Majima: J. Phys. Chem. B, 107 [46] (2003) 12838-12841. Kinetics of multi-step hole transfer in DNA by Monitoring the Transient Absorption of Pyrene Radical Cation , T. Takada, K. Kawai, S. Tojo, M. Fujitsuka, and T. Majima: J. Phys. Chem. B, 107 [50] (2003) 14052-14057.

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Design and Synthesis of Novel Spiro Pyridinium and Quinolinium Salts, M. L. Patil, S. Takizawa, and H. Sasai, Heterocycles, 61 (2003) 581. Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support, S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, Angew. Chem. Int. Ed., 42 (2003) 5711. Monolayer-protected Au Cluster (MPC)-supported Ti-BINOLate Complex, K. Marubayashi, S. Takizawa, T. Kawakusu, T. Arai, and H. Sasai, Org. Lett., 5 (2003) 4409. Synthesis of Novel Chiral Spiro Bis(pyrazole) Ligands, S. Takizawa, Y. Honda, M. A. Arai, T. Kato, and H. Sasai, Heterocycles, 60 (2003) 2551. Polymer Supported BisBINOL Ligands for the Immobilization of Multicomponent Asymmetric Catalysts, T. Sekiguti, Y. Iizuka, S. Takizawa, D. Jayaprakash, T. Arai, and H. Sasai, Org. Lett., 5 (2003) 2647. Enantioselective Synthesis of α-Methylene-γ-butyrolactones Using Chiral Pd(II)-SPRIX Catalyst, C. Muthiah, M. A. Arai, T. Shinohara, T. Arai, S. Takizawa, and H. Sasai, Tetrahedron Lett., 44 (2003) 5201. "Catalyst Analogue": A Concept for Constructing Multicomponent Asymmetric Catalysts (MAC) Using a Polymer Support, T. Arai, T. Sekiguti, K. Otsuki, S. Takizawa, and H. Sasai, Angew. Chem. Int. Ed., 42 (2003) 2144. Review Papers Hole Transfer in DNA using Pyrene-conjugated DNA, K. Kawai and T. Majima: Org. Synth. Chem. (in Japanese) 61 (2003), 614-619. Patents Damaging of Biomolecules and the Instruments, T. Majima and K. Kawai, 2003-338082 International Conferences Photochemical Control of Protein Activity, *T. Majima, The 21 Century COE Symposium -Towards Creating New Industries Based on Inter-Nanoscience- (INS-2003), 2003, Osaka, Japan, March 12, 2003. Photo-regulation of Hole Transfer in DNA Studied by Pulse Radiolysis-laser Flash Photolysis Combined Method (Poster), *T. Takada, K. Kawai, and T. Majima, 25th ACS National Meeting, New Orleans, LA, USA, March 22-27, 2003.

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Photochemitry of Short-lived Molecules (Invited), *T. Majima, CLEO Satelite meeting on Applications of Ultrafast Laser Systems, Baltimore, MD, USA, June 4, 2003. Hole Transfer in DNA by Adenine Hopping Mechanism (Invited), *T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Reactions Sensitized by Aromatic Hydrocarbons in the Higher Triplet Excited States (Poster), X. Cai, M. Hara, K. Kawai, S. Tojo, M. Fujitsuka, and *T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Hole Transfer Causes Long-Lived Charge Separated State which Leads to DNA Damage (Poster), *K. Kawai, and T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Charge Transfer in DNA via Consecutive Adenine Hopping (Poster), *T. Takada, K. Kawai, and T. Majima, 21st International Conference on Photochemistry (ICP21), Nara, Japan, July 26-31, 2003. Hole Transfer in DNA Studied by Pulse Radiolysis, K. Kawai, T. Takada, and *T. Majima, 12th International Congress on Radiation Research, Brisbane, Australia, August 17-22, 2003. Radiation Chemical and Photochemical Study of Z-DNA Modified by 2-Aminopurine and 8-Bromodeoxyguanosine (Poster), *T. Kimura, K. Kawai, and T. Majima, 12th International Congress on Radiation Research, Brisbane, Australia, August 17-22, 2003. Fast Hole Transfer by Adenine-Hopping for DNA Molecular Wire (Invited), K. Kawai, T. Takada, and *T. Majima, 10th Symposium of Intelligent Electrophotonic Materials and Molecular Electronics (SIEMME’10), Beijing, P.R. China, October 31-November 1, 2003. One-electron Oxidation during TiO

2 Photocatalytic Reactions Studied by Transient

Absorption Measurements (Invited), T. Tachikawa, S. Tojo, M. Fujitsuka, and *T. Majima, 10th Symposium of Intelligent Electrophotonic Materials and Molecular Electronics (SIEMME’10), Beijing, P.R. China, October 31-November 1, 2003. Fast Hole Transfer by Adenine-Hopping for DNA Molecular Wire, K. Kawai, T. Takada, and *T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. DNA Damaging using a Combination of Two-color Pulses (Poster), *K. Kawai, X. Cai, A. Sugimoto, S. Tojo, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003.

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Hole Transfer Causes Long-Lived Charge Separated State Leading to DNA Damage (Poster), *K. Kawai, T. Takada, T. Nagai, X. Cai, A. Sugimoto, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Charge Transfer in DNA via Adenine Hopping Mechanism (Poster), T. Takada, K. Kawai, and *T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. One-electron Oxidation of Aromatic Sulfides during TiO

2 Photocatalytic Reactions Studied

by Time-resolved Diffuse Reflectance Measurements (Poster), *T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. One-electron Oxidation of Aromatic Sulfides during TiO

2 Photocatalytic Reactions Studied

by Time-resolved Absorption Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Photochemistry of Oligothiophenes in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *M. Fujitsuka, Y. Oseki, M. Hara, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Photochemical Regulation of Protein Activity by Manipulating the Dimer Interface (Poster), *M. Endo, K. Nakayama, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Construction of DNA Nanostructures by Control of Double Helix DNA Assembly using Crosslinked Oligonucleotides (Poster), *M. Endo and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Aromatic Hydrocarbons in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *M. Fujitsuka, X. Cai, M. Sakamoto, M. Hara, and T. Majima, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Multi-laser Photochemistry (Invited), *M. Fujitsuka and T. Majima, Singapore International Chemical Conference 3 Frontiers in Physical and Analytical Chemistry, Singapore, December 8-9, 2003. Oligothiophenes in the Higher Triplet Excited States (Poster), *M Fujitsuka, Y. Oseki, M.

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Hara, and T. Majima, 7th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Rapid Exciton Migration and Fluorescent Energy Transfer in Helical Polyisocyanides with Regularly Arranged Porphyrin Pendants (Poster), *M. Fujitsuka, A. Okada, S. Tojo, F. Takei, K. Onitsuka, S. Takahashi, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. DNA Damaging by Two Lasers (Poster), *K. Kawai, X. Cai, A. Sugimoto, S. Tojo, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Effects of Hole Transfer on Photosensitized DNA Damaging (Poster), *K. Kawai, T. Takada, T. Nagai, X. Cai, A. Sugimoto, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Aromatic Sulfides during TiO

2 Photocatalytic Reactions: Part 1.

Time-resolved Absorption Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Aromatic Sulfides during TiO

2 Photocatalytic Reactions: Part 2.

Time-resolved Diffuse Reflectance Measurements (Poster), *S. Tojo, T. Tachikawa, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Photochemical Regulation of a Restriction Endonuclease BamHI by Manipulation of the Dimer Interface (Poster), *M. Endo, K. Nakayama, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Construction of DNA Nanostructures Using Crosslinked Oligonucleotides (Poster), *M. Endo and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Transient Absorption Measurement of Stilbene Radical Cation in the Higher Excited using

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ns and ps Two-laser Flash Photolysis (Poster), *M. Hara, S. Samori, X. Cai, M. Fujitsuka; and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Resonant Three Photon Ionization of Stilbene Derivatives using Two-color Two-laser Laser Flash Photolysis (Poster), *M. Hara, S. Samori, X. Cai, M. Fujitsuka; and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Rapid Cleavage of Naphthylmethyl-oxygen Bond in the Higher Triplet Excited States Studied by Two-color Two-laser Flash Photolysis (Poster), *X. Cai, M. Sakamoto, M. Hara, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Energy Transfer vs Electron Transfer during the Bimolecular Quenching of Aromatic Hydrocarbons in the Higher Triplet Excited States (Poster), *X. Cai, M. Sakamoto, M. Hara, S. Tojo, K. Kawai, M. Endo, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. One-electron Oxidation of Biphenyl Derivatives Strongly Coupled with TiO

2 Surface

(Poster), *T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, 7th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Hole Transport to Non-adsorbed Chemicals during TiO

2 Photocatalytic Reactions (Poster),

*T. Tachikawa, S. Tojo, M. Fujitsuka, and T. Majima, 7th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Competitive Quenching Processes of Naphthalene Derivatives in the Higher Triplet Excited States – Energy Transfer vs Electron Transfer (Poster), *M. Sakamoto, X. Cai, M. Hara, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, Jan. 13-14, 2004. Photochemical Control of Caspase-3 Activity for Induction of Apoptosis (Poster), *K. Nakayama, M. Endo, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004.

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2-Aminopurine-cytidine-7-deazaguanine (5’-ApCdz

G-3’) Trimer as a Fluorescent Unit for a Z-DNA Probe (Poster), *T. Kimura, K. Kawai, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Kinetics of Long-Distance Hole Transfer in DNA (Poster), *T. Takada, K. Kawai, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Long-Lived Charge-Separated State in DNA (Poster), *T. Takada, K. Kawai, M. Fujitsuka, and T. Majima, 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Charge Separation in DNA using the Consecutive Adenine Hopping (Poster), *K. Kawai, T. Takada, and T. Majima, International workshop on Advances in Molecular Electronics: From molecular materials to single-molecule devices, Dresden, BRD, February 23-27, 2004. Photosesitized Oxidation of DNA, *T. Majima, International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. DNA Supramolecular Chemistry, *M. Endo and T. Majima, International Workshop on Recent Progress in Organic Chemistry, Osaka, Japan, March 1-3, 2004. Manipulation of the Dimer Interface for Photochemical Regulation of the Activity of an Endonuclease BamHI (Poster), *K. Nakayama, M. Endo, and T. Majima, 227

th

ACS National Meeting, California, USA, March, 2004. Development of Multifunctional Asymmetric Catalysts (MAC) for Morita-Baylis-Hillman (MBH) Reaction (Poster), *K. Matsui, S. Takizawa, and H. Sasai, 12

th

Symposium on Organo-metallic Chemistry Directed Toward Organic Synthesis (OMCOS 12), Toronto, Canada, July, 2003. Design and Synthesis of Novel Spiro-Type Ligands (Poster), *T. Kato, K. Wakita, T. Shinohara, C. Muthiah, M. A. Arai, S. Takizawa, and H. Sasai, 12

th

Symposium on Organo-metallic Chemistry Directed Toward Organic Synthesis (OMCOS 12), Toronto, Canada, July, 2003. Development of Novel Multifunctional Asymmetric Catalysts (Poster), *S. Takizawa, H. Somei, K. Murai, T. Arai, D. Jayaprakash, and H. Sasai, The International Symposium on Dynamic Complexes (ISDC 2003), Tokyo, Japan, August, 2003..

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Enantioselective Catalysis Using Novel Spiro-type Ligands (Poster), *K. Wakita, M. A. Arai, T. Shinohara, T. Kato, C. Muthiah, S. Takizawa, T. Arai, and H. Sasai, The 15

th

International Symposium on Chirality (Chirality 2003), Shizuoka, Japan, October 2003. Enantioselective Catalysis Using Novel Spiro-type Ligands (Poster), *K. Wakita, T. Kato, T. Shinohara, C. Muthiah, M. A. Arai, S. Takizawa, T. Arai, and H. Sasai, The 9

th

International Kyoto Conference on New Aspects of Organic Chemistry (IKOCOC-9), Kyoto, Japan, November, 2003. Effective Immobilization of Mulitifunctional Asymmetric Catalysts. (Poster), *D. Jayaprakash, T. Sekiguti, Y. Iizuka, S. Takizawa, T. Arai, and H. Sasai, The 9

th

International Kyoto Conference on New Aspects of Organic Chemistry (IKOCOC-9), Kyoto, Japan, November, 2003. Dual Activation in a Homolytic Coupling Reaction Promoted by an Enantioselective Dinuclear Vanadium(IV) Catalyst (Poster), H. Somei, Y. Asano, T. Yoshida, *S. Takizawa, H. Yamataka, and H. Sasai, The 9

th

International Kyoto Conference on New Aspects of Organic Chemistry (IKOCOC-9), Kyoto, Japan, November, 2003. Aerobic Oxidation Catalyzed by Vanadium Compounds (Poster), *M. Kirihara, Y. Torii, K. Sato, S. Takizawa, Y. Ochiai, K. Okubo, N. Matsumoto, T. Uchiyama, S. Matsushita, A. Hatano, The 9

th

International Kyoto Conference on New Aspects of Organic Chemistry (IKOCOC-9), Kyoto, Japan, November, 2003. Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts (MACs) with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support (Poster), *S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Monolayer-protected Au Cluster (MPC)-supported Ti-BINOLate Complex (Poster), *T. Kawakusu, K. Marubayashi, S. Takizawa, T. Arai, and H. Sasai, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Metal-bridged Polymers as Insoluble Multicomponent Asymmetric Catalysts (MACs) with High Enantiocontrol: An Approach for the Immobilization of Catalysts without Using any Support (Poster), *S. Takizawa, H. Somei, D. Jayaprakash, and H. Sasai, International Symposium on Organic Reactions 2003 (ISOR-2003) Kaohsiung, Taiwan, December, 2003. Immobilization of Enantioselective Catalysts onto the Surface of Spherical Nanoparticles (Poster), *K. Marubayashi, S. Takizawa, F. Yonezawa, T. Kawakusu, D. Jayaprakash, M. L.

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Patil, T. Arai, T. Hanada, and H. Sasai, Second 21st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. The aza-Morita-Baylis-Hillman (aza-MBH) Reaction Promoted by Chiral Phosphine-BINOL as an Organocatalyst (Poster), *K. Matsui, S. Takizawa, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Design and Synthesis of Novel Spiro Chiral Phase Transfer Catalysts (Poster), *M. L. Patil, C. V. L. Rao, S. Takizawa, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Enantioselective Reactions Promoted by Pd(II)-SPRIX Catalysts (Poster), *C. Muthiah M. A. Arai, T. Shinohara, T. Arai, S. Takizawa, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. New Approach for the Immobilization of Multicomponent Asymmetric Catalysts with High Enantiocontrol (Poster), *S. Takizawa, D. Jayaprakash, H. Somei, T. Sekiguti, K. Otsuki, T. Arai, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Dual Activation in a Homolytic Coupling Reaction Promoted by an Enantioselective Dinuclear Vanadium(IV) Catalyst (Poster), H. Somei, Y. Asano, *T. Yoshida, S. Takizawa, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004. Design and Synthesis of Novel Spiro-Type Ligands (Poster), *T. Tsujihara, K. Wakita, T. Kato, T. Shinohara, M. A. Arai, S. Takizawa, T. Arai, and H. Sasai, Second 21

st

Century COE “Towards Creating New Industries Based on Inter-Nanoscience” 7

th

SANKEN International Symposium on “Hybridization of Chemistry, Biology, and Material Science- Perspectives in Nanoscience -”, Osaka, Japan, January 13-14, 2004.

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Immobilization of Multicomponent Asymmetric Catalysts, *S. Takizawa and H. Sasai, International Workshop on Advances in Molecular Electronics: From molecular materials to single-molecule devices, Dresden, BRD, February 23-27, 2004. Immobilization of Multifunctional Asymmetric Catalysts (MACs), D. Jayaprakash, S. Takizawa, T. Arai, and *H. Sasai, 227

th

ACS National Meeting, California, USA, March, 2004. Organizing Membership in International Meeting T. Majima, 21st International Conference on Photochemistry (ICP21) (Organizing member) Publications in Domestic Meetings 83rd Japan Chemical Society Meeting 6 papers Photochemistry Meeting 8 papers 45th Radiation Chemistry Meeting 2 papers 51th Organic Reaction Chemistry Meeting 1 papers 24th Japan Photomedical Science and Photobiology 3 papers 84th Japan Chemical Society Meeting 31 papers Symposium on Progress in Organometallic Chemistry 1 papers Symposium on Organic Synthesis 1 papers GSC Symposium 1 papers Symposium on Rare Earths 1 papers Symposium on Organic Chemistry -The Next Generation- 2 papers Symposium on Polymer Science 1 papers Congress of Heterocyclic Chemistry 2 papers Symposium on Progress in Organic Reactions 3 papers Sponsorship Grant-in-Aid for Scientific Research (A) (2) T. Majima Molecular Devices by Function-control of Conjugated ¥1,300,000 DNA Grant-in-Aid for Scientific Research in Special Area (2) T. Majima Fundamental Science and Technology of ¥24,600,000 Photofunctional Interfaces Grant-in-Aid for Encouragement of Young Scientists (B) M. Endo Apoptosis Conducted by Photochemical Functionalized ¥1,900,000 Biomolecules and its Application to Cancer Therapy

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Others S. Takizawa COE Fund

Development of Monolayer-protectedMetal Cluster (MPC)-supportedEnantioselective Catalyst and Its Analysisby Transmission Electron Microscope(TEM)

¥500,000

S. Takizawa S. Takizawa

Uehara Memorial Foundation Research Foundation for Materials Science

Synthesis of Chiral Heterocyclic Compounds as Drug Intermediates MPC-supported Asymmetric Catalysts

¥2,000,000

¥800,000

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Department of Nanobiology Professor: Masamitsu FUTAI Associate Professor: Toshihide OKAJIMA Outlines Proteins and those complexed with other biomolecules are regarded as nano bio devices. The research of our group is focused on structural and functional studies of the nano bio devices, as well as their applications in the interdisciplinary field. We are also interested in the development of highly sensitive biosensors and construction of nano machines driven by a molecular motor. Current Research Programs Structural and Functional Studies of Nano Catalytic Devices. The 3-D structures of catalytically interesting enzymes, copper amine oxidase and thermostable adenylate kinase, were analyzed by x-ray crystallography to shed light on their catalytic mechanisms. Combined with kinetic and spectroscopic studies, their highly efficient catalytic mechanisms were elucidated in nano scale details. Development of Highly Sensitive Biosensors. The spectroscopic ellipsometry was applied for sensitive detection of specific protein-protein interactions on SiO2/Si substrates. First, the change of ellipticity of the reflected polarized light (600 – 1100 nm) was correlated with the thickness of the protein layer immobilized on Si surfaces by measuring monomeric (myoglobin) and homotetrameric (hemoglobin) proteins with a similar monomer size. Protein-protein interactions were then measured with the antigen/antibody and cell-surface receptor/ligand systems; in each system either of the two proteins was bound to SiO2 substrates. Consequently, significant ellipticity changes were observed only for the cases where the interactions were specific. A specific antibody binding was also detectable with an antigen displayed on the surface of bacteriophage particles. These results show the usefulness of spectroscopic ellipsometry for sensitive detection of protein-protein interactions and its applicability to a detection method for the protein-based biochips to be developed in the future. Construction of Nano Machines Driven by a Molecular Motor. The rotating mechanism of molecular motor has been analyzed with engineered F- and V-ATPases. Both motors couple an electrochemical proton gradient and a chemical reaction through the rotation of its subunit assembly. Publications Original Papers Diversity of Mouse Proton-translocating ATPase: Presence of Multiple Isoforms of the C, d and G Subunits. G. -H. Sun-Wada, T. Yoshimizu, Y. Imai-Senga, Y. Wada, and M. Futai: Gene, 302 (2003) 147-153.

