Published by Maney Publishing (c) W.S Maney & Son Limited Materials Research Innovations Online 148 Elisabetta Bonometti, Mario Castiglioni, Paola Michelin Lausarot, Cristina Leonelli, Federica Bondioli, Gian Carlo Pellacani, Anna Angela Barba Amorphous Germanium(II) Sulfide Particles Obtained By Microwave Assisted Decomposition Of Germanium (IV) Sulfide Addresses for Correspondence: M.Castiglioni (E-mail: [email protected] , Tel: +39-11-6707584, Fax: +39-11-6707591) E.Bonometti, P.Michelin Lausarot, Dipartimento di Chimica Generale ed Organica Applicata, Università di Torino, C.so M. d’Azeglio, 48- 10125 Torino, Italy. C.Leonelli, F.Bondioli, G.C.Pellicani, Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Università di Modena e Reggio Emilia, Via Vignolese, 905- 41100 Modena, Italy. A.A.Barba, Dipartimento di Ingegneria Chimica ed Alimentare, Università di Salerno, Via Ponte Don Melillo, 84084 Fisciano, Italy Received: 18 May 2005 Accepted: 8 August 2005 Revised: 23 February 2006 Keywords: amorphous particles, germanium sulfides, microwaves, nanoparticles, sublimation INTRODUCTION Equilibrium reaction (1) has been used to calculate the standard molar enthalpy of formation for GeS 2 and for the chemical transport of Ge [1, 2]. Nevertheless the high temperature behavior of GeS 2 does not seem to be well understood [3]. 2GeS 2(s) 2GeS (g) + S 2 (g) (1) Stoichiometric germanium sulfides, namely GeS and GeS 2 are semiconductors and hence many of their chemical and physical properties in crystal and vitreous phase have been studied [4, 5, 6, 7]. Both sulfides can be prepared in bulk thin films and powders [8, 9]. Preparation of vitreous GeS 2 , by rapid quenching of the liquid has been reported [10]. Vitreous GeS has not been prepared in bulk but only in thin film [11, 12, 13]. Sol-gel technique and polycondensation of [(CH 3 ) 4 N] 4 -Ge 4 S 10 under acidic conditions have been used to prepare small particles of GeS 2 [8, 14]. Gas to particles conversion, under many different arrangements, is a widely used technique to prepare powders [9, 15, 16, 17]. It is quite a clean process but suffers the disadvantage of difficult control of particles agglomeration [18]. Though recently weakly protonated GeS 2 particles have been prepared by sublimation of GeS 2 + H 2 S at about 1020 K and 7·10 5 Pa, pure molecular GeS 2 can not be prepared in pure form by sublimation of solid GeS 2 because the equilibrium reaction (1) is shifted to the right by the temperature increase [19, 20]. Some different spectroscopic properties have been observed in glassy and crystalline GeS 2 as in glassy and crystalline GeS [12, 21]. We already reported on the preparation of crystalline small particles of GeS by microwave assisted sublimation of pure GeS [22]. This paper ©2006 Matrice Technology Limited Materials Research Innovations 10-2: 1433-075X
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Pub
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Materials Research Innovations Online 148
Elisabetta Bonometti Mario Castiglioni Paola Michelin Lausarot Cristina Leonelli Federica Bondioli Gian Carlo Pellacani Anna Angela Barba Amorphous Germanium(II) Sulfide Particles Obtained By Microwave Assisted Decomposition Of Germanium (IV) Sulfide Addresses for Correspondence MCastiglioni (E-mail mariocastiglioniunitoit Tel +39-11-6707584 Fax +39-11-6707591) EBonometti PMichelin Lausarot Dipartimento di Chimica Generale ed Organica Applicata Universitagrave di Torino Cso M drsquoAzeglio 48- 10125 Torino Italy CLeonelli FBondioli GCPellicani Dipartimento di Ingegneria dei Materiali e dellrsquoAmbiente Universitagrave di Modena e Reggio Emilia Via Vignolese 905- 41100 Modena Italy AABarba Dipartimento di Ingegneria Chimica ed Alimentare Universitagrave di Salerno Via Ponte Don Melillo 84084 Fisciano Italy Received 18 May 2005 Accepted 8 August 2005 Revised 23 February 2006 Keywords amorphous particles germanium sulfides microwaves nanoparticles sublimation INTRODUCTION Equilibrium reaction (1) has been used to calculate the standard molar enthalpy of formation for GeS2 and for the chemical transport of Ge [1 2] Nevertheless the high temperature behavior of GeS2 does not seem to be well understood [3] 2GeS2(s) 2GeS(g) + S2 (g) (1) Stoichiometric germanium sulfides namely GeS and GeS2 are semiconductors and hence many of their chemical and physical properties in crystal and vitreous phase have been studied [4 5 6 7] Both sulfides can be prepared in bulk thin films and powders [8 9] Preparation of vitreous GeS2 by rapid quenching of the liquid has been reported [10] Vitreous GeS has not been prepared in bulk but only in thin film [11 12 13] Sol-gel technique and polycondensation of [(CH3)4N]4-Ge4S10 under acidic conditions have been used to prepare small particles of GeS2 [8 14] Gas to particles conversion under many different arrangements is a widely used technique to prepare powders [9 15 16 17] It is quite a clean process but suffers the disadvantage of difficult control of particles agglomeration [18] Though recently weakly protonated GeS2 particles have been prepared by sublimation of GeS2 + H2S at about 1020 K and 7middot105 Pa pure molecular GeS2 can not be prepared in pure form by sublimation of solid GeS2 because the equilibrium reaction (1) is shifted to the right by the temperature increase [19 20] Some different spectroscopic properties have been observed in glassy and crystalline GeS2 as in glassy and crystalline GeS [12 21] We already reported on the preparation of crystalline small particles of GeS by microwave assisted sublimation of pure GeS [22] This paper
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Materials Research Innovations Online 149
will deal with the preparation of spherical amorphous small GeS particles by microwave assisted thermal decomposition of GeS2 according to reaction (1) EXPERIMENTAL Nanoparticles synthesis GeS2 was prepared by wet chemistry according to the literature and characterized by its Raman spectrum for checking chemical purity [8 23 24] 12 g of GeS2 were carefully mixed in an agate mortar with a threefold amount of graphite powder used as microwave absorber and to keep the system in reducing conditions [25] The mixture was transferred into an alumina crucible which was placed in a Pyrexreg glass container having inlet and outlet connections for gases and a small opening allowing the immersion in the mixture of a type K shielded and grounded thermocouple contained in an alumina pocket The entire system was then placed in the cavity of a custom made variable power singleminusmode microwave heating system working at 245 GHz The outlet tube of the glass container was connected to a series of gas washing bottles containing acetone to trap the sublimed GeS particles The system was washed in a stream of inert gas (He) flowing at a rate ranging from 600 to 2000 mlmin for approximately 10 min and then heated for 15 min at 600W power under continuous gas flow It is well known that when a solid sample is heated by microwave energy the temperature of the sample is not uniform because of the formation of hot spots [25] For this reason the temperature indicated by the thermocouple though in some degree reproducible by careful control of the amount of sample and of its position in the oven has been called ldquoobserved temperaturerdquo When the ldquoobserved temperaturerdquo reaches about 460K a white powder starts to sublime from the crucible At the ldquoobserved temperaturerdquo of 870K a dark brown powder is evolved and is collected on the upper part of the glass container and into the gas washing bottles The ldquoobserved temperaturerdquo was allowed to increase up to about 910K before stopping microwave irradiation The acetone suspension in the washing bottles was evaporated and the solid product mixed with the sublimed on the upper part of the glass reactor Nanoparticles characterization The nature and the purity of the sublimed matter were controlled by mass spectrometry using a Trace MS Plus Thermo Finnigan instrument heating the sample from room temperature to 520K at 25Kmin Raman spectra were obtained using a Bruker RFS 100 FT instrument the XRD spectra were collected using a Siemens D5000 (Cu Kα radiation and BraggminusBrentano geometry) instrument Scanning Electron Microscopy SEM images were obtained using a Leica Stereo Scan 420 instrument equipped with a microprobe for elemental analysis Transmission Electron Microscopy TEM images were obtained from a Jeol JEM 2010 equipped with GIF Gatan and Multiscan Camera 794 and EDS analysis device Link Inca 100 To calibrate the device for Ge and S standard samples of Ge metal and FeS2 were used TEM samples were prepared by ultrasonic stirring a small quantity of powder dispersed in doubly distilled water A drop of this suspension was dried out on a copper grid then coated with carbon Dielectric
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characterization of GeS2 reagent and GeS product was performed in the frequency range from 1 to 6 GHz using a network analyzer systemmdashthe 8753S Agilent Technologies instrument with the 85070D Agilent Technologies dielectric probe meter The measures were carried out on 6 mm in thick pellets of GeS2 and GeS obtained from pressed powders under 10 GPa