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Vacuolar H+ Pumping ATPase in Luminal Acidic Organelles and Extracellular Compartments: Common Rotational Mechanism and Diverse Physiological Roles. G. -H. Sun-Wada, Y. Wada, and M. Futai: J. Bioenerg. Biomemb. 35 (2003) 347-358. Specific Recognition of Leishmania major Poly-β-galactosyl Epitopes by Galectin-9: Possible Implication of Galectin-9 in Interaction between L. Major and Host Cells. I. Pelletier, T. Hashidate, T. Urashima, M. Futai, M. Hirashima, N. Nishi, T. Nakamura, K. Kasai, and J. Hirabayashi: J. Biol. Chem. 278 (2003) 22223-22230. Involvement of Syntaxin 7 in Human Gastric Epithelial Cell Vacuolation Induced by the Helicobacter pylori-produced Cytotoxin VacA. J. Suzuki, H. Ohnishi, A. Wada, T. Hirayama, H. Ohno, N. Ueda, H. Yasuda, T. Iiri, Y. Wada, M. Futai, and H. Mashima: J. Biol. Chem. 278 (2003) 25585-25590. From Lysosomes to Plasma Membrane: Localization of Vacuolar Type H+-ATPase with the a3 Isoform during Osteoclast Differentiation. T. Toyomura, Y. Murata, A. Yamamoto, T. Oka, G. -H. Sun-Wada, Y. Wada, and M. Futai: J. Biol. Chem. 278 (2003) 22023-22030. Revised Nomenclature for Mammalian Vacuolar-type H+-ATPase Subunit Genes. A. N. Smith, R. C. Lovering, M. Futai, J. Takeda, D. Brown, and F. E. Karet: Mol. Cell. 12 (2003) 801-803. Lysosome and Lysosome-related Organelles Responsible for Specialized Functions in Higher Organisms, with Special Emphasis on Vacuolar-type Proton ATPase. G. –H. Sun-Wada, Y. Wada, and M. Futai: Cell Struct. Funct. 28 (2003) 455-463. Mouse Proton Pump ATPase C Subunit Isoforms (C2-a and C2-b) Specifically Expressed in Kidney and Lung. G. -H. Sun Wada, Y. Murata, M. Namba, A. Yamamoto, Y. Wada, and M. Futai: J. Biol. Chem. 278 (2003) 44843-44851. Role of Copper Ion in Bacterial Copper Amine Oxidase: Spectroscopic and Crystallographic Studies of Metal-substituted Enzymes. S. Kishishita, T. Okajima, M. Kim, H. Yamaguchi, S. Hirota, S. Suzuki, S. Kuroda, K. Tanizawa, and M. Mure: J. Am. Chem. Soc. 125 (2003) 1041-1055. Rotation of Vacuolar-type Proton Pumping ATPase: Relative Rotation of the G and c Subunit. T. Hirata, A. Iwamoto-Kihara, G. H. Sun-Wada, T. Okajima, Y. Wada, and M. Futai: J. Biol. Chem. 278 (2003) 23714-23719. Detection of Protein-protein Interactions on SiO2/Si Surfaces by Spectroscopic Ellipsometry. S. Kodera, T. Okajima, H. Iwabuki, D. Kitaguchi, S. Kuroda, T. Yoshinobu, K. Tanizawa, M. Futai, and H. Iwasaki: Anal. Biochem. 321 (2003) 65-70.

Chemical and Kinetic Reaction Mechanisms of Quinohemoprotein Amine Dehydrogenase from Paracoccus denitrificans. D. Sun, K. Ono, T. Okajima, K.

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Tanizawa, M. Uchida, Y. Yamamoto, F. S. Mathews, and V.L. Davidson: Biochemistry 42 (2003) 10896-10903. Stereochemistry of 2-Phenylethylamine Oxidation Catalyzed by Bacterial Copper Amine Oxidase. M. Uchida, A. Ohtani, N. Kohyama, T. Okajima, K. Tanizawa, and Y. Yamamoto: Biosci. Biotechnol. Biochem. 67 (2003) 2664-2667. Review Papers New Progress in Research on Peptidyl Built-in Cofactors (In Japanese): T. Okajima and K. Tanizawa: Tanpakushitsu Kakusan Koso 48 (2003) 740-746. International Conferences Subunit Rotation of ATPase Synthase Embedded in Membranes: a or b Subunit Rotation Relative to the c Subunit Ring, *M. Futai, Experimental Biology 2003 Annual Meeting, San Francisco, CA, U.S.A., April 11-15, 2003. Diversity of V-ATPase: From Lysosome to Resorption Lacuna of Osteroclast, *M. Futai, Gordon Research Conference: Molecular and Cellular Bioenergetics, Boston, U.S.A., June 22-27, 2003. Mutational and Crystallographic Investigation of the Role of Aspartate 298 in the Catalysis of Bacterial Copper Amine Oxidase (Poster), *T. Okajima, Y. -C. Chiu, M. Uchida, Y. Yamamoto, H. Hayashi, and K. Tanizawa, 17th Annual Symposium of the Protein Society, Boston, MA, U.S.A., July 26-30, 2003. Involvement of a Hypothetical [Fe-S]-binding Protein in the Biogenesis of Quinohemoprotein Amine Dehydrogenase (Poster), *K. Ono, T. Okajima, and K. Tanizawa, Gordon Research Conference: Protein Derived Cofactors, Radicals And Quinones, Ventura, CA, U.S.A., January 11-16, 2004. Mechanism of Reductive Half-reaction of Bacterial Copper/TPQ-dependent Amine Oxidase (Poster), *T. Murakawa, Y.-C. Chiu, T. Okajima, and K. Tanizawa, Gordon Research Conference: Protein Derived Cofactors, Radicals And Quinones, Ventura, CA, U.S.A., January 11-16, 2004. Contributions to International Journals M. Futai Arch. Biochem. Biophys. (USA, Editorial Board) M. Futai J. Bioener. Biomemb. (USA, Editorial Board) M. Futai J. Biol. Chem. (USA, Editorial Board) M. Futai Biological Chemistry (USA, Editorial Board)

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Publications in National Meetings

Japanese Biochemical Society Japanese Society for Bioscience, Biotechnology, and Agriculture Protein Science Society of Japan Japan Bioenergetics Group The Chemical Society of Japan The Crystallographic Society of Japan

11 papers 1 paper 1 paper 1 paper 1 paper 1 paper

Sponsorship Grants-in-Aid for Scientific Research M. Futai Mechanism of Biological Nanomotors ¥17,900,000 M. Futai ATP Synthase: Mechanism with Subunit Rotation ¥11,100,000 T. Okajima Biogenesis of Built-in Cofactors ¥1,200,000

Entrusted Research M. Futai Japan Science and

Technology Corporation Molecular Mechanism of Proton Pump

¥27,700,000

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Department of Nanosystem Design

Guest Professor Masatoshi TAKAO (2003.4. - 2003.6.) Guest Associate Professor Yoshiyuki MIYAMOTO (2003.10. - 2003.12.)

Outlines

The joint project with nanosystem design division of nanotechnology industry application involves three items: (1) a promotion of academia-industry collaboration. (2) for activation of academic research and development motivations, scientific views for phase change type DVD-RAM recording materials, especially thermo dynamical stability based on random structure in some heavy elements as Ge, Sb and Te. (3) Management of Technology in academia and industry.

In this collaboration, we have established strategy for scientists who do the first-principles calculations. The two important activities are to perform material design with use of well-established software package and to explore new frontier of computational physics. (4) The first goal has been achieved by performing nanotube simulations for the purpose of defect identification and control. (5) The second goal has been achieve to develop computational formulation combining the time-dependent density functional theory (TDDFT) and molecular dynamics (MD) simulation. In this collaboration, we have share key knowledge of computational technique and prepared for future collaborations.

Achievements

1. It is recognized that management of technology MOT is important not only in industry but also in academia including academia-industry mutual collaboration. In Japan, MOT is behind from US, therefore outputs of the academia had not been intensively transferred to Japanese industries. In order to recovering industrial activity, a MOT educational program has been introduced from US to industrial management training curriculum. It is important that the essence of the MOT is an execution by top managements by them. In the new independent government like National Universities, management of technology is more essential as same as industries 2. Thermo-dynamical stability and reversibility of order-disorder phase transformation in multi-elemental alloy system of Ge-Sb-Te is discussed in nano-second order high speed thermal increasing and quenching. The quenching speed in this condition is over 1010K/sec. This value is several orders higher than that of ordinary method, thus diffusions of atoms are prohibited. In case of crystallization from amorphous, the symmetry of first appeared crystalline state should be higher as like as isotropic state of liquid or amorphous in which state long range crystalline order will be expired. In order to obtaining the isotropy, cubic structure is universally realized with more than 25% atomic vacancies in a unit cell. The high crystalline symmetry plays an important role in so many re-writing in DVD-RAM of optical recording media. 3. It was discussed on capabilities of high efficient thermo-electrical transforming devices: Zeebeck element or Pertier element. Theoretical and computational material design will give a possible new material whose figure of merit ZT is more than 3. After obtaining a new material, electric power generation from widely dispersive low

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temperature energy will be realized and mechanismless refrigerator or air conditioner will be also obtained. 4. The development of the combination of the TDDFT and classical MD for the purpose of investigating the excited-state chemical reactions.: (i) Expression of valence wave functions with use of plane wave basis set with full FFT grid in the reciprocal space and application of the Suzuki-Trotter Split operator method to repeatedly operate the time-evolution operator on each wave function were found to be key technique of the TDDFT-MD method. (ii) The extrapolation and interpolation of the self-consistent field along real time axis and efficient parallelization of the computational code were found to accelerate the computational speed. Thus the present code is suitable to the supercomputer system at the Osaka University. 5. Simulation of defect control in carbon nanotubes: (i) Identification of a topological defect was proposed from the TDDFT-MD simulation. Electronic excitation that cause localized vibration can be used to identify a topological defect and combination of the electronic excitation and vibration measurement was found to be a useful experimental method to identify the defect. (ii) An efficient method of nanotube de-oxidation was proposed. In order to avoid a risk of giving damage on C-C network, electronic excitation which causes local C-O breaking, was proposed according to the present TDDFT-MD simulations. This will be one of promising method to purify the carbon nanotubes. 6. Future aspect of the first-principles simulation was given. An important computation is a coupling the time-dependent Schrödinger equation with time-dependent Maxwell equation that enable us to compute the induction of electromagnetic field with dynamically modulated current and to compute the self-inductance of running nano-devices. 7. Lectures were given on April 28, 2003. Prof. M. Takao: “Nanotech in Matsushita Electric and our expectation for academism” May 16, 2003. Prof. M. Takao: “DVD supporting materials, - dirty materials are the most useful for electronic devices” June 6, 2003 Prof. M. Takao: “Energy creation and inorganic materials” June 27, 2003. Prof. M. Takao: “Management technology and academia-industries collaborations” October 16, 2003. Assoc. Prof. Y. Miyamoto: “Value of first-principles simulations in the market.” October 23, 2003. Assoc. Prof. Y. Miyamoto: “Application of TDDFT on femtosecond dynamics” November 20, 2003. Assoc. Prof. Y. Miyamoto: “Simulations of carbon nanotubes” December 8, 2003. Assoc. Prof. Y. Miyamoto: “Future of the first-principles simulations: speed or accuracy?”

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Department of Nanosystem Design

Guest Associate Professor Jun’ichi KANASAKI (2003.4. - 2003.6.)

Outlines

The purpose of this project is to elucidate fundamental processes of excitation-induced atomic processes on semiconductor surfaces for future application of the processes for a new nano-processing to fabricate highly functional nano-structured devices. Laser light and low-energy electron beam with high energy resolution were used as sources of surface excitation, and structural changes were directly imaged by using scanning tunneling microscope (STM).

Achievements

1.A scanning tunneling microscopy study reveals the removal of P and In atoms at intrinsic surface sites of InP (110)-(1x1) through an electronic mechanism under ns-laser excitation. Femtosecond non-resonant ionization spectroscopy detects desorption of P and In atoms associated directly with the bond rupture, and shows their translational energies characteristic of electronic bong breaking. The rate of P-atom removal is four times higher than that of In-atom removal, revealing a prominent species-dependent effect in the excitation-induced instability on semiconductor surfaces. 2.A scanning tunneling microscopy study reveals the site-selective removal of adatoms of the Si(111)-(7x7) surface under low-energy electron beam excitation at 293 K. The rate of center-adatom removal is four times higher than that of corner-adatom removal, similar to the case of ns-laser excitation. However, the rate of bond breaking is almost in proportion to the electron-beam intensity, showing a strong contrast to the case of laser excitation, where the rate shows super-linear dependence on the excitaiton intensity. Publications International Conference Electronic bond rupture of Si-dimers on Si(001)-(2x1) induced by pulsed laser excitation, J. Kanasaki, The 7th International Conference on Laser Ablation, Hersonissos, Greece, October 5-10, 2003.

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Department of Nanosystem Design Guest Professor Toshiaki TAMAMURA (2003.7.-9.)

Outlines Exposure sources for lithography have been photon beam. However, in the fabrication of nanoscale dimension, quantum beam such as electron and EUV is the most promising candidate of exposure sources for the mass production. The elemental technologies for lithography were investigated. Achievements 1.Hole array and LS (line and space) patterns were fabricated by electron beam lithography. With the optimization of process condition, fine patterns were achieved. 2.Nanogap electrodes were fabricated by lift-off method with electron beam lithography.

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Department of Nanosystem Design Guest Associate Professor Hirofumi YAMADA (2003.7. - 2003.9.) Outlines

Atomic Force Microscopy (AFM) is capable of investigating a wide variety of

surface properties on a nanometer scale by detecting selectively local interactions between a tip and a sample. In this study we have discussed the feasibility of realistic applications of nanoprobe techniques based on AFM, especially advanced Dynamic mode Force Microscopy (DFM) , to nanoscale evaluations of various materials. Achievements

The feasibility of an "advanced function nanoprobe" with novel capabilities of

functional nanosensing and nanoprocessing have been explored in terms of scanning probe microscopy technology combined with advanced measurement techniques, biosensing and MEMS technologies. Several specific issues for the development have been clarified. In addition SPM measurement conditions for nanoscale investigations of electrical properties of organic molecules as well as biofunctions have been indicated. Furthermore, we have discussed the possibility of direct measurements of magnetic property change in photo-induced melting of the spin glass or the high-to-low spin state transition by magnetic force microscopy based on DFM.

Original Papers Remanent Polarization of Evaporated Films of Vinylidene Fluoride Oligomers, K. Noda, K. Ishida, A. Kubono, T. Horiuchi, H. Yamada, K. Matsushige : J. Appl. Phys., 93 [5] (2003) 2866-2870. Two-Dimensional Dopant Profiling by Scanning Capacitance Force Microscopy, K. Kimura, K. Kobayashi, H. Yamada, K. Matsushige : Appl. Surf. Sci., 210 (2003) 93-98. Phase-Separated Alkanethiol Self-Assembled Monolayers Investigated by Non-Contact AFM, T. Ichii, T. Fukuma, K. Kobayashi, H. Yamada, K. Matsushige : Appl. Surf. Sci., 210 (2003) 99-104. Effect of Wafer Adsorption on Microscopic Friction Force on SrTiO3 (001), K. Iwahori, S. Watanabe, M. Kawai, K. Kobayashi, H. Yamada, K. Matsushige : J. Appl. Phys., 93 [6] (2003) 3223-3227. Fabrication of Nanogap Electrodes Using Ultrathin Film, T. Miyazaki, K. Kobayashi, K. Ishida, S. Hotta, T. Horiuchi, H. Yamada, K. Matsushige : Jpn. J. Appl. Phys., 42 (2003) 4173-4176. Investigation of Ferroelectric Properties of Vinylidene Fluoride Oligomer Evaporated

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Films, K. Noda, K. Ishida, K. Mochizuki, A. Kubono, T. Horiuchi, H. Yamada, K. Matsushige : Mat. Res. Soc. Symp. Proc., 751 (2003) 217-222. Nanoscale Investigation of Optical and Electrical Properties by Dynamic-Mode Atomic Force Microscopy Using a Piezoelectric Cantilever, N. Satoh, K. Kobayashi, S. Watanabe, T. Fuji, T. Horiuchi, H. Yamada, K. Matsushige : Jpn. J. Appl. Phys., 42 (2003) 4878-4881. Nanoscale Electrical Properties of Molecular Films in the Vicinity of Platinum Ultrathin Film Electrode, T. Miyazaki, K. Kobayashi, K. Ishida, S. Hotta, T. Horiuchi, H. Yamada, K. Matsushige : Jpn. J. Appl. Phys., 42 (2003) 4852-4855. Orientation Control of Poly (vinylidenefluoride-trifluoroethylene) Crystals and Molecules Using Atomic Force Microscopy, K. Kimura, K. Kobayashi, H. Yamada, T. Horiuchi, K. Ishida, K. Matsushige : Appl. Phys. Lett., 82 (2003) 4050-4052. Pyroelectricity of Ferroelectric Vinylidene Fluoride-Oligomer-Evaporated Thin Films, K. Noda, K. Ishida, T. Horiuchi, H. Yamada, K. Matsushige : Jpn. J. Appl. Phys., 42 (2003) L1334-L1336.