RESULTS AND DISCUSSION Figure 1 shows the dielectric behavior of the starting material GeS2 as a function of the frequency of the electromagnetic radiation in the 1 to 6 GHz range Both dielectric constant (εprime) and loss factor (εprimeprime) are reported The measurements are referred to at room temperature As reported on Fig 1 at 245 GHz the loss factor (εprimeprime) of GeS2 is low but steadily increasing as the frequency increases at the same time the dielectric constant (εprime) is higher and constant The ability of a material to interact with electromagnetic energy is related to the material complex dielectric constant (εlowast) εlowast = εprime + iεprimeprime The dielectric constant εprime (the real part of εlowast) is a measure of how much energy from an external electric field is stored in the material the loss factor εprimeprime (the imaginary part of εlowast) quantifies the efficiency with which the electromagnetic energy is converted to heat Therefore a material with a high loss factor is easily heated by microwaves [26] The behavior of both εprime and εprimeprime depicted in Fig 1 indicates that for GeS2 the efficiency with which the electromagnetic energy is converted in thermal energy is very low Also GeS (Fig 2) shows a low efficiency in converting electromagnetic energy in thermal energy as previously observed [22] As a consequence using 245 GHz radiation the heating of GeS2 starting from room temperature is minimum Thus to obtain sublimation a better energy absorber as graphite is necessary The addition of graphite to GeS2 also keeps the system under strong reducing conditions avoiding oxidation reactions of both reactant and products with oxygen impurities Although reaction (I) is reported by the literature as an ldquohigh temperature reactionrdquo it seems to take place at a quite low temperature 470K leading to white sulfur vapors and black crystals with a beautiful metallic sheen of GeS which start to sublime as a brown powder as the ldquoobserved temperaturerdquo reaches 870K [2 3 10] The white material which starts to sublime at 460K observed temperature has been found to be sulfur by mass spectrometry (Fig 3) The brown powder obtained at 870K was found to be a mixture of sulfur and GeS by MS analysis (Fig 4) After repeated washing with CS2 the sublimed material was free of sulfur as indicated by the mass spectrum reported on Fig 5 Unwashed samples of the sublimed material were submitted to TEMminusEDS analysis Figure 6 shows a large dark spherical particle presenting on its left side a small agglomerate of clearer material The EDS analysis (Fig 7) indicates for the larger particle a SGe ratio very close to 1 and for the agglomerate a SGe ratio close to 2 hence the large particle is sublimed GeS while the agglomerate consists of undecomposed GeS2 in agreement with equilibrium reaction (I) The amount of sublimed GeS2 is very small despite according to the literature it starts to sublime at a temperature somewhat higher than 870K [27] In fact the disulfide has not been detected by both MS (Figs 3ndash5) and
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Materials Research Innovations Online 151
Raman which shows for both CS2 washed and unwashed samples the same scattering peaks displayed by commercial 9999 GeS (Aldrich) at 268 237 212 112 and 94 cmminus1 in good agreement with the literature data [28] The presence of considerable amounts of sulfur from reaction (I) can also be observed from the EDS analysis of the particle shown on Fig 8 The particle has been collected on the walls of the glass reactor close to the crucible containing GeS2 and graphite The particle consists of an agglomerate containing carbon sulfur and a very small amount of germanium (Fig 9) Figures 10 and 11 are SEM pictures of materials obtained at a He flow rate of 06 and 20 liters per minute respectively In both cases the material consists in spherical particles with diameter ranging from lt 01 to about 3 microm On both pictures the particle size distribution has been calculated For the particles obtained al 06 Lmin the distribution (Fig 12) shows a maximum in the 05minus07 microm range whereas the size distribution of the particles obtained at 20 Lmin shows a maximum in the 03minus05 microm range (Fig 13) Moreover the entire particle size distribution is shifted to smaller size as the He flow increases and the particle sizes are smaller than in the case of sublimation of GeS in Ar flow [22] The thermal conductivity of He is more than eight time larger than that of Argon leading to a faster cooling of the subliming particles [27] The increase of the flow rate of the carrier gas leads to a more rapid removal of the particles from the hot subliming system Both the above conditions are in good agreement with the requirements that the hot primary particles should rapidly be cooled by the carrier gas and as the carrier gas flows faster should rapidly be removed from the hot subliming zone moreover rapid cooling rate and minimum time at high temperature prevent agglomeration [29 30] TEM observation (Fig 14) shows that spherical particles with diameters as small as 10minus20 nm can be obtained The interference fringes exhibited by the particle in the bottom right corner of Fig 14 do not fit with the reticular planes of GeS or graphite and are considered as moireacute interference fringes Though according to the XRD spectrum of CS2 washed samples reported in Fig 15 and to the absence of interference fringes on TEM photograph of Fig 14 the material is amorphous and it appears to be metastable In facts after 10 months aging at room temperature the compound becomes crystalline as shown by the XRD spectrum reported on Fig 16 CONCLUSIONS Microwave assisted sublimation of GeS has already been demonstrated to be a useful method for the preparation of crystal spherical particles of GeS [22] A similar preparation method is proposed for the preparation of GeS amorphous though metastable spherical small particles by microwave assisted sublimationminusdecomposition of GeS2 At the proposed conditions some contamination from GeS2 and S could be present nevertheless the amount of GeS2 is negligible being detectable only by TEMminusEDS analysis and the material can be easily purified from sulfur by repeated CS2 washing ACKNOWLEDGEMENTS This work received the financial support of MIUR (Progetti di Rilevante Interesse Nazionale 2001 ldquoSintesi di nanoparticelle assistita da microonderdquo)
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REFERENCES
1 OrsquoHare PAG (1995) Thermochimica Acta 2671 2 Schaumlfer H Trenkel M (1979) Z Anorg Allg Chem 458234 3 OrsquoHare PAG (1987) J Chem Thermodynamics 19675 4 Chandrasekhar HR Humphreys RG Cardona M (1977) Phys Rev B 162981 5 Drummond G Barrow RF (1953) Proc Phys Soc 65A277 6 Feltz A (1993) Amorphous Inorganic Materials and Glasses VCH Weinheim Basel
Cambridge New York 223 7 Nemanich RJ (1977) Phys Rev B 16165 8 Stanić V Etsell TH Pierre AC Mikula RJ (1997) J Mater Chem 7105 9 Vollath D Szabo DV Taylor RD Willis JO (1997) J Mater Res 122175 10 OrsquoHare PAG Volin KJ Susman S (1995) J Chem Thermodynamics 2799 11 Tomaszkiewicz I OrsquoHare PAG (1994) J Chem Thermodynamics 26727 12 Drahokoupil J Smotlacha O Fendrych F Klokočniacutekovaacute H Koslov MA (1986) J
nonminusCryst Solids 8843 13 Yabumoto T (1958) J Phys Soc of Japan 13559 14 MacLachlan MJ Petrov S Bedard RL Manners I Ozin GA (1998) Angew Chem Int 372076 15 Martinez B Roig A Molins E GonzalezminusCarrentildeo T Serna CJ (1998) J Appl Phys
833256 16 Kammler HK Maumldler L Pratsinis SE (2001) Chem Eng Technol 24583 17 Ford Q (1998) Ceram Ind 31 18 Pratsinis SE Vemury S (1996) Powder Technol 88267 19 Sutherland JT Poling SA Belin RC Martin SW (2004) Chem Mater 161226 20 Friesen M Junker M Schnoumlckel H (1999) Heteroatom Chem 10658 21 Černošek Z Černoškovaacute E Beneš L (1997) J Mol Structure 435193 22 Agostino A Bonometti E Castiglioni M Michelin Lausarot P (2004) Mat Res Innovat 841 23 Inorganic Syntheses (1946) Vol II Conrad Fernelius W Ed 102 24 Perakis A Kotsalas IP Pavlatou EA Raptis C (1999) Phys Stat Sol 211421 25 Microwave Processing of Materials (1994) Publication NMABminus473 National
Academy Press Washington DC 3068 26 Mingos DMP Baghurst DR (1991) Chem Soc Rev 201 27 Handbook of Chemistry and Physics (1992minus93) 73rd Ed CRC Press Bminus103 E12 E13 28 Hsueh HC Warren MC Vass H Ackland GJ Clark SJ Crain J (1996) Phys Rev 5314806 29 Flagan RC Luden MM (1995) Mater Sci Eng A204113 30 Haggerty JS (1987) Design of New Materials Cocke DL and Clearfield A (ed) Plenum Press New York 95
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Materials Research Innovations Online 153
1 2 3 4 5 60
1
2
3
4
5
6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
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Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
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Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
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Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
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Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
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Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
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Materials Research Innovations Online 149