International Conference Structures and Piezoelectric Properties of P(VDF-TrFE) Copolymer Ultrathin Films, *K. Kobayashi, H. Masuda, K. Kimura, H. Yamada and K. Matsushige, 3rd International Conference on Scanning Probe Microscopy of Polymers, The Netherlands, July 15-18, 2003. Submolecular-Resolution Non-Contact AFM Study on Metal-Phthalocyanines, *T. Fukuma, K, Kobayashi, H. Yamada, K. Matsushige, 12th International Conference on Scanning Tunneling Microscopy / Spectroscopy and Related Techniques, Eindhoven, The Netherlands, July 21-25, 2003. A Novel 2D Dopant Profiling Technique: Scanning Capacitance Force Microscopy, * K. Kobayashi, K. Kimura, H. Yamada, K. Matsushige, 12th International Conference on Scanning Tunneling Microscopy / Spectroscopy and Related Techniques, Eindhoven, The Netherlands, July 21-25, 2003. Investigations of Organic Molecules by Non-contact Atomic Force Microscopy (Invited), *H. Yamada, T. Fukuma, K. Kobayashi, T. Ichii, K. Matsushige, 6th International Conference on Non-Contact Atomic Force Microscopy (NC-AFM 2003) ,Dingle, Ireland, August 31-September 3, 2003. Submolecular-Resolution on NC-FM on Metal Phthalocyanines, *T. Fukuma, T. Ichii, T. Yoda, K. Kobayashi, H. Yamada and K. Matsushige, 6th International Conference on Non-Contact Atomic Force Microscopy (NC-AFM 2003) , Dingle, Ireland, August 31-September 3, 2003.

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Surface Potential Measurements by Dissipative Force Modulation Method (Poster), *T. Fukuma, K. Kobayashi, H. Yamada and K. Matsushige, 6th International Conference on Non-Contact Atomic Force Microscopy (NC-AFM 2003) , Dingle, Ireland, August 31-September 3, 2003. Imaging Semiconductors by Scanning Capacitance Force Microscopy in Dynamic Mode (Poster), *K. Kobayashi, K. Kimura, H. Yamada, K. Matsushige, 6th International Conference on Non-Contact Atomic Force Microscopy (NC-AFM 2003) ,Dingle, Ireland, August 31-September 3, 2003. Surface Potential Measurements of Phase-separated Self-assembled Monolayers by non-contact Atomic Force Microscopy (Poster), *T. Ichii, T. Fukuma, K. Kobayashi, H. Yamada and K. Matsushige, 6th International Conference on Non-Contact Atomic Force Microscopy (NC-AFM 2003) ,Dingle, Ireland, August 31-September 3, 2003. Applications of Dynamic Force Microscopy to Molecular-scale Investigations of Organic Molecular Films (Invited), *H. Yamada, T. Fukuma, K. Kobayashi, T. Ichii, K. Matsushige, Kyoto University SPM Workshop (Dr. Rohrer's Award Workshop), Kyoto, Japan, February 5, 2004. Characterization of Nanoscale Electronic Devices Utilizing Force Microscopy (Invited), *K. Kobayashi, K. Kimura, H. Yamada, K. Matsushige, Kyoto University SPM Workshop (Dr. Rohrer's Award Workshop) , Kyoto, Japan, February 5, 2004.

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Department of Nanosystem Design

Guest Professor Shinji MATSUI (2003.10. - 2003.12.) Outlines

Recently DNA properties have been investigated to realize new functional

bio-devices. However, there are few reports on DNA nano-patterning to make bio-nanodevices. Therefore, we have developed a new DNA nano-patterning process by applying a nanoimprint method.

Achievements

On a glass substrate coated with poly-L-lysine (PLL) which is known as a

material for DNA immobilization by UV radiation, 1 µg/µl DNA solution was dropped at about 100 µl and was dried at 70 ˚C for an hour, and was irradiated by UV for 2 min. After the DNA was modified with a dye, 4 % polyvinyl alcohol (PVA) solution was coated on the substrate. The substrate was imprinted at 100 ˚C and 6 MPa for 5 min, and a mold was applied with a SiO2 on Si substrate fabricated by electron beam lithography and dry etching. Etching of the DNA substrate was done by reactive ion etching in O2 atmosphere. Finally, the PVA layer washed down by water.

Using the newly developed nanoimprint process, DNA nano-patterning was achieved, which was confirmed by fluorescence microscope.

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Department of Nanosystem Design

Guest Professor Masahiro IRIE (2004.1. - 2004.3.)

Outlines The ultimate goal of optical memory is to store the optical information in each

molecule. To reach this goal it is required to develop molecules, which reversibly change the fluorescence intensity upon irradiation with light of two different wavelengths. The aim of this study is to design and synthesize robust photochromic molecules with a fluorescence unit and evaluate the photo-switching behavior at the single-molecule level.

Achievements

For single-molecule optical memory it is required to develop molecules which reversible change the fluorescence intensity upon irradiation with light of two different wavelengths. The molecules should also exhibit high durability, high sensitivity, rapid response and high fatigue-resistant performance upon coloration/decoloration cycles. We have designed and synthesized a molecule, which has both photochromic diarylethene and fluorescent perylene units. The diarylethene and perylene units are well know to show fatigue resistant property even after prolonged photoirradiation. When the molecules were dispersed in a polymer film, the molecules showed a digital fluorescence switching upon alternate irradiation with ultraviolet and visible light at single-molecule level.

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Department of Nanosystem Design Guest Associate Professor: Yasushi AOKI (2003.1.-3.)

Outlines The aim was the development of a new high performance electron linac and

a femtosecond pulse radiolysis system for quantum beam nanofabrication under the corroboration with the department of beam science for nanofabrication. Achievements

The performance of the new S-band electron linac with a laser photo cathode RF gun was investigated. The final performance was estimated. To get the high time-resolution in the pulse radiolysis, the new detection system was designed.

The following lectures were given. “Research and Development in Private Company” (Feb. 12, 2004)

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Division of Beam Science for Nanotechnology Outlines

The division of beam science for nanotechnology belongs to the nano-science and

nanotechnology center was founded in 2002. The division is composed of five departments with research fields: beam science for nanofabrication, quantum beams for nanotechnology, beam processing for nanotechnology, advanced nanofabrication, and ultra-fast spectroscopy of nanostructures.

Quantum beam science is one of the most important fields for nanoscience and nanotechnology. The researches are performing by using ultra-short electron pulse, slow positron beam, ion beam, electron lithography system and so on. The new trials for nano-science and nanotechnology, such as time-space reaction analysis, positron analysis and nano beam process, will produce a new nano quantum beam science. Achievements

・ Primary Process of Quantum Beam-Induced Nanofabrication ・ Spur Effect in Nanospace of Resits ・ Development of S-band Linac with Laser Photo Cathode RF gun ・ Femtosecond Pulse Radiolysis ・ Atosecond Pulse Radiolysis ・ Optical Device by Using Quantum Beam ・ Improvement of the S-band Linac ・ Generation of the Intense Slow Positron Beam ・ Study of the Annihilation Process of Positronum using AMOC ・ Development of a Pulsing System of the Positron Beam ・ Positron Diffraction Experiment ・ Development of New Resist Materials Based on the Analysis Using the Positron

Beam ・ Electronic Structure and Physical Properties of Molecular Nano-wires ・ Reaction Mechanisms in Polymeric Materials for Micro- and Nano-electronics ・ 1-D Nanostructure Formation by Charged Particle ・ Gas Evolution from Nanoelectronic Materials ・ Radiation-Induced Reactions in Nanoscopic Region ・ Radiation-Induced Reactions in Aromatics

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Department of Beam Science for Nanofabrication Professor: Yoichi YOSHIDA Assistant Professor: Jinfeng YANG Graduate Students: Kouji TAKEYA, Hiroshi TOMOSADA, Takumi SHIMADA,

Takahiro FUJII Research Students: Kouichi KAN Support Staff: Mie TERASHITA Outline

Elucidation of ultrafast reactions in nano-space of the materials is very important for

the development of ultimate fabrications with quantum beam for the next nanotechnology. A new femtosecond pulse radiolysis system has been developed by a laser photocathode electron accelerator and a femtosecond laser. It is expected for the study of quantum-beam-induced reactions in a femtosecond time region, and the development of quantum-beam fabrication processes for nanotechnology.

The developments of an attosecond beam and a time-space reaction analysis in an attosecond time region and nano-space are considered for the control of ultrafast reactions in nano-space in the next ultimate fabrication. It is also expected for the researches in femtosecond science and attosecond science. Current Research Programs 1. Development of Femtosecond Pulse Radiolysis for the Analysis of Radiation-

induced Reactions in nano-space A femtosecond pulse radiolysis was developed in this department for the analysis of

the radiation-induced phenomena in the femtosecond time region. However, in order to achieve femtosecond time resolution, the developments of the three technologies are required: (1)a femtosecond electron pulse, (2)a synchronized analysis femtosecond light source, and (3)a reduction of the degradation due to the velocity difference between the electron and the analysis laser light in samples.

To produce such short electron pulse, a laser-driven photocathode RF gun based a linear accelerator and a magnetic pulse compressor was constructed. The electron pulse produced from the photocathode RF gun was accelerated by a linear accelerator with energy modulation, and then compressed by a magnetic pulse compressor. It was known that the efficiency of electron pulse compression depends on the beam quality. The photocathode RF gun produces a low emittance short-bunch electron beam, such as <1 mm-mrad at 3 ps, resulting in an effective pulse compression into <100 fs. Another advantage by using the RF gun is easy to synchronize the analysis laser light with the electron pulse.

In the pulse radiolysis system, an electron-synchronized femtosecond laser light was used to analyze. A jitter compensation technique was considered to reduce the time jitter between the electron pulse and the analysis femtosecond laser. The time interval of the analysis laser light and the Cherenkov light emitted from the electron pulse in air is measured precisely by a femtosecond streak camera. The data is used to compensate the effect of the time jitter with shot-by-shot in the measurement.

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Finally, the time resolution of pulse radiolysis is limited by the degradation due to velocity difference between the electron and the laser light in samples. The use of a thin sample leads to a higher time-resolution, but the S/N ratio would be decreased in the measurement. In the new pulse radiolysis system, an oblique incidence method of the analysis light was designed. A high S/N ratio can be obtained in this method. Finally, the new pulse radiolysis system with a time resolution of <100 fs can be expected for the elucidation of the primary process of the quantum beam-induced reaction, and the challenge of the ultimate fabrication in nanotechnology. 2. Attosecond Pulse Radiolysis and Attosecond Science

An attosecond pulse radiolysis was considered for the future time-space reaction analysis into attosecond time region. In order to achieve the attosecond time resolution, an attosecond electron beam and an attosecond analysis light, which should be synchronized with each other without time jitter, are required.

A double-decker electron accelerator system was designed to generate such pulses. In the system, two electron pulses with different time and different positions are generated from the photocathode by the irradiation of two laser lights produced from a mode-locked laser, and are compressed into attosecond after acceleration. The former of the electron pulses is used to produce an analysis light by coherent radiation, while the latter is used as an irradiation pulse. The analysis laser light is not used in the system, resulting in no time jitter between the electron pulse and the analysis laser. A time resolution of attosecond can be obtained in the system. However, the production of the attosecond electron beam is a key technique in the next research.

3. Spur Reactions and Nanofabrication The spatial resolution of the nanofabrication is limited with bulk reactions which occur after the spur reactions in material. The reaction mechanism of the spur and bulk reactions and their correlation were studied by using the time-space reaction analysis with a subpicosecond pulse radiolysis. As an example, the primary process of radiation in halocarbon was investigated. The geminate decay of cation radical produced by the irradiation of electron beam was measured with subpicosecond pulse radiolysis and compared with a spur model based on diffusions of a thermalized electron and a positive ion (geminate ion pair, generated by the ionization) in irradiated non-polar liquid under the Coulomb attracting potential. The length of the initial distribution of the electrons, which corresponds to the spur size, was observed to be 1-2 nm, which is shorter than that in alkanes (5-7nm). It is due to the reactions of the electron before its thermalization. Therefore, the reduction of the spur size should be important in the next nanofabrication. Publications Original Papers Subpicosecond Pulse Radiolysis Study of Geminate Ion Recombination in Liquid Benzene, K. Okamoto, A. Saeki, T. Kozawa, Y. Yoshida and S. Tagawa: Chem. Lett., 32 (2003), 834-835. Spatial Beam Profiles of Femtosecond X-ray Pulses Generated by Laser Compton

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Scattering from a Low-emittance Electron Beam, M. Yorozu, J. Yang, Y. Okada, T. Yanagida, F. Sakai, S. Ito, and A. Endo: Appl. Phys., B76 (2003), 293-297. Quantum Efficiencies of Mg Photocathode under Illumination with 3rd and 4th Harmonics Nd:LiYF4 Laser Light in RF Gun, T. Nakajyo, J. Yang, F. Sakai, and Y. Aoki: Jpn. J. Appl. Phys., 42 (2003), 1470-1474. Adjacent Effect on Positive Charge Transfer from Radical Cation of n-Dodecane to Scavenger Studied by Picosecond Pulse Radiolysis, Statistical Model, and Monte Carlo Simulation, A. Saeki, T. Kozawa, Y. Yoshida, and S. Tagawa: J. Phys. Chem., 108 (2003), 1475-1481. International Conferences Femtosecond Pulse Radiolysis for Nanofabrication, *Y. Yoshida, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Control of Spur Size in Material for Nano-fabrication: Study of Primary Process of Radiation Chemistry of Halocarbon by using Subpicosecond Pulse Radiolysis (Poster), *K. Takeya, K. Kan, H. Tomosada, J. Yang, T. Kozawa, Y. Yoshida, and S. Tagawa, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. A New Femtosecond Pulse Radiolysis for Reaction Analysis in Nano-space (Poster), *H. Tomosada, K. Kan, K. Takeya, J. Yang, T. Kozawa, Y. Yoshida, and S. Tagawa, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Development of a Femtosecond Electron Photocathode Linac for Nanoscience and Nanotechnology (Poster), *J. Yang, K. Kan, H. Tomosada, K. Takeya, T. Yamamoto, T. Kozawa, Y. Honda, Y. Yoshida, and S. Tagawa, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Application of Positron for the Nano-structural analysis of Polymers (Poster), *T. Shimada, Y. Honda, M. Tashiro, Y. Terashima, T. Fujii, Y. Yoshida, S. Tagawa, and G. Isoyama, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. The Relation between Spatial Resolution and Reaction Mechanism of Chemically Amplified Resists for Electron Beam Lithography (Poster), *T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida, and S. Tagawa, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Development of a Femtosecond Electron Photocathode Linac for Nanoscience and Nanotechnology (Poster), *J. Yang, K. Kan, H. Tomosada, K. Takeya, T. Yamamoto, T. Kozawa, Y. Honda, Y. Yoshida, and S. Tagawa, 7th SANKEN International Symposium on Hybridization of Chemistry, Biology and Material Science, Osaka, Japan, Jan. 13-14, 2003. Study of Primary Process of Radiation Chemistry of Halocarbon by using Subpicosecond Pulse Radiolysis: Control of Spur Size in Material for Nano-fabrication (Poster), *K. Takeya, K. Kan, H. Tomosada, J. Yang, T. Kozawa, Y. Yoshida, and S. Tagawa, 7th SANKEN International Symposium on Hybridization of Chemistry, Biology and Material Science, Osaka, Japan, Jan. 13-14, 2003.

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252

Publications in Domestic Meetings The Japan Society of Radiation Chemistry 7 papers Linear accelerator Meeting in Japan 5 papers Chemical Society of Japan 1 paper Atomic Energy Society of Japan 8 papers Symposium on Accelerator Science and Technology 5 papers Symposium on Extreme Accelerator 1 paper Symposium on RF Electron Gun 1 paper Symposium on TIARA 2 papers Academic Degrees Master Degree of Engineering Kouji Takeya Study of Spur Reactions for Nanofabrication Sponsorship Grant-in-Aid for Basic Research (A) (2) Y. Yoshida Basic Research on Subfemtosecond and Attosecond Pulse Radiolysis ¥8,500,000 Collaborative Researches

Y. Yoshida RIKEN, Univ. Tokyo High time resolution study on radiation-induced reaction in nanostructure

JAERI Tokai Pulse radiolysis study on Lanthanide solution JAERI Takasaki Mechanism of micro sphere generation in

phenol solution JAERI Takasaki Radiation damage of new recycle chemical

system Sumitomo Heavy Industries,Ltd Development of picosecond laser and double

beam optics Sumitomo Heavy Industries,Ltd Research on photocathode RF gun and high

brightness electron beam Hiroshima Univ. Photonic crystal radiation

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Department of Quantum Beams for Nanotechnology Professor, Director: Goro ISOYAMA Associate Professor: Yoshihide HONDA Research Associate: Norio KIMURA Outlines

For the purpose of research and development of quantum beams and their applications, which are expected to form bases for nanotechnology, we conduct research, in this department, on electron linear accelerators (linacs) for pursuing higher performance and development of quantum beams as well as on new measurement methods for the nanometer range and applications using the beams. The pulse radiolysis technique is commonly used for the reason that the understanding of chemical reaction processes induced by incident electrons helps the fabrication in nanometer range. In order to study the ultra high-speed reactions taking place in nanometer range, development of the linac with higher quality is desired. The high-energy linac is also used to produce a slow positron beam. Positrons have the nature to concentrate in holes and free volumes in materials and consequently measurements using positrons are considered to be an effective method to analyze the sizes and distributions of free volumes. The positron beam is highly expected to play an important role in the analysis of not only the sizes but also the distributions of nanometer size spaces and free volumes in porous materials such as polymers. We conduct research on analyses of free volumes, surfaces and interfaces in thin polymer films, which will be useful to develop new materials by promoting better understandings of interactions of positrons and positroniums, which are formed by an electron and a positron as a bound state, with materials. In order to make these analyses practical, we also conduct researches on the production of intense slow positron beam and on the process of making high brightness beam and short-pulsed beam using an electron linac, and on the development of new measurement methods. We take part in management and operation of the Radiation Laboratory, which has the experimental apparatuses for these studies. Current Research Programs 1. Improvement of the S-band Linac A part of the S-band linac was replaced last year with high quality systems such as modulator system and well-regulated water system relating to the installation of a new RF-gun equipped S-band linac. The RF power units of the S-band linac were shifted to another room for the convenience of experiments and maintenance, and these are shared with two linacs, which are usual 145 MeV linac and new linac. The control system and interlock system were maintained as a result of this change. Preliminary operations of these linacs were also made to find initial troubles. 2. Generation of the Intense Slow Positron Beam In order to study annihilation processes of positrons and positroniums in matter, a positron beam, which is produced with a radioisotope or an electron linac, must be intense to reduce data acquisition time and to get higher S/N. One of the important

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factors determining the intensity is the conversion efficiency of a moderator, which moderates kinetic energy of positrons and produces slow positrons. We designed and fabricated a new moderator to improve the conversion efficiency and to reduce beam diameter. This new moderator will be equipped before the experiment. 3. Study of the Annihilation Process of Ortho-Positronium Using AMOC The lifetime of positrons is usually divided into three components, i.e. lifetimes of para-positronium (p-Ps), free positron and ortho-positronium (o-Ps). The energy spread in the photopeak of annihilation γ-rays, which is represented by S-parameter, consists of these three kinds of annihilation γ-rays in adding to the resolution of detector. These contributions can not be separated in usual measurement, however, AMOC (simultaneous mesurement system of the lifetime of positron and the energy spread of annihilation γ-rays) makes it possible and so AMOC is suitable to study the annihilation process of positron and Ps. The AMOC experiments were carried out in this year for polystyrene related materials using 22Na source, since the slow positron beam based on linac could not be available. Results showed that S-parameters estimated from three kinds of annihilation processes were different. This means that the kinetic energy of annihilation electrons are different among annihilation processes and polymers, which suggests that the o-Ps stays preferentially at special location in polymers. The analysis of potential distribution in polymers was started using molecular orbital theory. 4. Positron Diffraction Experiment Positrons can be used for surface analysis like electrons and have several advantages against electron. To execute such experiments, intense high quality positron beam is required. It is possible to improve the quality such as the emittance, the energy spread and the beam size, by making use of the re-emission process. To find differences between positron and electron, usual RHEED and AES devices are also equipped on the sample chamber. The preliminary experiments of these apparatuses were started. 5. Influence of Functional Groups on Positronium Formation in Polymers We measured the lifetime spectrum of positronium annihilation on polymers containing a functional group, such as OH, Cl, CH2Cl, C6H5CH2O, OH and COOH. The results showed a lowering of the o-Ps yield. These findings indicate that resists containing reactive functional groups react readily with free electrons. The positron annihilation lifetime spectroscopy method may thus be useful to investigate the radiation chemistry of electron-beam resists, because the first event in an electron beam resist material is the ejection of free electrons. Publications Original Papers Behavior of Positronium in Polystyrene and Its Derivatives, Y. Honda, M. Watanabe, M. Tashiro, Y. Terashima, K. Miyamoto, N. Kimura and S. Tagawa : Radiat. Phys. Chem. 68 (2003), 463-465.