will deal with the preparation of spherical amorphous small GeS particles by microwave assisted thermal decomposition of GeS2 according to reaction (1) EXPERIMENTAL Nanoparticles synthesis GeS2 was prepared by wet chemistry according to the literature and characterized by its Raman spectrum for checking chemical purity [8 23 24] 12 g of GeS2 were carefully mixed in an agate mortar with a threefold amount of graphite powder used as microwave absorber and to keep the system in reducing conditions [25] The mixture was transferred into an alumina crucible which was placed in a Pyrexreg glass container having inlet and outlet connections for gases and a small opening allowing the immersion in the mixture of a type K shielded and grounded thermocouple contained in an alumina pocket The entire system was then placed in the cavity of a custom made variable power singleminusmode microwave heating system working at 245 GHz The outlet tube of the glass container was connected to a series of gas washing bottles containing acetone to trap the sublimed GeS particles The system was washed in a stream of inert gas (He) flowing at a rate ranging from 600 to 2000 mlmin for approximately 10 min and then heated for 15 min at 600W power under continuous gas flow It is well known that when a solid sample is heated by microwave energy the temperature of the sample is not uniform because of the formation of hot spots [25] For this reason the temperature indicated by the thermocouple though in some degree reproducible by careful control of the amount of sample and of its position in the oven has been called ldquoobserved temperaturerdquo When the ldquoobserved temperaturerdquo reaches about 460K a white powder starts to sublime from the crucible At the ldquoobserved temperaturerdquo of 870K a dark brown powder is evolved and is collected on the upper part of the glass container and into the gas washing bottles The ldquoobserved temperaturerdquo was allowed to increase up to about 910K before stopping microwave irradiation The acetone suspension in the washing bottles was evaporated and the solid product mixed with the sublimed on the upper part of the glass reactor Nanoparticles characterization The nature and the purity of the sublimed matter were controlled by mass spectrometry using a Trace MS Plus Thermo Finnigan instrument heating the sample from room temperature to 520K at 25Kmin Raman spectra were obtained using a Bruker RFS 100 FT instrument the XRD spectra were collected using a Siemens D5000 (Cu Kα radiation and BraggminusBrentano geometry) instrument Scanning Electron Microscopy SEM images were obtained using a Leica Stereo Scan 420 instrument equipped with a microprobe for elemental analysis Transmission Electron Microscopy TEM images were obtained from a Jeol JEM 2010 equipped with GIF Gatan and Multiscan Camera 794 and EDS analysis device Link Inca 100 To calibrate the device for Ge and S standard samples of Ge metal and FeS2 were used TEM samples were prepared by ultrasonic stirring a small quantity of powder dispersed in doubly distilled water A drop of this suspension was dried out on a copper grid then coated with carbon Dielectric
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 150
characterization of GeS2 reagent and GeS product was performed in the frequency range from 1 to 6 GHz using a network analyzer systemmdashthe 8753S Agilent Technologies instrument with the 85070D Agilent Technologies dielectric probe meter The measures were carried out on 6 mm in thick pellets of GeS2 and GeS obtained from pressed powders under 10 GPa
RESULTS AND DISCUSSION Figure 1 shows the dielectric behavior of the starting material GeS2 as a function of the frequency of the electromagnetic radiation in the 1 to 6 GHz range Both dielectric constant (εprime) and loss factor (εprimeprime) are reported The measurements are referred to at room temperature As reported on Fig 1 at 245 GHz the loss factor (εprimeprime) of GeS2 is low but steadily increasing as the frequency increases at the same time the dielectric constant (εprime) is higher and constant The ability of a material to interact with electromagnetic energy is related to the material complex dielectric constant (εlowast) εlowast = εprime + iεprimeprime The dielectric constant εprime (the real part of εlowast) is a measure of how much energy from an external electric field is stored in the material the loss factor εprimeprime (the imaginary part of εlowast) quantifies the efficiency with which the electromagnetic energy is converted to heat Therefore a material with a high loss factor is easily heated by microwaves [26] The behavior of both εprime and εprimeprime depicted in Fig 1 indicates that for GeS2 the efficiency with which the electromagnetic energy is converted in thermal energy is very low Also GeS (Fig 2) shows a low efficiency in converting electromagnetic energy in thermal energy as previously observed [22] As a consequence using 245 GHz radiation the heating of GeS2 starting from room temperature is minimum Thus to obtain sublimation a better energy absorber as graphite is necessary The addition of graphite to GeS2 also keeps the system under strong reducing conditions avoiding oxidation reactions of both reactant and products with oxygen impurities Although reaction (I) is reported by the literature as an ldquohigh temperature reactionrdquo it seems to take