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Influence of Radiation-Induced Species on Positronium Formation in poly (methylmethacrylate) at Low Temperature, M. Tashiro, C.Y. Tseng, S. Seki, Y. Honda and S. Tagawa : Radiat. Phys. Chem. 68 (2003) 475-479. The Study of Nano-Space in PHS/PS Bilayer by Slow Positron Beam, Y. Terashima, M. Tashiro, K. Miyamoto, Y. Honda and S. Tagawa : Radiat. Phys. Chem. 68 (2003) 589-592. The Effects of Free Volumes on Charge Carrier Transport of Polysilanes Probed by Positron Annihilation, S. Seki, T. Terashima, Y. Kunimi, T. Kawamori, M. Tashiro, Y. Honda and S. Tagawa : Radiat. Phys. Chem. 68 (2003) 501-505. International Conferences Temporal Evolution of Ortho-Positronium in Polystyrene Related Polymers Using AMOC (Poster), Y. Honda, T. Shimada, N. Kimura, Y. Terashima, M. Tashiro, Y. Yoshida, G. Isoyama and S. Tagawa, 13th International Conference on Positron Annihilation, Kyoto, Japan, Sep. 7-12, 2003. Study of Interfaces in Polymer Bilayers by Slow Positron Beam (Poster), Y. Terashima, S. Seki, K. Miyamoto, M. Tashiro, Y. Honda and S. Tagawa, 13th International Conference on Positron Annihilation, Kyoto, Japan, Sep. 7-12, 2003. Development of a Femtosecond Electron Photocathode Linac for Nanoscience and Nanotechnology (Poster), J. Yang, K. Kan, H. Tomosada, K. Takeya, T. Yamamoto, T. Kozawa, Y. Honda, Y. Yoshida, and S. Tagawa, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Application of Positron for the Nano-Structural Analysis of Polymers (Poster), T. Shimada, Y. Honda, M. Tashiro, Y. Terashima, T. Fujii, Y. Yoshida, S. Tagawa and G. Isoyama, International Symposium on Scientific and Industrial Nanotechnology, Osaka, Japan, Dec. 8-9, 2003. Development of a Femtosecond Electron Photocathode Linac for Nanoscience and Nanotechnology (Poster), J. Yang, K. Kan, H. Tomosada, K. Takeya, T. Yamamoto, T. Kozawa, Y. Honda, Y. Yoshida and S. Tagawa, 7th SANKEN International Symposium

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on Hybridization of Chemistry, Biology and Material Science, Osaka, Japan, Jan. 13-14, 2003. The Interaction between Polymer Thin Films and Positron from Slow Positron Beam, K. Miyamoto, Y. Terashima, M. Tashiro, Y. Honda and S. Tagawa, The 20th Conference of Photopolymer Science and Technology /The International Symposium 2003 Materials & Processes for Advanced Microlithography and Nanotechnology, Chiba, Japan, June 24-27, 2003. Study of Nano-Space in Au-Polysilane Interfaces by Slow Positron Beam, Y. Terashima, S. Seki, M. Tashiro, Y. Honda and S. Tagawa, The 20th Conference of Photopolymer Science and Technology /The International Symposium 2003 Materials & Processes for Advanced Microlithography and Nanotechnology, Chiba, Japan, June 24-27, 2003. Contributions to International Conferences and Journals Publications in Domestic Meetings Japanese Society of Radiation Chemistry 1 papers Linear Accelerator Meeting 8 papers The Atomic Energy Society of Japan 1 papers The Japan Society of Applied Physics 1 papers

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Department of Beam Science for Nanotechnology Professor: Seiichi TAGAWA Associate Professor: Shu SEKI Associate Professor: Takahiro KOZAWA Outlines The targets of the present department are the establishment of initiatives of quantum beams for nanoscience and nanotechnology. Quantum beams mean both beams such as photons and beams inducing interactions with materials in the nanoscopic level of quantum mechanics. The beams potentially have an applicability for imaging with ultra fine patterns, and the present department aims to use the fine patterns as the probes for nano-structured material sciences and devices. Current Research Programs 1. Electronic Structure and Physical Properties of Molecular Nano-wires Polysilanes and polygermanes containing only silicon and germanium in the backbone attracted considerable attention because of their interesting electro-optical properties which are due to conjugated bondings in the main chain. The electronic structure of conjugated skeleton is investigated in the present program, which leads to an improvement the physical properties of the conjugated polymers. 2. Reaction Mechanisms in Polymeric Materials for Nanolithography Chemically amplified resist system is one of the most practical candidates in the future technology in the fabrication of semiconductor and nanotechnology-related products. Reaction mechanisms in the system are analyzed upon exposure to electron beams, X-rays, and laser beams to design a new lithography technique in the present program. 3. 1-D Nanostructure Formation by Charged Particle High density energy deposition by charged particles causes non-homogeneous crosslinking reaction of polysilane derivatives within a nano-sized cylindrical area along an ion trajectory, and gives β-SiC based nano-wires of which sizes (length, thickness) and number densities are completely under control by changing the parameters of incident ion beams and molecular sizes of target polymers. 4. Gas Evolution from Nanoelectronic Materials

Gas evolved from resists deposits on optical system during lithographic exposure, leading to serious optical contamination. This is therefore one of the most grave issues in next generation optical lithography. Dependence of gas evolution on resist structure was investigated by using quadrupole mass spectrometer in order to obtain information on design of contamination-free resist.

5. Radiation-Induced Reactions in Nanoscopic Region

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Electron beam lithography has the highest resolution among top-down writing systems. The ultimate spatial resolution is closely related to the reaction mechanism of resist materials. The relation between a spatial resolution and reaction mechanisms was investigated by a subpicosecond pulse radiolysis. 6. Radiation-Induced Reactions in Aromatics Aromatics have high radiation resistance. The characteristic has been used in electron beam lithography. Especially, the radiation–induced reaction of aromatics is important to improve and understand the resist materials. Primary process of irradiated aromatics from nano- to picosecond time scale is investigated by electron beam pulse radiolysis. Publications Original Papers Subpicosecond Pulse Radiolysis Study of Geminate Ion Recombination in Liquid Benzene, K. Okamoto, A. Saeki, T. Kozawa, Y. Yoshida and S. Tagawa: Chem. Lett., 32 (2003) 834-835. Pulse Radiolysis Study of Radical Cations of Polysilanes, T. Kawaguchi, S. Seki, K. Okamoto, A. Saeki, Y. Yoshida and S. Tagawa: Chem. Phys. Lett., 374 (2003) 353-357. Transient Absorption Spectroscopy of Radical Ions of Rigid Anti- and Syn-tetrasilane, S. Seki, Y. Matsui, S. Tagawa, H. Tsuji, A. Toshimitsu and K. Tamao: Chem. Phys. Lett., 380 (2003) 141-145. Nonisothermal Crystallization Kinetics of Biodegradable Random Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Block One, S. Chanprateep, K. Kikuya, H. Shimizu, S. Seki, S. Tagawa and S. Shioya: J. Chem. Eng. Jpn., 36 (2003) 639-646. Study of Nano-Space in Au-Polysilane Interfaces by Slow Positron Beam: Y. Terashima, S. Seki, M. Tashiro, Y. Honda and S. Tagawa, J. Photopolym. Sci .Technol., 16 (2003) 445-446. Cross-linked Polymer Nanowires with Controlled Shape and Orientation by High Energy Single Ion Hitting, S. Tsukuda, S. Seki, S. Tagawa, M. Sugimoto, A. Idesaki and S. Tanaka: J. Photopolym. Sci .Technol., 16 (2003) 433-434. Relation between Spatial Resolution and Reaction Mechanism of Chemically Amplified Resists for Electron Beam Lithography, T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida and S. Tagawa: J. Vac. Sci. Technol. B21 (2003) 3149-3152. Nano-wire Formation and Selective Adhesion on Substrates by Single Ion Track Reaction in Polysilanes, S. Seki, S. Tsukuda, Y. Yoshida, T. Kozawa, S. Tagawa, M. Sugimoto and S. Tanaka: Jpn. J. Appl. Phys., 43 (2003) 4159-4161.

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Dependence of Outgassing Characters at a 157nm Exposure on Resist Structures, Y. Matsui, S. Umeda, S. Seki, S. Tagawa, S. Ishikawa and T. Itani: Jpn. J. Appl. Phys., 43 (2003) 3894-3899. Influence of Radiation-induced Species on Positronium Formation in Poly(methylmethacrylate) at Low Temperature, M. Tashiro, C.Y. Tseng, S. Seki, Y. Honda and S. Tagawa: Radiat. Phys. Chem., 68 (2003) 475-479. The Effects of Free Volumes on Charge Carrier Transport in Polysilanes Probed by Positron Annihilation, S. Seki, Y. Terashima, K. Kunimi, T. Kawamori, M. Tashiro, Y. Honda, S. Tagawa: Radiat. Phys. Chem., 68 (2003) 501-505. International Conferences Pulse Radiolysis Study on Proton and Charge Transfer Reactions in Poly (methyl methacrylate), A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Adjacent Effect on Positive Charge Transfer from Radical Cation of n-Dodecane to Scavenger Studied by Supbicosecond Pulse Radiolysis, Statistical and Monte Carlo Approach, A. Saeki, T. Kozawa, Y. Yoshida and S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Oriented Nano-wire Formation by Single Ion Track Reaction in Polysilanes, S. Seki, S. Tsukuda, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka and A. Oshima, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Subpicosecond Pulse Radiolysis Study of Solvated Electron in Alcohols, T. Kozawa, Y. Numata, A. Saeki, K. Okamoto, Y. Yoshida, S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Modeling of Nano-wires by Single Ion Hitting for Si-based Polymers, S. Tsukuda, S. Seki, S. Tagawa, 12th International Congress of Radiation Research, Brisbane, Australia, Aug. 17-22, 2003. Outgassed Species from Various Triphenylsulfonium Salts during 157 nm Exposure, Y. Matsui, S. Seki, S. Tagawa, S. Irie and T. Itani, 4th International Symposium on 157 nm Lithography, Yokohama, Japan, Aug. 25-28, 2003. Effects of Ester Groups on Proton Generation and Diffusion in Polymethacrylate Matrices, A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa, Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28-31, 2003. Polymer Screening Method for Chemically Amplified Electron Beam and X-ray Resists, H. Yamamoto, A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa, Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28-31, 2003.

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Outgassed Species from 157-nm-Irradiated Triphenylsulfonium Salts, Y. Matsui, S. Seki, S. Tagawa, S. Irie and T. Itani, Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28-31, 2003. Applications of Polysilanes for a Negative-Tone Resist in Ion Beam Lithography, Y. Matsui, S. Seki, S. Tsukuda, T. Kozawa and S. Tagawa, Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28-31, 2003. Fabrication of Molecular Photoelectronic Devise using Polysilane Nanowires, S. Tsukuda, S. Seki, A. Saeki, T. Kozawa, S. Tagawa, M. Sugimoto, A. Idesaki, S. Tanaka, Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28-31, 2003. The Relation between Spatial Resolution and Reaction Mechanism of Chemically Amplified Resists for Electron Beam Lithography, T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida and S. Tagawa, The 47th International Conference on Electron, Ion and Photon Beam Technology and Nanofabrication, Florida, USA, May 27-30, 2003. Contributions to International Conferences and Journals Publications in Domestic Meetings The Japan Society of Radiation Chemistry 7 papers Chemical Society of Japan 6 papers Atomic Energy Society of Japan 5 papers The Japan Society of Applied Physics: 6 papers Society of Polymer Science, Japan 4 papers Sponsorship Grant-in-Aid for Scientific Research(A)(2) S. Tagawa Femtosecond Pulse Radiolysis Study on

Radiation-Induced Reactions in Nanoscopic Region ¥13,800,000

Grant-in-Aid for Scientific Research(B)(2) S. Seki Isolated Nanowire Formation along Ion Projectiles ¥2,800,000 Grant-in-Aid for Scientific Research, Exploratory Research S. Seki Development of TRMC ¥1,500,000 Grant-in-Aid for Scientific Research, Encouragement of Young Scientist(A)(2) T. Kozawa Subpicosecond Pulse Radiolysis Study on Reaction

Mechanisms of Resist Materials for Nanolithography ¥900,000

Entrusted Research S. Tagawa, S. Seki

Advanced Semiconductor Engineering and Technology

Mechanisms of Polymer Etching Processes by Ultra Low Energy Ion Beams

¥4,000,000

S. Tagawa Advanced Reaction Mechanism in Chemically ¥1,575,000

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Semiconductor Engineering and Technology

Amplified Resist Materials

S. Tagawa, S. Seki

Semiconductor Leading Edge Technology Inc.

Outgassing Characters from F2 Laser Resist Materials

¥5,250,000

Cooperative Research S. Tagawa, S. Seki

Japan Atomic Energy Research Institute

Ion Beam Pulse Radiolysis in Condensed Matter

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Department of Ultrafast Spectroscopy of Nanostructures Guest Associate Professor: Wenjie Guan (2003.5.1. – 2003.7.31.) Outlines

Ferromagnetism of the V dope ZnO is related to the carrier concentration in a thin film from the past research. Ferromagnetic substance was aimed by using an oxygen vacancy as a donor until now, but there is a problem in reproducibility. Therefore, we focus on the chemical doping method for controlling the amount of carrier to get the ferromagnetic substance of the V dope ZnO.

Achievements The magnetic properties of (Zn, V)O:Al thin film which is formed by a pulsed laser deposition method are investigated. This work is based on the work of H. Saeki in Tabata laboratory. In his work, the films which are deposited under the oxygen pressure of 1 mTorr show an insulative conduction and a paramagnetic feature. On the contrary, films with a low resistance show a ferromagnetic feature. But it is quite hard to control the conductivity by changing the amount of oxygen vacancy which acts as a donor in ZnO. In this work, Dr. Guan formed the Al doped (Zn,V)O thin films to avoid the problem of reproducibility. The (Zn,V)O:Al films deposited under the oxygen pressure of 5mTorr have low resistivity because of Al ions acts as n-type donor in this film and these films show ferromagnetic hysteresis curve at 300K. The temperature dependency of magnetization indicates that the Curie temperature of this film is higher than 360K. From these results, the carrier density in (Zn,V)O thin films can be controlled by a doping Al ions. The chemical doping method is more effective to improve the reproducibility than the method of an oxygen pressure control.

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Department of Ultrafast Spectroscopy of Nanostructures Guest Professor: Jai Pal MITTAL (2003.11.1 – 2004.1.31) Outlines

Quantum beam-induced fast reaction processes were studied by using picosecond and nanosecond pulse radiolysis. The reaction mechanisms in nano-scale were studied by the time-space analysis method and are expected to be applied in the quantum beam nanotechnology. Achievements

The formation mechanisms of nano particles were studied for the application of the quantum beam nanotechnology. The solvated electron and OH radical played an important role in the mechanisms. Final nano particle products can be controlled by investigating the primary process in femtosecond and attosecond pulse radiolysis.

The following lectures were given. “Radiation Chemical Synthesis of Metallic Nano-Particles: Their Characterization and Catalytic Properties” (Int. Symp. Sci. Industrial Nanotech., Dec.9, 2003) “Site Selectivity in the Reactions of eaq

- and oh Radicals with Solvent Pulse Radiolysis Investigation” (Int. Workshop “Beam Sci. Nanotech., Jan.15, 2004) “What is the Next Problem in Primary Process of Radiation Chemistry?” (Jan.30, 2004)

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Division of Nanoscience and Nanotechnology for Industrial Applications Outlines

This division involves five laboratories, i.e., Department of Nanomaterials and Envirmentally Conscious Technology, Department of Computational Nanomaterials Design, Department of Nano-Bio-Intelligent Systems Science, Department of Propatent Strategy for Nanotechnology(Domestic visiting researcher), Department of Nanotechnology Transfer(Foreign visiting researcher). All of these laboratories have the same direction to make contribution to society and industries through their own nanotechnology. Through the activity of these laboratories in the first year, establishments are listed as follows. Achievements Suganuma Lab.

Basic science and technology for lead-free soldering have been focused on in this laboratory as one of the key environmental conscious technologies. The best composition range for Sn-Ag-Cu solder alloy becomes clear based on the formation of coarse intermetallic compounds. The guideline of designing reliable Sn-Zn soldering was established. The interface nano-structures of solder/Cu and Ni plating were identified by TEM. As other research subjects, heat-resistant materials, biomaterials and fullerene materials are investigated as follows. Processing conditions and properties of Ni, Fe, Ti based aluminides were investigated and nano-to-micro scale designing concept was established. Ti-PVA/porous apatite bio cartridges were developed. Atomic design, HREM observation and simulation and three-dimensional imaging techniques were established and C・BN fullerene materials were investigated. Mizoguchi Lab. ・ Extension of the preliminary nanotech-ontology developed last year. ・ Development of functional decomposition trees for nano-particles/films and ・ Development of prototype system for supporting creative design of nanomaterials

at the functional level. ・ Development of Cell Signaling Networks Ontology.

Katayama-Yoshida Lab. ・ Development of ab initio molecular dynamics simulation (OSAKA-2003-Nano) ・ Electronic excitation induced nano-structure-process design (From graphite to

Nano-diamond) ・ Tc-enhanced Co-doping and Nano-scale delta-doping method for diluted

magnetic semiconductors. ・ Materials design of high-efficient thermo-electric Nano-materials. ・ Design of nano-structure gettering center in silicon. ・ Mechanism of CN-treatment of dangling-bond in amorphous siliconand high

efficient photovoltaic solar cels.

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265

・ Development of method by ab initio molecular dynamics simulation in high-temperature and high-pressure.

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Department of Nanomaterials and Environmentally Conscious Technology Professor: Katsuaki SUGANUMA Associate Professor: Takeo OKU Research Associates: Shunro YAMAGUCHI, Masahiro INOUE Research Assistant: Kimiaki TANIHATA Post Doctoral Fellow: Kim KEUN-SOO Research Promotion Staff: Mariko HATAMURA Graduate Students: Kim YOUNG-SUN, Masayuki NAKATA, Shinsuke AOKI,

Hwang CHI-WON, Munenori YAMASHITA, Ichihito NARITA, Toshinori MATUURA,

Tokuji MIYAMOTO, Takayuki IMANISHI, Atsushi NISHIWAKI, Yuusuke YAMASAKI

Support Staff: Naomi URAYAMA Outlines

Through nanotechnologies and knowledge for organic/inorganic materials, we are conducting the development of environmentally conscious fine technologies for electronics packaging area, i.e., lead-free soldering and conductive adhesives, the composite materials based on metals and intermetallic compounds, the structural characterization of BCN fullerenes, and the bio mimetic bone structures. We set our route towards contributions to our society in near future. Current Research Programs 1. Environmentally Conscious Electronics Packaging The development of environmentally conscious fine technologies for electronics packaging area, i.e., lead-free soldering and conductive adhesives, and the establishment of scientific basis required for those technologies are our goals. For lead-free soldering, we found that solidification phenomena become critical rather than the conventional leaded alloys. By using simulation and the in-situ observation method for soldering solidification, the mechanisms and the various factors influencing on CSP defect formation became clear. The suppression method of solidification defects was proposed. Interface nano structures were identified by HREM and the precise interface formation mechanism, especially on the interface of Ni-P/Sn-Ag-Cu, was proposed. The composite mixture rules were adopted for understanding the properties of nanopaste and conductive adhesives and it was proved that the interface bonding nature has key role for understanding the practical conductive adhesives. 2. Atomic Structure Analysis and Electronic Properties of New B-C-N Fullerene Materials

Synthesis and HREM structure analysis of the new B-C-N fullerenes, nanotubes and nanocapsules. Structural optimization, electronic state calculation and physical property

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prediction by ab initio molecular orbital and molecular dynamics calculation. Establishment of quantitative HREM of 3D atomic arrangement in nano scale region. 3. Biomimetic Approach to Artificial Joint

As an artificial joint model, a cultured cartilage fixed with porous apatite was fabricated. By incorporation of growth factor in the porous apatite, calcination inside of the porous apatite was promoted to afford tight fixation between the cultured cartilage and porous apatite. 4. Development of Bioactive Bone Cement

For bone cements the following characteristics were required. 1) biocompatibility, 2) mechanical strength, 3) shortening of hardening, 4) resorption of bone cement. As new bone cements satisfied with the requirement, we are developing a resorbable bone cement which consists of organic-calcium phospate nanocomposite and nanocomposite-PMMA bone cement with self-repairing function. 5. Surface Functionalization of Metallic and Intermetallic Materials Novel chemical processes for surface modification of metallic and intermetallic materials are developed in order to realize several functions including catalysis, biocompatibility and durability. 1) Fabrication of functional ceramic thin films by sol-gel electrophoresis process 2) Direct formation of graded functional ceramic layers by reactive plasma process 3) Surface modification of conductive fillers by self-assembled monolayers Publications Original Papers Improvement of Properties of Sn-Cu Lead-free Solder by Third Element Alloying and Its Reliability for Through-hole Circuit Assembly, S. –H. Huh, K. –S. Kim and K. Suganuma : Adv. In Tech. of Mat. And Mat. Proc. J. , 5[1] (2003) 1-6. Effect of Intermetallic Compounds on Properties of Sn-Ag-Cu Lead-free Soldered Joints, K.-S. Kim, S. -H. Hwuh and K. Suganuma: J. Alloys Compounds, 352[1-2] (2003) 226-236. Effect of Composition Cooling Rate on the Microstructure and Tensile Properties of Sn-Zn-Bi Solder Alloy , Y.-S. Kim, K.-S. Kim, C.-W. Hwang, K. Suganuma: J. Alloys Compounds , 352[1-2] (2003) 237-245. Effects of Fourth Alloying Additive on Microstructures and Tensile Properties of Sn-Ag-Cu Alloy and Joints with Cu, K.-S. Kim, S. -H. Hwuh and K. Suganuma: Microelectronics Reliability, 43 (2003) 259-267. In situ Observation and Simulation of Solidification Process in Soldering SOP with Sn-Ag-Cu Lead-free Alloy, K. S. Kim, M. Haga and K. Suganuma: J. Electron. Mater., 32[12] (2003) 1483-1489. Interfacial Microstructure between Sn-3Ag-xBi Alloy and Cu Substrate with or without

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Electrolytic Ni Plating, C. Hwang, J.-G. Lee, K.Suganuma and H. Mori: J. Electron. Mater. , 32[2](2003) 52-62. Influence of Ag Addition to Sn-Bi Eutectic Alloy on Microstructure and on Mechanical Properties (in Japanese) , K.Suganuma, T.Sakai and K.-S.Kim : J.Japan.Inst.Electron. Packaging 6・5 (2003) 414-419. Effects of Fourth Alloying Additives on Interfacial Microstructure of Sn-Ag-Cu Lead-free Soldered Joints, K.-S. Kim, K. Suganuma, T. Shimozuki and C. G. Lee: Mater. Sci. Forum, 439 (2003) 7-11. Interfaces in Lead-free Soldering, C.-W. Hwang, K.-S. Kim and K. Suganuma: J. Electron. Mater. , 32[11] (2003) 1249-56. Interface Microstructure between Fe-42Ni Alloy and Pure Sn , C.W. Hwang, K. Suganuma, J.-G. Lee and H. Mori,: J. Mater. Res. , 18 (2003) 1202-1210. Interface Microstructure between Fe-42Ni Alloy and Pure Sn, C.-W. Hwang, K. Suganuma, J.-G. Lee and H. Mori: J. Mater. Res. , 18 (2003) 2540-2543. A New Approach to an Artificial Joint Based on Bio-cartilage / Porous β-tricalcium Phosphate System, S. Aoki, S. Yamaguchi, A. Nakahira and K. Suganuma: J. Euro. Ceram. Soc. 23 , (2003) 2939–2946. Spreading of Sn-Ag Solders on Fe-Ni Alloys, E. Saiz, C.-W. Hwang, K. Suganuma and A. P. Tomsia: Acta Mater. , 51[11] (2003) 3185-3197. Wetting and Strength Issues at Al/α-Alumina Interfaces, E. Saiz, A. P. Tomsia, and K. Suganuma: J. Euro. Ceram. Soc. , 23 (2003) 2787–2796. Effect of the Joining Pressure on Ag-epoxy Conductive Adhesive/Sn Interfaces Exposed to Heat, M. Yamashita and K. Suganuma: J. Mater. Sci. Lett. , 22[19] (2003) 1311-1313. Bioactive Glass Coatings for Orthopedic Metallic Implants, S. Lopez-Esteban, E. Saiz, S. Fujino, T. Oku, K. Suganuma and A. P. Tomsia: J. Euro. Ceram. Soc., 23 (2003) 2921-2930. The Catalytic Activities of Nanoclusters Dispersed on Apatite, J. Ichihara, K. Iteya, H. Kawaguchi, Y. Sasaki, H. Nakayama, S. Yamaguchi: J. Ceram. Proc. Res. ,4 (2003) 42-44. Cetylpyridinium Dodecatungstate on Fluorapatite: Efficient and Reusable Solid Catalyst for Solvent-free Epoxidation, J. Ichihara, A. Kambara, K. Iteya, E. Sugimoto, T. Shinkawa, A.Takaoka, S. Yamaguchi, Y. Sasaki: Green Chemistry , 5 (2003) 491-493. Twin Structures of Rhombohedral and Cubic Boron Nitride Prepared by Chemical Vapor Deposition Method, T. Oku, K. Hiraga, T. Matsuda, T. Hirai and M. Hirabayashi:

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Diamond Relat. Mater. , 12 (2003) 1138-1145. Effects of Catalytic Metals for Synthesis of BN Fullerene Nanomaterials, I. Narita and T. Oku: Diamond Relat. Mater. ,12 (2003) 1146-1150. Synthesis, Argon/Hydrogen Storage and Magnetic Properties of Boron Nitride Nanotubes and Nanocapsules, T. Oku and M. Kuno: Diamond Relat. Mater., 12 (2003) 840-845. Direct Observation of B84 and B156 Clusters by High-resolution Electron Microscopy and Crystallographic Image Processing, T. Oku: Sol. State Comm., 127 (2003) 689-693. Formation and Structures of Multiply-twinned Nanoparticles with Fivefold Symmetry in Chemical Vapor Deposited Boron Nitride, T. Oku, K. Hiraga, T. Matsuda, T. Hirai and M. Hirabayashi: Diamond Relat. Mater. , 12 (2003) 1918-1926. Direct High-resolution Electron Microscopy of BN Nanotubes with Hexagonal Zigzag Network, I. Narita and T. Oku, Chem. Phys. Lett.: 377 (2003) 354-358. Synthesis of Boron Nitride Nanotubes by Using NbB2, YB6 and YB6/Ni Powder, I. Narita and T. Oku: Diamond Relat. Mater. , 12 (2003) 1912-1917. Formation and Structure of B24N24 Clusters, T. Oku, A. Nishiwaki, I. Narita and M. Gonda:Chem. Phys. Lett. ,380 (2003) 620-623. Iron Nanoparticles Coated with Boron Nitride Nanolayers by a Solid Phase Reaction, H. Tokoro, S. Fujii and T. Oku: IEEE Trans. Mag., 39 (2003) 2761-2763. First-principles Study of La-B36N36 cage, Q. Wang, Q. Sun, T. Oku, Y. Kawazoe: Physica B, 339 (2003) 105-109. Reviews Environmental technology trend of electronics packaging concerning with lead-free soldering (in Japanese) . K.Suganuma : Surface Mount Technology Magazine, 1 (2003) 2-9.

Current status and prospect of lead-free packaging technology (in Japanese) . K.Suganuma : RCJ Kaihou, 29・4 (2003) 2-11.

European registration on electronics waste and technological trend of lead-free soldering (in Japanese). K.Suganuma : Denshizairyou 5 (2003) 2-10. Basic science and technology trends of lead-free soldering and halogen-free (in Japanese). K.Suganuma : Surface Mount Technology Magazine, 6 (2003) 16-21.

European registration on electronics waste and practical advanced technology for lead-free soldering (in Japanese). K.Suganuma : Kinzoku, 73 (2003) 40-51. Advanced adhesive technology as lead-free advanced packaging (in Japanese).

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K.Suganuma : Hitachi-Kasei Technical Report, 41 (2003) 5-6. Current Status of Low Temperature Lead-Free Soldering in Market (in Japanese). K.Suganuma : J.Japan.Inst.Electron.Packaging, 6・5 (2003) 369-374. Ink jet printing becoming advanced factory(in Japanese). K.Suganuma : Zikkyou Rika Shiryo, 54 (2003) 8-13. Current Status of Lead-free Soldering, K.Suganuma : SMT China, Nov/Dec (2003) 42-49.

The World of Oxide -Atomic Fluctuation- High-resolution Image of Ag2SnO3 (in Japanese) , T.Oku : Gendaikagaku 382 (2003) 52-53.

The World of BN and Diamond –Shining Five Stars- High-resolution Image of Multiply Twined Particles (in Japanese) , T.Oku and K.Hiraga : Gendaikagaku 383 (2003) 52-53.

The World of Carbon –Onion Synthesis- High-resolution Image of Carbon Onion (in Japanese), T.Oku and I.Narita : Gendaikagaku 384 (2003) 52-53.

The World of Self-organization –What is Beautiful Harmony?- High-resolution Image of Au Nanoparticles and Zeolite (in Japanese) , T.Oku : Gendaikagaku 385 (2003) 32-33.

Modulated Structure of the Composite Crystal [Ca2CoO3]0.62CoO2, Y. Miyazaki, M. Onoda, T. Oku, Y. Ishii, Y. Morii, T. Kajitani:JAERI-Review (2003) 66-67. Book Wettability and interfacial structure of lead-free solder. (Fine printing condition optimization and troubleshooting) (in Japanese), K.Suganuma, Gijyutujyouhou-kyoukai, (2003) 39-52. The lead-free solder packaging technology. - From basic science to lift-off countermeasure- (in Japanese), K.Suganuma, Coronasya,(2003) 1-19, 22-41, 193-205. Research and Development in Japan , K. Suganuma, Handbook of Lead (Pb)-Free Technology for Microelectronic Assemblies (2003) Visual eco-materials (in Japanese), K.Suganuma, Kougyou-chosakai, (2003) 54-57. Advanced conductive adhesive technology (in Japanese), K.Suganuma, Kougyou- chosakai, (2003). Science, Technology and Education of Microscopy: an Overview-Atomic Structure Analysis of Advanced Materials by High-Resolution Electron Microscopy(Edited by A. Mendez-Vilas)T. Oku, FORMATEX,. (2003) 224-234. Art and Science of Healing (in Japanese) , T. Oku, Sankeisya, (2003).

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International Conference In situ Observation and Simulation of Solidification Process in Soldering SOP with Sn-Ag-Cu Lead-Free Alloy, M. Haga, *K.-S. Kim and K. Suganuma,132nd TMS Annual Meeting & Exhibition, San Diego, California, March 2–6, 2003. Interface Microstructure between 42 Alloy and Sn-based Lead-free Solder, *C. -W. Hwang, J. G. Lee, H. Mori and K. Suganuma, 132nd TMS Annual Meeting & Exhibition, San Diego, California, March 2–6, 2003. Interfaces in Lead-free Soldering(Invited), *C.-W. Hwang, K.-S. Kim and K. Suganuma, 132nd TMS Annual Meeting & Exhibition, San Diego, California, March 2–6, 2003. Analysis of Surface Reaction Behavior for Generating Atomic Hydrogen on Ni3Al Surfaces, *M. Inoue and K. Suganuma, 132nd TMS Annual Meeting & Exhibition, San Diego, California, March 2–6, 2003. Squeeze Casting for Low Cost Fabrication of Advanced Materials and Joints, *K. Suganuma, M. Inoue and K. Tanihata, Proc. US-Japan workshop on Low Cost Production of Ceramics and Related Materials, Osaka, March 17, 2003, 83-89. Solderability and Interface Property of Sn-Zn-Bi on Metal Substrates,*Y-S.Kim, C-W.Whang, K.Suganuma, International Conference on Electronics Packaging (ICEP2003), JIEP, Tokyo, April 16-18, 2003, 345-348. Interfacial Reaction of Sn-based Lead-free Solder with Fe-42Ni Substrate,*C-W. Hwang, K.Suganuma, International Conference on Electronics Packaging (ICEP2003), JIEP, Tokyo, April 16-18, 2003, 360-365. Joining Silicon Carbide/Aluminum Composite, *M. Nakata, K.Tanihata and K.Suganuma, International Conference on Electronics Packaging (ICEP2003), JIEP, Tokyo, April 16-18, 2003, 381-386. Solderability and Interface Property of Sn-Zn-Bi on Metal Substrates, Y. S. Kim, K. S. Kim,C. W. Hwang, and *K. Suganuma, International Conference on Electronic Packaging (ICEP 2003),April16-18,Tokyo 2003, 345-348. Current Technology of Low Temperature Lead-Free Soldering and JIEP Project, *K. Suganuma, T. Kiga, M. Takeuchi, Q. Yu, K. Tanabe, K. Toi, H. Tanaka, Y. Kato, K. Sasaki, K. Takahashi, M. Tadauchi, T. Tsukui, T. Suga and T. Makimoto, Internatiuonal Conference on Lead Free Electronics “Towards Imprementation of the RHS Directive”, IPC/Soldertech, Brussels, June 10-11, 2003, 97-104. Interfacial stability of Sn-Ag-Cu Lead-free Solder with Ni-P Alloy Plating, *K. Suganuma, C.-W. Hwang, M. Kiso and S. Hashimoto, Interl Technology Symposium,