place at a quite low temperature 470K leading to white sulfur vapors and black crystals with a beautiful metallic sheen of GeS which start to sublime as a brown powder as the ldquoobserved temperaturerdquo reaches 870K [2 3 10] The white material which starts to sublime at 460K observed temperature has been found to be sulfur by mass spectrometry (Fig 3) The brown powder obtained at 870K was found to be a mixture of sulfur and GeS by MS analysis (Fig 4) After repeated washing with CS2 the sublimed material was free of sulfur as indicated by the mass spectrum reported on Fig 5 Unwashed samples of the sublimed material were submitted to TEMminusEDS analysis Figure 6 shows a large dark spherical particle presenting on its left side a small agglomerate of clearer material The EDS analysis (Fig 7) indicates for the larger particle a SGe ratio very close to 1 and for the agglomerate a SGe ratio close to 2 hence the large particle is sublimed GeS while the agglomerate consists of undecomposed GeS2 in agreement with equilibrium reaction (I) The amount of sublimed GeS2 is very small despite according to the literature it starts to sublime at a temperature somewhat higher than 870K [27] In fact the disulfide has not been detected by both MS (Figs 3ndash5) and
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 151
Raman which shows for both CS2 washed and unwashed samples the same scattering peaks displayed by commercial 9999 GeS (Aldrich) at 268 237 212 112 and 94 cmminus1 in good agreement with the literature data [28] The presence of considerable amounts of sulfur from reaction (I) can also be observed from the EDS analysis of the particle shown on Fig 8 The particle has been collected on the walls of the glass reactor close to the crucible containing GeS2 and graphite The particle consists of an agglomerate containing carbon sulfur and a very small amount of germanium (Fig 9) Figures 10 and 11 are SEM pictures of materials obtained at a He flow rate of 06 and 20 liters per minute respectively In both cases the material consists in spherical particles with diameter ranging from lt 01 to about 3 microm On both pictures the particle size distribution has been calculated For the particles obtained al 06 Lmin the distribution (Fig 12) shows a maximum in the 05minus07 microm range whereas the size distribution of the particles obtained at 20 Lmin shows a maximum in the 03minus05 microm range (Fig 13) Moreover the entire particle size distribution is shifted to smaller size as the He flow increases and the particle sizes are smaller than in the case of sublimation of GeS in Ar flow [22] The thermal conductivity of He is more than eight time larger than that of Argon leading to a faster cooling of the subliming particles [27] The increase of the flow rate of the carrier gas leads to a more rapid removal of the particles from the hot subliming system Both the above conditions are in good agreement with the requirements that the hot primary particles should rapidly be cooled by the carrier gas and as the carrier gas flows faster should rapidly be removed from the hot subliming zone moreover rapid cooling rate and minimum time at high temperature prevent agglomeration [29 30] TEM observation (Fig 14) shows that spherical particles with diameters as small as 10minus20 nm can be obtained The interference fringes exhibited by the particle in the bottom right corner of Fig 14 do not fit with the reticular planes of GeS or graphite and are considered as moireacute interference fringes Though according to the XRD spectrum of CS2 washed samples reported in Fig 15 and to the absence of interference fringes on TEM photograph of Fig 14 the material is amorphous and it appears to be metastable In facts after 10 months aging at room temperature the compound becomes crystalline as shown by the XRD spectrum reported on Fig 16 CONCLUSIONS Microwave assisted sublimation of GeS has already been demonstrated to be a useful method for the preparation of crystal spherical particles of GeS [22] A similar preparation method is proposed for the preparation of GeS amorphous though metastable spherical small particles by microwave assisted sublimationminusdecomposition of GeS2 At the proposed conditions some contamination from GeS2 and S could be present nevertheless the amount of GeS2 is negligible being detectable only by TEMminusEDS analysis and the material can be easily purified from sulfur by repeated CS2 washing ACKNOWLEDGEMENTS This work received the financial support of MIUR (Progetti di Rilevante Interesse Nazionale 2001 ldquoSintesi di nanoparticelle assistita da microonderdquo)
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
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Lim
ited
Materials Research Innovations Online 152
REFERENCES