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“Sesigning for next generation Computing Platforms”, San Jose, Sep.16-17, 2003, p.18. Curing Characteristics of Nano Paste for Fine Printed Circuits, *K.-S. Kim, M. Hatamura, S. Yamaguchi and K. Suganuma, Proc.3rd International IEEE Conference on Polymers and Adhesives in Microelectronics and Photonics (Polytronics 2003), Montreux, Switzerland, 2003, 369-374. Development of New Sn-Ag-Cu Lead-free Solders Containing Fourth Elements, K.-S. Kim, *K. Suganuma,Third International Symposium on Environmentally Conscious Design and Inverse Manufacturing Tokyo, Japan, December 8-11 2003, 165-166. The Cultured Cartilage / Porous β-tricalcium Phosphate (TCP) System as an Artificial Joint Model, *S. Aoki, S. Yamaguchi and K. Suganuma, 3rd Asian BioCeramics Symposium (ABC2003), Fukuoka, Japan, November 18-20, 2003. Synthesis and Aldehyde Absorption Properties of Asp-OCP Inclusion Compound, *S. Aoki, A. Nakahira, H. Nakayama, K. Sakamoto, S. Yamaguchi and K. Suganuma, 12th International Symposium on Intercalation Compounds, Poznan, June1-5,2003. Formation and Atomic Structures of BnNn (n = 24-60) Clusters Studied by Mass Spectrometry, High-resolution Electron Microscopy and Molecular Orbital Calculation, *T. Oku, A. Nishiwaki and I. Narita, 14th European Conference on Diamond, Diamond-Like Materials, Carbon Nanotubes, Nitrides and Silicon Carbide, Salzburg, Austria, Sept. 7-12(8), 2003, Abst. 5. 7. 12. Atomic Structures and Stabilities of Zigzag and Armchair-type Boron Nitride Nanotubes Studied by High-resolution Electron Microscopy and Molecular Mechanics Calculation, *T. Oku and I. Narita, 14th European Conference on Diamond, Diamond-Like Materials, Carbon Nanotubes, Nitrides and Silicon Carbide, Salzburg, Austria, Sept. 7-12(8), 2003, Abstract Book 5. 8. 10. Formation, Atomic Structural Optimization and Electronic Structures of Tetrahedral carbon onion, *T. Oku, I. Narita and A. Nishiwaki, 14th European Conference on Diamond, Diamond-Like Materials, Carbon Nanotubes, Nitrides and Silicon Carbide, Salzburg, Austria, Sept. 7-12(11), 2003, Abstract Book 15. 6. 2. B12@B12@B60 and B12@(B12)12 Giant Clusters with Doping Atoms Observed by High-resolution Electron Microscopy, *T. Oku, International Symposium on Novel Carbon-Rich Organic Materials, Osaka, Sept. 29-30(29), 2003, Abstracts p. 50. Synthesis and Atomic Structures of Boron Nitride Cage Clusters and Nanotubes, *T. Oku, I. Narita and A. Nishiwaki, International Symposium on Novel Carbon-Rich Organic Materials, Osaka, Sept. 29-30(29), 2003, Abstracts p. 51. Molecular Orbital Calculations of Endohedral B36N36 Clusters with Doping Elements, A. Nishiwaki and T. Oku, International Symposium on Novel Carbon-Rich Organic

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Materials, Osaka, Sept. 29-30(29), 2003, Abstracts p. 52. Three-dimensional Nanostructural Characterization of B12-based Cluster Solids by HREM and Crystallographic Image Processing, T. Oku, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Dec. 8-9(8), 2003, Abstracts p. 55. Atomic Structures and Electronic States of Boron Nitride Nanocage Clusters and Nanotubes, T. Oku, I. Narita and A. Nishiwaki, Nanoscience and Nanotechnology on Quantum Particles 2003, Tokyo, Dec. 15-17(15), 2003, Abstracts p. 39. Formation and Atomic Structures of Boron Nitride Nanohorns, A. Nishiwaki, T. Oku, Nanoscience and Nanotechnology on Quantum Particles 2003, Tokyo, Japan, 15-17 December, 2003, p. 19. Nanostructural Characterization of B12-based Cluster Solids by HREM and Crystallographic Image Processing, *T. Oku, Nanoscience and Nanotechnology on Quantum Particles 2003, Tokyo, Dec. 15-17(15), 2003, Abstracts p. 18. Contributions to International Conferences and Journals K. Suganuma EcoDesign2003 Symposium committee Publications in Domestic Meetings Japan Institute of Electronics Packaging 5papers Japan Institute of Metals 2papers Others 2papers Sponsorship Grant-in-Aid for Scientific Research on Scientific Research (A)(2) K. Suganuma Prevention of Formation of Solidification Defects for

Lead-free Soldering ¥2,200,000

Grant-in-Aid for JSPS Research Fellowships for Young Scientists I.Narita Structures and Properties of New BCN Nanoclusters ¥1,500,000 Other Allocations K. Suganuma M. Inoue

21st Century COE Program 21st Century COE Program for Young Scientists

¥8,110,000

¥1,000,000 K-S. Kim 21st Century COE Program for Young Scientists ¥1,000,000 S. Aoki Y-S.Kim C-W.Hwang

21st Century COE Program for Young Scientists 21st Century COE Program for Young Scientists 21st Century COE Program for Young Scientists

¥400,000

¥400,000

¥400,000

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M.Yamashita

21st Century COE Program for Young Scientists

¥400,000

I. Narita 21st Century COE Program for Young Scientists ¥650,000 Entrusted Research Japan Society for the Promotion of Science K. Suganuma Research System for Materials Science System ¥3,500,000 Other Research Fund The Shinsei foundation K. Suganuma Dynamically Reliability of Conductive Adhesives ¥800,000

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Department of Computational Nanomaterials Design Professor: Associate Professor: Research Associate: Visiting Scientist: Research Technical Experts:

Post Doctoral Fellows:

Research Students: Graduate Students:

Under Graduate Student: Support Staff:

Hiroshi KATAYAMA-YOSHIDA Koun SHIRAI Kazunori SATO Shunichi YANAGIYA Kiichi AMAYA, Ayao OKIJI, Mitsuhiro MOTOKAWA Akira MASAGO, Van An DINH, Hiroyuki NAKAYAMA, Ikutaro HAMADA YunHee CHANG Takayoshi MATSUMURA, Naoki MITSUDA, Kunihiko YAMAUCHI, Hiroki FUNASHIMA, Hideyuki MATSUOKA, Yuki OHISHI, Michito SUZUKI, Masayoshi SEIKE, Toshiyuki MICHIKITA, Hidetoshi KIZAKI, Kazuhide KENMOCHI, Masayuki TOYODA, Tetsuya FUKUSHIMA Hideaki MOTOSHIMA Mika ASADA

Outlines The primary activities of this department are theoretical study of electronic properties of nanomaterials, which are different from those of bulk crystals. The first-principles calculations based on the density-functional theory are used, in order to exclude any empirical parameters. More importantly, we wish to predict unknown features of new nanostructure and design novel nanomaterials. Lead of the area of material research from the theoretical viewpoint is one of our goals. At the same time, efforts are continued to keep development in the methodologies in order to solve difficult problems encountered in this field, because nanoscience is different from study of bulk materials with many respects. Current Research Programs 1. Spintronics and Materials Design Using Semiconductor Nanostructurs. Based upon ab initio electronic structure calculation, we have proposed the materials design to control the spin interaction for II-VI and III-V compound semiconductors. We have designed the transparent half-metallic ferromagnets for GaN-, AlN-, ZnO-, ZnS-based diluted magnetic semiconductors. We also design the p-type and n-type carrier-concentration dependence of Curie temperature (Tc) and 3d transition atom dependence of Tc in above diluted ferromagnetic semiconductors. New functional 4d-transition-metal (4d-TM)-doped K2S diluted magnetic semiconductors with transparent and half-metallic ferromagnetism are designed based upon the first principles calculations. We have systematically investigated the magnetism in 4d-TM-doped K2S DMSs. K2S is a

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transparent semiconductor with anti-CaF2 crystal structure and has large lattice spacing due to its large ionic radius of K. It is found that Zr-, Nb-, Tc-, Ru- and Rh-doped K2S show the half-metallic and high-spin ferromagnetism and that Zr- or Nb-doped K2S are promising candidate for high-Tc ferromagnetic DMSs with transparency and large magneto-optical effect.. 2. Materials Design and Valence Control of Wide Band-gap Semiconductors. Based upon ab initio electronic structure calculation, we have proposed codoping method for the fabrication of the low-resistive p-type CuAlO2, and n-type diamond. Our predictions of co-doping for the valence control are confirmed by the experiment. We have calculated the formation energy of P, N, and B in diamond, and oxygen-interstitial, Cu-vacancy, Al-vacancy, Be-acceptor, Mg-acceptor in CuAlO2.We also proposed the possibility of high efficient thermo-electric material (ZT>3) and transparent superconductivity upon slightly p-type or heavily p-type doped CuAlO2. 3. Development of Pseudopotential Electronic-structure Calculation Codes “Osaka2002_nano” Improvement and extension of our original first-principles calculation code 'Osaka2002_nano' have been in progress. In particular, in this year, nonlinear core-correction was implemented. This improves accuracy for transition metals and alkaline metals. For molecular dynamic simulation, Nose algorithm has been implemented, which enables us to perform molecular dynamic simulation at a constant temperature in a realistic manner. 4. Structures of Solid Borons Growing interests are addressed to solid borons because of its superconducting transition at high pressures. Electronic structure study of borons is barely progressed, because of many complicated structures. We have determined the most stable structure of borons by our electronic structure calculations. Furthermore, by taking phonons into account, the effect of finite temperature is considered. From this, the transition temperature between different crystal structure is determined. 5. Material Design for Cu Gettering in Crystal Si Cu atom exhibits very fast diffusivity in crystal Si. This is a serious problem in Si technology, i.e., impurity pollution. In order to depress this pollution, gettering method by introducing dopant atoms is employed, such as B. Mechanisim of fast diffusion of Cu and gettering by B has been studied. Our dynamic simulation well reproduces experimental facts. Furthermore, various coupling of dopant and impurities has been surveyed in order to achieve efficient gettering. 6. Material Design for Light-induced-degradation Proof Amorphous Silicon Application of amorphous silicon to solar cells encounters a big problem of light-induced degradation. In order to overcome this issue, a new material design has been studied. It is demonstrated that insertion of CN ion near dangling bonds in amorphous silicon is useful. 7. Ab intio Molecular Dynamic Simulation of Electronic Excitation-induced Atomic

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Migration. We have developed new simulation method for the application of the electronic excitation-induced atomic migration, and applied for the materials design to use the atomic migration through the metastable atomic position. We have designed new fabrication process from graphite to diamond at the normal condition by using the core electron excitations. Publications Original Papers MBE growth and properties of GaCrN, H. Hashimoto, Y.K. Xhou, M. Kanamura, H. Katayama-Yoshida and H. Asahi: J. Crystal Growth. 251 (2003) 327-330. Materials Design for Semiconductor Spintronics by Ab initio Electronic-structure Calculation (Invited), H. Katayama-Yoshida and K. Sato: Physica B327 (2003) 337-343. Engineering of Nested Fermi Surface and Transparent Conducting p-type Delafossite CuAlO2: Possible Lattice Instability or Transparent Superconductivity?, H. Katayama-Yoshida, T. Koyanagi, H. Funashima, H. Harima and A. Yanase: Solid State Commun. 126 (2003) 135- 139. Curie Temperatures of III-V Diluted Magnetic Semiconductors Calculated from First-Principles in Mean Field Approximation (Invited), K. Sato, H. Katayama-Yoshida and P. H. Dederichs: J. Supercond. Inc. Novel Magnetism, 16 (2003) 31-35. Spin and Charge Control Method of Ternary II-VI and III-V Magnetic Semiconductors for Spintronics: Theory vs. Experiment (Invited), H. Katayama-Yoshida and K. Sato: J. Phys. Chem. Solid. 64 (2003) 1447-1452. A Structural Study of CN Treated Amorphous Silicon, Y. Yamazaki, K. Shirai and H. Katayama-Yoshida: Solid State Commun. 126 (2003) 597-600. Direct Conversion of Graphite into Diamond Through Electronic Excited States (Invited), H. Nakayama and H. Katayama-Yoshida: J. Phys.:Condens. Matter 15 (2003) R1077-R1091. Charge and Spin States of Transition-Metal Atoms in a Hemoprotein Based on the Extended Haldane-Anderson Model, K. Yamauchi, H. Maehashi and H. Katayama-Yoshida: J. Phys. Soc. Japan, 72 (2003) pp.2029-2032. Materials Design of 4d-Transition-Metal-Doped Transparent and Half-Metallic Ferromagnets with K2S-Based Diluted Magnetic Semiconductors, M. Seike, A. Yanasse, K. Sato and H. Katayama-Yoshida: Jpn. J. Appl. Phys. 42 (2003) L1061 -L1063. Tc-Enhanced Codoping Method for GaAs-Based Dilute Magnetic Semiconductors, Van An Dinh, K. Sato and H. Katayama-Yoshida: Jpn. J. Appl. Phys. 42 (2003) L888-L891.

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Theoretical Aspect of Doping of Photovoltaic Materials (Invited), H. Katayama-Yoshida: Mat. Res. Soc. Symp. Proc. 763 (2003) B1.1, 3-12. Magnetic Impurities and Materials Design for Semiconductor Spintronics. (Invited), K. Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky: Physica B340-342 (2003) 863-869. Ab initio materials Design and Curie Temperature of GaN-based Ferromagnetic Semiconductors, K. Sato, P. H. Dederichs, K. Araki and H. Katayama-Yoshida: Phys. Stat. Sol. c, 7 (2003) 2855-2859. Materials Design of p-type Transparent Conducting Oxides of Delafossite CuAlO2 by Super-cell FLAPW Method, T. Koyanagi, H. Harima, A. Yanase and H. Katayama-Yoshida: J. Phys. Chem. Solids 64 (2003) 1443-1446. Mechanism of Suppression of Light-induced Degradation in Amorphous Silicon by CN Treatment, Y. Yamazaki, K. Shirai and H. Katayama-Yoshida: Proc. 26th Int. Conf. Phys. Semicond., Edinburgh 2002, eds. A. R. Long and J. H. Davies, IOP Conf. 171 (2003) L.3.6. Pressure-induced Phase Transitions of BNs, K. Shirai, H. Fujita, and H. Katayama-Yoshida: Physica Status Solidi (b) 235 (2003) 526-530. Association Simulation by a Metallic Car-Parrinello Dynamics, S. Kawamoto, T. Oda and I. Hamada: International Journal of Quantum Chemistry 91, (2003) 165 Structure and Magnetism on Iron Oxide Clusters FenOm(n=1-5): Calculation from First Principles, H. Shiroishi, T. Oda, I. Hamada and N. Fujima: Euro. Phys. J. D. 24, (2003) 85. Possibility of Pressure-induced Superconductivity by Phonon Mechanism in Pd, K. Yanai, T. Takezawa, I. Hamada, N. Suzuki: Physica C 388-389 (2003) 596. The Electronic Structure of Beta-boron and the Pressure Dependence, K. Shirai, A. Masago and H. Katayama-Yoshida: Physics of Semiconductors 2002, 171(2003) D210. Patents “Magnetic Random Access Memory (MRAM)” H. Katayama-Yoshida, K. Sato, TW 92116467 “Magnetic Random Access Memory (MRAM)” H. Katayama-Yoshida, K. Sato, PCT/JP03/07447 “Transparent Ferromagnetic Alkali-chalcogene Compound Containing Transition Metal or Rare-earth Metal, and Control Method of Ferromagnetic Properties.” H. Katayama-

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Yoshida, M. Seike, K. Sato, A. Yanase, JP2003-127602 “Ferromagnetic VI-th Semiconductor, Ferromagnetic III-V Compound Semiconductor, or Ferromagnetic II-VI Compound Semiconductor, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Araki, K. Sato, PCT/JP03/07161 “Ferromagnetic VI-th Semiconductor, Ferromagnetic III-V Compound Semiconductor, or Ferromagnetic II-VI Compound Semiconductor, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Araki, K. Sato, TW 92115303 “Fabrication Method of Diamond from Graphite by Electronic Excitations” H. Katayama-Yoshida, H. Nakayama, PCT/JP03/06426 “Fabrication Method of Diamond from Graphite by Electronic Excitations” H. Katayama-Yoshida, H. Nakayama, TW 92114330 “Circular-polarized Semiconductor Laser by Using Magnetic Semiconductors, and Method of Circular-polarized CW-lasing” H. Katayama-Yoshida, K. Sato, WO 03/065525A1 “Gettering Method of Transition Atom Impurities in Crystalline Silicon” H. Katayama-Yoshida, WO03/060981A1 “II-VI Group or III-V Group Based Single Crystal Ferromagnetic Compound and Method for Adjusting Its Ferromagnetic Characteristics” H. Katayama-Yoshida, K. Sato, Korea 2003-7011104 “Fabrication Method of Highly-light Emitting Semiconductor Materials” H. Katayama-Yoshida, S. Nakajima, JP Patent No.3464618 “Transparent Ferromagnetic Compound Doped by Incomplete Shell without Magnetic Transition Metal and Magnetic Rare-earth Metal Impurities, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Kenmochi, M. Seike, K. Sato, JP2004-055017 “Transparent Ferromagnetic Compound Doped by Incomplete Shell without Magnetic Transition Metal and Magnetic Rare-earth Metal Impurities, and Control Method of Ferromagnetic Properties.” H. Katayama-Yoshida, K. Kenmochi, M. Seike, K. Sato, PCT/JP04/003373 “Thermoelectric materials using natural super-lattices and its control method” H. Katayama-Yoshida, H, Funashima, I. Hamada, H. Harima, A. Yanase, JP2004-085615 International Conferences

Theoretical Aspects of Doping of Photovoltaic Materials (Invited), *H. Katayama-Yoshida, 2003 MRS Spring Meeting, San Francisco, California, April 21-25, 2003

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Ab initio Materials Design and Curie Temperature of GaN Compound-based Ferromagnetic Semiconductors, K. Sato, P. H. Dederichs, *H. Katayama-Yoshida, ICNS-5: 5th International Conference on Nitride Semiconductors, Nara, Japan, May 25-30, 2003 Codoping Methods of Mn and N for GaAs-based Diluted Magnetic Semiconductors, *Dinh Van An, K. Sato, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Materials Design of 4d-Transition-Metal Doped Transparent and Half-metallic Ferromagnetism with Diluted Magnetic Semiconductors in Anti-CaF2 structures of K2S, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Effects of Anti-site Defects on Half-metallicity in Zinc-blends CrAs, *M. Shirai, M. Seike, K. Sato, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Material Design of the Powerful Faraday Rotator, *A. Yanase, H. Katayama-Yoshida, PASPS-9: The 9th Symposium on the Physics and Application of Spin-Related Phenomena in Semiconductors, Tokyo, Japan, June 11-12, 2003 Magnetic Mechanism and Materials Design of Diluted Magnetic Semiconductors from First Principles ~Guideline for High-Tc and Application to II-VI, III-V, IV, and I2-VI Semiconductors (invited), *H. Katayama-Yoshida, K. Sato and P. H. Dederichs, International Workshop on Diluted Magnetic Semiconductors, CECAM, Lyon, June 12-14, 2003 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors (invited), *K. Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky, International Workshop on Diluted Magnetic Semiconductors, CECAM, Lyon, June 12-14, 2003 Group Theoretical Classification of the Electronic Structure of LiNiO2, *A. Masago, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1, 2003 Mechanism of Enhanced Ferromagnetism in Delta-doped(Ga, Mn)As Studied by ab initio Electronic Structure Calculation, *Y. Ohishi, K. Sato, H. Katayama-Yoshida, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Theoretical Study on Anti-site Defects in Half-metallic Zinc-blende Ferromagnets, *M. Shirai, M. Seike, K. Sato and H. Katayama-Yoshida, ICM2003: International

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Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Electronic Structures and CDW of Transition Metal Dichalcogenides, *M. Suzuki and H. Harima, ICM2003: International Conference on Magnetism, Roma, Italy, July 27-August 1,2003 Magnetic Impurities and Materials Design for Semiconductor Spintronics, *K. Sato, P. H. Dederichs, H. Katayama-Yoshida and J. Kudrnovsky, ICDS-22: International Conference on Defects in Semiconductors, Aarhus, Denmark, July 28-August1, 2003 Materials Design of 4d-transition-metal Doped K2S Diluted Magnetic Semiconductors with Transparent and Half-metallic, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, SPINTECH2: International Conference and School Semiconductor Spintronics and Quantum Information Technology, Brugge, Belgiujm, August 4-8, 2003 Mechanism of Enhanced Ferromagnetism in Delta-doped (Ga,Mn)As Studied by ab initio Electronic Structure Calculation, *Y. Ohishi, K. Sato, H. Katayama-Yoshida, SPINTECH2: International Conference and School Semiconductor Spintronics and Quantum Information Technology, Brugge, Belgiujm, August 4-8, 2003 Electronic Structure, Ferromagnetic Mechanism, and Curie Temperature of 3d- and 4d-Transition Atom Doped Diluted Magnetic Semiconductors (invited), *H. Katayama-Yoshida, The 4th Korea-Japan Workshop on Strongly Correlated Systems and The First Japan-Korea-Taiwan Workshop on Condensed Matter Physics “Spectroscopy of Correlated Materials and their Nano-Structures”, Nagano, Japan, September 24-26, 2003 Band Structure Calculations and Fermi Surfaces of YNi2B2C, *Y. Yamauchi, H. Katayama-Yoshida, A. Yanase, H. Harima, 16th International Symposium on Superconductivity, Tsukuba, Japan, October 27-29, 2003 Diamond Transition from Graphite Induced by Electronic Excitations, *H. Nakayama and H. Katayama-Yoshida, The 6th Asian Workshop on First-Principles Electronic Structure Calculations, Tsukuba, November 10-12, 2003 Pressure-induced Phase Transitions of BN, *K. Shirai, H. Fujita, and H. Katayama-Yoshida, The 6th Asian Workshop on First-Principles Electronic Structure Calculations, Tsukuba, November 10-12, 2003 Design of High-Tc Curie Temperature with Transparent and Half Metallic Ferromagnetism in Zr- and Nb-doped K2S Diluted Magnetic Semiconductors, *M. Seike, A. Yanase, K. Sato and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 Design of a Method to Raise Curie Temperature by Delta-doping and Co-doping, *Y. Ohishi, Dinh Van An, K. Sato, H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003

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An Application of Molecular Dynamics Simulation to Diffusion of Impurity in Solids, *K. Shirai and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 Ab-initio Molecular Dynamics Simulation of CN in Amorphous Silicon, *N. Mitsuda, K. Shirai and H. Katayama-Yoshida, International Symposium on Scientific and Industrial Nanotechnology 2003, Osaka, Japan, December 8-9, 2003 Materials Design for Spin-electronics by Ab-initio Electronic Structure Calculation (invited), *H. Katayama-Yoshida, 31st Conference on The Physics and Chemistry of Semiconductor Interface (PCSI-31), Kailua-Kona, Hawaii, USA, January 18-22, 2004 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors, *K. Sato, International Symposium on the Creation on Novel nanomaterials, Osaka, Japan, January 20-22, 2004 Hyperfine Interactions and Magnetism of 3d impurities in magnetic semiconductors (invited), *K. Sato, International Workshop on Nanomaterials, Magnetic Ions and Magnetic Semiconductors studied mostly by Hyperfine Interactions (IWNMS – 2004), Vadodara (Baroda), Gujarat, India, February 10-14, 2004 Exchange Interactions and Curie Temperatures in Diluted Magnetic Semiconductors, *K. Sato, P. H. Dederichs, H. Katayama-Yoshida, APS(American Physical Society) March Meeting, Montreal, Quebec, Canada, March 22-26, 2004 Contributions to International Conferences and Journals

H. Katayama-Yoshida 3rd International Conference on Physics and Application of Spin-related Phenomena in Semiconductors: PASPS3 (International Advisory Committee and Program Committee)

H. Katayama-Yoshida 24th International Conference on Defects in Semiconductors : ICDS24 (Chairman)

Publications in Domestic Meetings

The Physical Society of Japan 13papers The Japan Society of Applied Physics 6papers Academic Degrees Master Degree of Science

M. Suzuki CDW and Electronic Band Structures of Transition Metal Di-chalcogenides

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Master Degree of Engineering

Y. Ohishi Material Design on the GaAs-based Diluted Magnetic Semiconductor using First Principles Calculation.

M. Seike Materials Design of New Root Half-Metalic and Room-Temperature Ferromagnets in Diluted Magnetic Semiconductors

T. Michikita Ab initio Calculations of Cu Gettering in Crystalline Silicon Sponsorship Grant-in-Aid for Scientific Research (C) K. Shirai Ab Initio Calculation of Phonon-phonon Interaction

for High Thermal Conductivity ¥600,000

Other allocations Grant-in-Aid for Scientific Research (A) (H. Hirayama) H. Katayama-Yoshida Fabrication and Application of High Density p-type

Nitride Semiconductor Thin Film Crystal by Alternative Codoping

¥500,000

Grant-in-Aid for Scientific Research on the Priority Area (M. Shirai) H. Katayama-Yoshida Design for Opto-spintronics and Spin Prove Entrusted Research Special Coordination Funds for Promoting Science and Technology H. Katayama-Yoshida Design and Fabrication of Nanospintronics

Computational Nanomaterials and Device Design ¥19,964,000

Ministry of Education, Culture, Sports, Science and Technology Grant-in-Aid for the Creation of Innovations through Business-Academic-Public Sector Cooperation H. Katayama-Yoshida Research on selective and low-temperature impurity

diffusion in semiconductor by infra-red laser excitation

¥4,500,000

Japan Science and Technology Corporation H. Katayama-Yoshida Core Research for Evolutional Science and Technology

(H. Kobayashi) Silicon Thin Film Solar Cells with New Chemical Bonds

Japan Science and Technology Corporation H. Katayama-Yoshida Research and development Applying Advanced Computational

Science and Technology (H. Akai) Computational Nano-materials Design

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New Energy and Industrial Technology Development Organization (NEDO) H. Katayama-Yoshida Development of Method for Nano-materials Simulation

(H. Akai) Cooperative Research H. Katayama-Yoshida Institute for Materials Research,

Tohoku Univ. Materials and Device Design for Functional Wide-band Gap Semiconductors

H. Katayama-Yoshida Spring8 Mechanism of New Materials Fabrication Using Electronic Excitation

H. Katayama-Yoshida International Institute of Advanced Study

Materials Science and System Design

H. Katayama-Yoshida Jülich Institute (Germany) Computational Materials and Devices Design for Nanospintronics

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Department of Nano-Bio Intelligent Systems Science Professor: Riichiro MIZOGUCHI Research Associate: Kouji KOZAKI Outlines

The research on development of Nano-Bio intelligent help system, data mining from

the nano-bio data, systematization of nano-bio knowledge, ontology engineering is conducted aiming at amalgamation of knowledge research and nano-biotechnology. Special emphasis is placed on systematization of nanotechnology.

It is highly expected that bridging the gap between several domains of nanotechnology to facilitate creative design by enabling reuse of knowledge across these domains. Ontology engineering is an advanced AI technology which has a great potential to achieve the goal. This is why we have been intensively involved in ontology engineering. The concrete objectives include development of nanotechnology ontology, development of function achievement ways for nanomaterials and development of a system for supporting creative design of nanomaterials at the functional level together with an ontology engineering environment.

Current Research Projects 1. Development of Nanotechnology Ontology

In the domains including chemical engineering, we develop a common ontology in the light of nanotechnology knowledge systematization. A preliminary ontology has been developed by analyzing textbooks, papers and patents under the consultation of the domain experts. Its brief explanation is given below. (a)Four top-level categories - Top-level categories are composed of Process, Structure, Function and Matter

(b)Distinction between Structure and Shape - Shape: figure or form attributed to a primitive and concrete thing such as sphere. - Structure: abstract concept representing topological relation among elements

(c)Function and quality - Quality: Characteristics attributed to matters - Function: Teleological conceptualization of a role played by thing

2. Development of a System for Supporting Creative Design of Nanomaterials

Aiming at bridging required functions stated by engineers in industries and basic functions(or quality) and at facilitating the creative design, systematization of function achievement ways in a particular domain and development of a support system of

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functional design of materials are currently conducted in parallel. In general, a function is achieved by performing multiple sub-functions. The

achievement is supported by a physical principle and/or structure of the device or materials which is conceptualized as Function achievement way. The decomposition is continued concerning each sub-function to eventually form a function decomposition tree for each device/material. There exist multiple ways of functional decomposition so that the computer can help device/material designers to help their design process by giving possible alternative ways stored in a function achievement way server.

We have conducted the cross-over collaboration between us and Niihara & Kawai Labs. The concrete results on this collaboration include development of functional decomposition trees of Nano-film and nano-particle together with a prototype system of creative design support system using a function achievement way server we developed.

3. An Environment for Ontology Development and its Use We developed Hozo, an ontology engineering environment, which enables a user to build and use an ontology and instance models. It consists of Ontology editor, Concept factory and ontology server. Ontology editor

It provides a friendly user interface as well as powerful functions necessary for ontology building and editing. Concept factory

A guidance system based on AFM(Activity-First Method) has been implemented to guide ontology developers who build an ontology from technical documents. Ontology server

A server for ontologies and models has been developed. It is based on the client-server architecture and enables human/computer agents to access them through internet.

Publications Original Paper Cell Signaling Networks Ontology, T. Takai-Igarashi and R. Mizoguchi: In Silico Biol. 4 (2003) 0008 International Conferences An Environment for Distributed Ontology Development Based on Dependency Management, *E. Sunagawa, K. Kozaki, Y. Kitamura and R. Mizoguchi, Proc. of the Second International Semantic Web Conference (ISWC2003), pp.453-468, Sanibel Island, FL, USA, Oct., 2003. Systematization of Nanotechnology Knowledge Through Ontology Engineering - A

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Trial Development of Idea Creation Support System for Materials Design based on Functional Ontology – (Poster), *K. Kozaki, Y. Kitamura and R. Mizoguchi, The Second International Semantic Web Conference (ISWC2003), Sanibel Island, FL, USA, Oct., 2003. Hozo: Treatment of “Role”, “Relationship” and Dependency Management (Poster), *K. Kozaki, Y. Kitamura and R. Mizoguchi, The Second International Semantic Web Conference (ISWC2003), Sanibel Island, FL, USA, Oct., 2003. A Trial Development of Idea Creation Support System for Materials Design based on Functional Ontology (Poster) , *K. Kozaki, Y. Kitamura and R. Mizoguchi, International Symposium on Scientific and Industrial Nanotechnology 2003 (ISSIN-2003), Osaka, Japan, December 8-9, 2003. Contributions to International Conferences and Journals Riichiro Mizoguchi International Conference on Computers in Education

2003(ICCE2003)(Conference Chair) Riichiro Mizoguchi International Conference on Artificial Intelligence in

Education 2003(AIED2003)(Conference Chair) Riichiro Mizoguchi International Conference on Computers and Advanced

Technology in Education 2003 (CATE-2003)(PC member) Riichiro Mizoguchi The 8th Ibero-American Conference on Artificial Intelligence

IBERAMIA'03(PC member) Riichiro Mizoguchi The Second International Semantic Web Conference 2003

(ISWC2003)(PC member) Riichiro Mizoguchi The 9th International Conference on User Modeling (UM03)

(PC member) Riichiro Mizoguchi IEEE International Conference on Advanced Learning

Technologies (ICALT 2003) (PC member) Riichiro Mizoguchi La Conferencia de la Asociación Española para la Inteligencia

Artificial (CAEPIA2003)(PC member) Riichiro Mizoguchi International Conference on the Convergence of Knowledge, Culture,

Language and Information Technologies (Convergences03) (PC member)

Riichiro Mizoguchi The 1st European Semantic Web Symposium (ESWS2004) (PC member)

Riichiro Mizoguchi IEEE International Workshop on Wireless and Mobile Technologies in Education (WMTE2003)(PC member)

Riichiro Mizoguchi President of Asia-Pacific Chapter of AACE Riichiro Mizoguchi President of International Artificial Intelligence in Education

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Society Riichiro Mizoguchi International Journal of Artificial Intelligence in Education

(Editorial board) Riichiro Mizoguchi International Journal of Advanced Engineering Informatics

(Editorial board) Riichiro Mizoguchi International Journal of Web Semantics(Editorial board) Riichiro Mizoguchi International Journal of Computer and Engineering

Management(Editorial board) Riichiro Mizoguchi International Journal of Web Engineering and Technology

(Editorial board) Publications in Domestic Meeting Japanese Society for Artificial Intelligence 4 papers

Sponsorship Cooperative Research R. Mizoguchi The Society of

Chemical Engineers, Japan

New Energy and Industrial Technology Development Organization Nanotechnology Materials Program "Structuralization of Materials Technology Know-How" Nanotechnology ontology studies and development of an ontology server

¥5,250,000

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Department of Nanotechnology Transfer Guest Researcher: Horng-Show Frank KOO (2002.11.-2003.7.) Outlines

The aim of this department is to transfer research results to the industry, and to create new industrial field. Achievements

In order to develop novel nano-materials, fabrication of ferroelectric nano-scale thin films, selective construction of nano-structure by using molecular self assembly and their observation by scanning probe microscope have been discussed. Investigations on the trend of nanotechnology have also been carried out by attending conferences and workshops.

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Department of Nanotechnology Transfer Guest Associate Professor: Wolfgang SPRENGEL (2003.9.-12.) Outlines

The aim of this department is to transfer research results to the industry, and to create new industrial field. Achievements

The intermetallic compound Nd2Fe14B is a base material for high-performance permanent magnets. In this nanocrystalline structure, interfaces play a prominent role for tailoring the magnetic properties of the solid. In addition, in Nd-rich nanocrystalline (n-) Nd2Fe14B the phenomenon of intergranular phase melting at temperatures far below the melting temperature of the bulk material is observed. These aspects are of importance for the processing and the understanding of the physics of these high-performance permanent magnets. In the present project self-diffusion (volume/interface diffusion) studies of 59Fe have been carried out in Nd2Fe14B by the radioactive tracer method to elucidate the structure of the interfaces and atomic processes therein.

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Radiation Laboratory Professor, Director: Seiichi TAGAWA Professors Goro ISOYAMA, Tetsuro MAJIMA, Yoichi YOSHIDA Associate Professors: Yukio YAMAMOTO, Ryuko KATO, Yoshihide HONDA,

Shu SEKI, Mamoru FUJITSUKA, Takahiro KOZAWA Research Associates: Toshiji IKEDA, Norio KIMURA, Kazuo KOBAYASHI, Sachiko TOJO, Kiyohiko KAWAI, Masayuki ENDO,

Shigeru KASHIWAGI, Jinfeng YANG, Akinori SAEKI Technical Staff: Tamotsu YAMAMOTO, Kumiko BABA Support Staff: Ai MATSUSHIMA Outlines

Radiation Laboratory (RL) was newly established at 2002 fiscal year keeping the same name as before. The new RL belongs to Nanoscience and Nanotechnology Center of ISIR and is comprised of three electron linear accelerators (linacs), Co-60 irradiation facility and other small facilities related to quantum beams which were all belonged to the old RL. The new RL is managed by the organization consisting of the staffs, which belong to Division of beam science for nanotechnology, which also started as a division of Nanoscience and Nanotechnology Center, Division of quantum beam science and technology, and other related departments in ISIR. The maintenance of the facilities and the protection management against radiation hazard are also made by these staffs. The new RL is also opened for collaborations and these are taken care by the staffs mentioned above.

Concerning L-band electron linac, the development of new control system and operations using this system were started. The repetition stability of RF peak power was achieved within 0.1%, however, discharges took place in the RF transporting system. Troubleshooting of the discharges, improvement of the software for control system and measurements of several parameters were performed. In the case of new S-band electron linac with RF-gun, the specification of new RF power unit was tested and the stability of 0.2 % at peak power was obtained, which satisfied specification. The preliminary operation was started. The control system and interlock system were maintained as the S-band RF power sources are shared with two linacs. Co-60 gamma-ray irradiation facility was operated for 2893 hours for 14 subjects.

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Nanotechnology Process Foundry Professor: Tomoji KAWAI Visiting Associate Professor: Masakazu MURASUGI Visiting Research Associates: Yoshinori MATSUI Yuichi SASAJIMA (to Oct. 31)

Kazumasa OKAMOTO Takahiro OHNO (from Dec. 16)

Supporting Staff: Yoko TAKEBAYASHI (to Feb. 29) Outlines

Nanotechnology Process Foundry was founded in Nanoscience and Nanotechnology Center on the basis of Nanotechnology Support Project, supported by MEXT, Japan. The purpose to start up the foundry is to build a platform supporting Nanotechnology R&D totally in Japan, especially for researchers outside Osaka University. It was the second year of this project in 2003, and most of our efforts resulted in setting up the research environment, including its system and equipments. The foundry system was organized to realize the requests that researchers in private laboratories and R&D projects needed opportunities to use special facilities and equipments for their Nanotechnology R&D.

Institute of Science and Industrial Research, Osaka University has played an important role in Nanotechnology field by means of providing technology and information. In particular, thin film deposition works covering oxides and organic materials were presented a lot of impressed results. Based on the excellent works, Nanotechnology Process foundry focuses the following supports. (1) Thin film deposition of oxides, organic materials, and high melting point metals. (2) Nanofabrication for oxide and organic material devices. (3) Characterization of thin films and devices made of oxides and organic materials. Achievements

More than 20 research themes have been accepted since the foundry started its support. Considering they were applied by researchers in companies, universities, and national laboratories, we can see that Nanotechnology Process foundry activates Nanotechnology field clearly. There are three points on our achievements in FY2002 in the followings: 1. Bring-up Nanotechnology Process Foundry. Nanotechnology Process Foundry was founded to support Nanotechnology researchers through thin film deposition, nanofabrication, and characterization. These supports are provided in the type of (a) consulting, (b) collaboration, (c) equipment use, and (d) research support. 2. Break-through toward functional Nanotechnology R&D. The foundry supports advanced Nanotechnology R&D as well as fundamental research. The research on functional integration and system building based on nanomaterials is acceptable in the foundry. 3. Fusion between top-down and bottom-up Nanotechnologies. Many useful equipments for top-down and bottom-up Nanotechnologies are in operation. The fusion between top-down and bottom-up Nanotechnologies will bring a lot of important progresses on Nanotechnology in the near future.

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Publications Original Papers Subpicosecond Pulse Radiolysis Study of Geminate Ion Recombination in Liquid Benzene, K. Okamoto, A. Saeki, T. Kozawa, Y. Yoshida, and S. Tagawa: Chem. Lett. 32 (2003) 834-835. Dependence of Outgassing Characters at a 157 nm Exposure on Resist Structures, Y. Matsui, S. Umeda, S. Seki, S. Tagawa, S. Ishikawa T. Itani: Jpn. J. Appl. Phys. 43 (2003) 3894-3899. Pulse Radiolysis Study of Radical Cations of Polysilanes, T. Kawaguchi, S. Seki, K. Okamoto, A. Saeki, Y. Yoshida, S. Tagawa: Chem. Phys. Lett. 374 (2003) 353-357. Transient Absorption Spectroscopy of Radical Ions of Rigid Anti- and Syn-tetrasilane, S. Seki, Y. Matsui, S. Tagawa, H. Tsuji, A. Toshimitsu, K. Tamao: Chem. Phys. Lett. 380 (2003) 141-145. Dependence of Outgassing Characters and Total Amount of Outgassed Species at 157 nm Exposure on the Structures of Resist Base Polymer, Y. Matsui, S. Umeda, S. Matsui, S. Seki, S. Tagawa, S. Ishikawa, T. Itani: Proc. SPIE 5039 (2003) 121-128. International Conferences Outgassed Species from Various Triphenylsulfonium Salts during 157 nm (poster), Y. Matsui, S. Seki, S. Tagawa, S. Irie, T. Itani: 4th International Symposium on 157 nm Lithography, Tokyo, Japan, Aug. 25-28, 2003. Effects of Ester Groups on Proton Generation and Diffusion in Polymethacrylate Matrices (poster), A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Polymer Screening Method for Chemically Amplified Electron Beam and X-Ray Resists, H.Yamamoto, A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Outgassed Species from 157-nm-Irradiated Triphenylsulfonium Salts (poster), Y. Matsui, S. Seki, S. Tagawa, S. Irie, T. Itani: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Applications of Polysilanes for a Negative-Tone Resist in Ion Beam Lithography (poster), Y. Matsui, S. Seki, S. Tsukuda, T. Kozawa, and S. Tagawa: Microprocess and Nanotechnology Conference, Tokyo, Japan, Oct. 28- 31, 2003. Pulse Radiolysis Study on Proton and Charge Transfer Reactions in Poly (Methyl Methacrylate) (poster), A. Nakano, K. Okamoto, T. Kozawa and S. Tagawa: 12th International Congress of Radiation Research, Brisbane, Australia Aug. 17-22, 2003. Outgassing Characteristics of Acetal Resists for 157 nm Lithography Investigated by Time-Resolved Measurement, *Y. Matsui, S. Seki, S. Matsui, S. Tagawa, S. Irie and T. Itani, SPIE’s 29th Annual International Symposium, Microlithography, Santa Clara, USA, February 23-27, 2004.

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Nanotechnology Foundry Activities in Osaka University(Invited), *K. Okamoto, M. Murasugi and T. Kawai, Asian Nano-Foundry Workshop, Tokyo, Japan, March 17, 2004. Sponsorship Entrusted Research T. Kawai MEXT (RR2002) Nanotechnology ¥82,000,000

Support Project

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Materials Analysis Center Professor, Director: Tetsuro MAJIMA Associate Professor: Masami SAWADA Research Associate: Yoshio TAKAI Outlines The Materials Analysis Center was founded in 1977, whose project includes (1) analysis of samples provided from other research sections in ISIR and (2) original research for developing novel analytical methods coupled with various analytical instruments. Current Research Programs 1. Novel Analytical Methods: Host-Guest Chiral Recognition Mass Spectrometry Until recently, various methods were used for determining chiral recognition of the chiral host compounds such as crown ethers, cyclodextrins, porphyrins, etc. Examples are the methods of extraction/NMR, extraction/polarimetry, titration NMR, induced circular dichromism, liquid chromatography (LC), capillary electrophoresis, transport, etc. Mass spectrometry (MS) is highly sensitive but not generally considered as sensitive to chiral difference and convenient for detecting host-guest chiral recognition properties because of the absence of mass differences between their host-guest diastereomeric isomers. We have proposed a new technique of the mass spectrometry (MS)/enantiomer labeled (EL) Guest method. In this method, one of the enantiomeric guests is isotopically labeled, and a 1/1 mixture of a labeled and an unlabeled enantiomeric guest is complexed with a chiral host. Therefore, the new method has been called the EL-guest method. The method can be used for the detection and quantitative evaluation of chiral recognition ability of the hosts toward the guests. The other one, which we have proposed, is another new technique of the MS/EL-Host method. In this method, one of the enantiomeric hosts is isotopically labeled, and a 1/1 mixture of a labeled and an unlabeled enantiomeric host is complexed with an ee-unknown guest. Therefore, the new method has been called the EL-Host method. The method can be used for the determination of enantiomeric excess (ee) of a given chiral guest.

Chiral recognition in the host-guest complexation systems of chiral crown ethers and amino esters was thoroughly examined using the electrospray ionization (ESI) mass spectrometry (MS)/enantiomer labeled (EL)-guest method. In our earlier report (1996), we had described that the apparent chiral recognition abilities using a mass spectrometer with a homemade ESI interface were depressed about one tenth compared with the corresponding abilities by FABMS. Now, the enantioselective complexation behaviors of various combinations of chiral crown hosts with chiral guests were further investigated in detail mainly using a modern commercial ESI/ion trap (IT) mass spectrometer. Consequently, it was found that the apparent IRIS values from the ESIMS/EL-guest method significantly change depending upon the instruments, in

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particular, upon the ESI interfaces. Moreover, under the specific measuring conditions in the ESIITMS, the degrees of depression of the apparent chiral recognition abilities are roughly grouped into three classes, depending upon the number (or probably the type) of the hydrophobic substituents of the hosts. Representing the degrees by the slopes when plotting the apparent IRIS values in ESIMS versus those in FABMS, the slopes of the three classes are (1) 1.0, (2) 0.7, and (3) 0.3; the higher the hydrophobicity of the hosts (and then, the host-guest complex ions), the lower the slope (the apparent enantioselectivity). Strengthening the depression degrees may be caused by the increase in the local concentration of the host close to the surface of the droplets produced during the electrospary ionization process. The chiral recognition ability (KR/KS) in an equilibrated solution agrees quite well with the IRIS value in FABMS rather than that in ESIMS. Publications Original Paper Depression of the Apparent Chiral Recognition Ability Obtained in the Host-Guest Complexation Systems by Electrospray and Nano-Electrospray Ionization Mass Spectrometry, M. Sawada, Y. Takai, H. Yamada, M. Yoshikawa, R. Arakawa, H. Tabuchi, M. Takada, J. Tanaka, M. Shizuma, H. Yamaoka, K. Hirose, K. Fukuda, and Y. Tobe, Eur. J. Mass Spectrom., 10 (2004) 27-37. Review Paper The Unexpected Fruit of Persistent Work (for the Nobel Prize Winner, Koichi Tanaka), M. Sawada and Hiroshi Yamaoka, “The Chemical Society of Japan: A 125-Year Quest for Excellence. 1878-2003”, ed. by the Chemical Society of Japan, (2003) pp.53-54. International Conferences Development of Novel Linear-type Chiral Recognizable Host Compounds for Binding Amine Guests through the Mass Spectrometric Screening of Combinatorial Host-Guest Mixtures: Application of the Enantiomer-Labeled Guest Method (Poster), *M. Sawada, Y. Takai, and M. Shizuma, 16th International Mass Spectrometry Conference, Edinburgh, United Kingdom, September 2, 2003. Qauntitative Chiral Recognition in Host-Guest Complexations by Mass Spectrometry, *M. Sawada, Y. Takai, M. Shizuma, H. Yamaoka (Invited), 10th Kyushu International Symposium on Physical Organic Chemistry (KISPOC-X), Fukuoka, Japan, September 30, 2003. Quantitative Chiral Recognition in Host-Guest Complexations by Mass Spectrometry, *M. Sawada, Y. Takai (Poster), 2nd 21st Century COE Program: 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka, Japan, January 13, 2004. Inclusion of Permethylated Inulin with Alkali Metal Ions, *Y. Takai, M. Sawada

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(Poster), 2nd 21st Century COE Program: 7th SANKEN International Symposium on Hybridization of Chemistry, Biology, and Material Science, Osaka, Japan, January 14, 2004. Contributions to International Conferences and Journals M. Sawada European Journal of Mass Spectrometry (Editor) Publications in Domestic Meetings The Chemical Society of Japan 4 papers The Mass Spectrometry Society of Japan 6 papers Others 1 papers Sponsorship Grant-in Aid for Scientific Research (C)(2) M. Sawada Quantitative Host-Guest Chiral Recognition Mass ¥1,900,000

Spectrometry

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Service Facilities Workshop Director Professor: Shigetoshi TAKAHASHI Outlines

The workshop consists of a metal processing shop and a glass blowing shop. In the former, various apparatuses made from metallic materials are designed and assembled for experiments. It is equipped with lathes and fraises in addition to drilling, rolling, and welding machines. In 2000-2001 academic year, a computer-controlled machine (machining center) was newly equipped. In the latter, sophisticated glass apparatuses are made according to researcher’s requirements. It is equipped with an electric furnace, glass lathes, and glass cutting machines.

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Electronic Processing Laboratory Professor: Hajime ASAHI Associate Professor: Takuya MATSUMOTO Associate Professor: Tatsuo YOSHINOBU Associate Professor: Shigehiko HASEGAWA Research Associate: Yi-Kai ZHOU Research Associate: Tetsuya YOSHIDA Outlines Electronic Processing Laboratory was established as a sort of device fabrication work-shop in 1991. The aim of this laboratory is to contribute to the development of researches by setting up the equipment and systems for fabrication, required commonly for the researches related to the areas such as photonic and electronic materials, molecular device materials and organic device materials and by improving process technology for various device materials. The equipment and systems are a small-size clean room, a photolithography system, a high vacuum evaporation system, an electron beam evaporation system, a sputter deposition system, a reactive ion etching system, a crystal cleaving system, a wire bonding system, a double crystal X-ray diffractometer, an atomic force microscope and personal computers for data analysis. This laboratory is utilized for experimental researches of surface structure analysis and electrode formation, for the measurements of electronic and other properties of various materials and also for the fabrication of photonic, electronic and molecular devices.

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Electron Microscope Laboratory Professor: Yoshihiko HIROTSU Research Associate: Takeshi HANADA Outlines

Electron microscope laboratory was organized in 1951 to contribute to micro structural investigation in I.S.I.R. We have a 300 kV high resolution analytical electron microscope with a field emission gun and a scanning electron microscope.

These electron microscpoes serve to make atomic scale structural observations, nano-area electron diffraction analyses, and nano-area chemical analyses in response to each research division. Current Research Programs 1. Nano-Structures of Amorphous Fe-Cu-Nb-Si-B Alloys and Their Relations to

the Nano-crystalline Structures on Annealing. Nano-crystalline Fe-Cu-Nb-Si-B soft magnetic alloys so called finmet exhibit good

saturation magnetization and permeability. The nano-crystalline structure with bcc-Fe(Si) nano-crystals embedded in amorphous matrix is developed by annealing a melt spun Fe73.5Cu1Nb3Si13.5B9 amorphous ribbon at an optimum temperature, 823 K. In this alloy, a Cu addition affects the nano-crystalline structure and soft magnetic property. An addition of 1 at.% Cu leads to the formation of bcc-Fe(Si) nano-crystallites with a size of 10 nm, and B and Nb rich amorphous matrix. We have investigated the amorphous structures of this alloy annealed below crystallization temperature to reveal the crystallization mechanism of nano-crystalline structure by mean of high resolution electron microscopy and electron diffraction techniques. Nano-beam electron diffraction technique revealed the formation of bcc-Fe(Si) and boride clusters in the as-formed amorphous ribbon. The annealing of amorphous ribbon enhances the formation of bcc-Fe(Si) nano-crystals, and the 1 at.% Cu addition accelerates the reaction. The electron diffraction pair distribution analysis and reverse monte carlo simulation suggested that the annealing leads to a random replacement of Fe atoms by Nb in the Fe-B trigonal prism structures in the amorphous, with increase of bcc-Fe(Si) clusters. The formation of Fe-Nb bonds and also Fe-B bonds in the trigonal prisms is considered to inhibit Fe diffusion, resulting in the inhibition of the bcc-Fe(Si) nano-crystal growth. 2. TEM Observation of Organic/metal Composite Materials.

Three-dimensional porphyrin monolayer-protected gold and silver clusters (MPCs) have been prepared to examine the effects of chain length and metal on the structure and photophysical properties, in comparison with self-assembled monolayers (SAMs) of the porphyrins on a flat gold surface. The size distribution of nano-metal-cluster embedded in porphyrin monolayer with a systematic series of alkyl spacers is examined by transmission electron microscope (TEM). The three-dimensional porphyrin MPCs exhibit the electrochemical and photophysical properties, which are much closer to those of a porphyrin reference compound in solution than those of two-dimensional

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porphyrin SAMs on the flat gold surface. The three-dimensional architectures of porphyrin MPCs with large surface area have improved the light-harvesting efficiency relative to the corresponding porphyrin SAM on the two-dimensional flat gold surface. The time-resolved single-photon counting fluorescence and transient absorption spectroscopic studies have demonstrated that the undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three dimensional MPCs is much suppressed, as compared to the quenching of the porphyrin SAMs on the two-dimensional flat gold surface. Both the quenching rate constants of the porphyrin excited singlet state by the surfaces of bulk gold and gold nanocluster reveal extremely weak distance dependence of the energy transfer quenching (i.e., weak chain length effect). Structure and photophysical properties of porphyrin silver MPC are virtually the same as those of the corresponding porphyrin gold MPC.

Publications Original Papers Local Atomic Structures of Amorphous Nd4.5Fe77B18.5 Alloys Formed under Different Cooling Rates and Their Relations to the Structures in the Early Stage of Crystallization, T. Hanada, T. Sakamoto, T. Ohkubo, Y. Hirotsu, H. Kanekiyo and S. Hirosawa: Mater. Trans. 44 (2003) 2042-2047. International Conferences Variation of Short Range Order with the Composition in an Amorphous-Al-Pt Alloy Existing in a Wide Compositional Range, *J. L. Lábár, A Kovács, B.P. Barna, T. Hanada, M. Ishimaru, Y. Hirotsu, I.-T. Bae, 6th Multinational Congress on Microscopy – A Regional Meeting with European Extension, Pula, Croatia, June 1-5, 2003. Effect of Cu Addition on the Annealing Process of FeNbSiB Glass (Poster), *T. Hanada, T. Matsumoto, Y Hirotsu, T.Ohkubo, S. Fijii, Y. Yoshizawa, Bulk Metallic Grass III, Beijing, October 12 to 16, 2003. Publications in Domestic Meetings The Japan Institute of Metals 2 papers The Chemical Society of Japan 2 papers Japan Society of Microscopy 1 paper

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Office of Information Network Professor: Akihito YAMAGUCHI Outlines

Office of Information Network was inaugurated in March, 1999, to organize the operation of the information network in ISIR, which had been started with support by volunteers, because of the rapid spread of the information network and the growth of its importance in the research environment. The information was constructed as a prototype by the departments in the division of Intelligent System Science in the late 1980's and has been expanded to the whole of ISIR with the development of ODINS (Osaka University Information Network System). Recently it has played an important role in ISIR to release/access the information available in the Internet. Office of Information Network is now supporting researchers and students on the variety areas.

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Laboratory for Radio-isotope Experiments Professor: Akihito YAMAGUCHI Outlines The laboratory is specially designed for experiments using radioactive compounds labeled with 3H, 14C, 32P, 35S. The main equipments are liquid scintillation counters and image scanner. This laboratory is essential for the research in the field of biochemistry and molecular biology. Contributions of the facilities to each project are described in the section of each department. The use of radioisotopes is regulated with the national law for the prevention of radiation hazard. The facilities are inspected regularly with authorities and pass the required standard. Radioisotope users are mandatory to be educated every year to get the knowledge for the safe use of radioisotopes.

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Library Professor: Hikaru KOBAYASHI Staff: Taiko FURUTA Outlines

The ISIR Library houses only technical books and journals for researchers. Most materials are on open shelves directly available to faculty and students. The library has two reading rooms and a workroom with photocopiers on the second floor of the administration building, and the storage facility on the first floor of the research building.

The library office offers the following services; orders for books and magazines, survey and inquiry of literature, Interlibrary Loan services, photocopy request, and so on. Guide to the Library could be found on its home page (http://www.sanken.osaka-u.ac.jp/labs/lib-web/).

(As of March 1, 2004) Number of books Journals Newspapers Japanese 12,431 301 titles 4 titles Foreign 46,313 979 titles 1 title

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Technical Division Head: Yoshiyuki OKUDA Outlines The technical division was established in 1982 in order to establish the role and duties of technicians so that they can give better service to researchers. In the ISIR organization, the technician group is independent of the management and the research groups. The organization was the first one among similar organizations to be established in the national universities of Japan. The technical division consists of the machine and the measurement group. The machine group consists of the machine/circuit section and the glass section, and the measurement group consists of the measurement/information system section and the analysis/data treatment section. Technicians belonging to the latter group work at the materials analysis center, the workshop, the Office of information network, the electronic processing laboratory and the nanotechnology center. The technical division gives not only high-quality service to research groups but also technical training necessary for researchers and students. The annual report is published to help and encourage training and activities of the members of the division.

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