1 OrsquoHare PAG (1995) Thermochimica Acta 2671 2 Schaumlfer H Trenkel M (1979) Z Anorg Allg Chem 458234 3 OrsquoHare PAG (1987) J Chem Thermodynamics 19675 4 Chandrasekhar HR Humphreys RG Cardona M (1977) Phys Rev B 162981 5 Drummond G Barrow RF (1953) Proc Phys Soc 65A277 6 Feltz A (1993) Amorphous Inorganic Materials and Glasses VCH Weinheim Basel
Cambridge New York 223 7 Nemanich RJ (1977) Phys Rev B 16165 8 Stanić V Etsell TH Pierre AC Mikula RJ (1997) J Mater Chem 7105 9 Vollath D Szabo DV Taylor RD Willis JO (1997) J Mater Res 122175 10 OrsquoHare PAG Volin KJ Susman S (1995) J Chem Thermodynamics 2799 11 Tomaszkiewicz I OrsquoHare PAG (1994) J Chem Thermodynamics 26727 12 Drahokoupil J Smotlacha O Fendrych F Klokočniacutekovaacute H Koslov MA (1986) J
nonminusCryst Solids 8843 13 Yabumoto T (1958) J Phys Soc of Japan 13559 14 MacLachlan MJ Petrov S Bedard RL Manners I Ozin GA (1998) Angew Chem Int 372076 15 Martinez B Roig A Molins E GonzalezminusCarrentildeo T Serna CJ (1998) J Appl Phys
833256 16 Kammler HK Maumldler L Pratsinis SE (2001) Chem Eng Technol 24583 17 Ford Q (1998) Ceram Ind 31 18 Pratsinis SE Vemury S (1996) Powder Technol 88267 19 Sutherland JT Poling SA Belin RC Martin SW (2004) Chem Mater 161226 20 Friesen M Junker M Schnoumlckel H (1999) Heteroatom Chem 10658 21 Černošek Z Černoškovaacute E Beneš L (1997) J Mol Structure 435193 22 Agostino A Bonometti E Castiglioni M Michelin Lausarot P (2004) Mat Res Innovat 841 23 Inorganic Syntheses (1946) Vol II Conrad Fernelius W Ed 102 24 Perakis A Kotsalas IP Pavlatou EA Raptis C (1999) Phys Stat Sol 211421 25 Microwave Processing of Materials (1994) Publication NMABminus473 National
Academy Press Washington DC 3068 26 Mingos DMP Baghurst DR (1991) Chem Soc Rev 201 27 Handbook of Chemistry and Physics (1992minus93) 73rd Ed CRC Press Bminus103 E12 E13 28 Hsueh HC Warren MC Vass H Ackland GJ Clark SJ Crain J (1996) Phys Rev 5314806 29 Flagan RC Luden MM (1995) Mater Sci Eng A204113 30 Haggerty JS (1987) Design of New Materials Cocke DL and Clearfield A (ed) Plenum Press New York 95
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 153
1 2 3 4 5 60
1
2
3
4
5
6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
ublis
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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Man
ey amp
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Lim
ited
Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ublis
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(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey amp
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Lim
ited
Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
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Lim
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
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Man
ey amp
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Lim
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
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ited
Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Man
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Lim
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Man
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Lim
ited
Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Man
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Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey P
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(c)
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Man
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Lim
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Man
ey amp
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Lim
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey P
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(c)
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Man
ey amp
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Lim
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey P
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(c)
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Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 150
characterization of GeS2 reagent and GeS product was performed in the frequency range from 1 to 6 GHz using a network analyzer systemmdashthe 8753S Agilent Technologies instrument with the 85070D Agilent Technologies dielectric probe meter The measures were carried out on 6 mm in thick pellets of GeS2 and GeS obtained from pressed powders under 10 GPa
RESULTS AND DISCUSSION Figure 1 shows the dielectric behavior of the starting material GeS2 as a function of the frequency of the electromagnetic radiation in the 1 to 6 GHz range Both dielectric constant (εprime) and loss factor (εprimeprime) are reported The measurements are referred to at room temperature As reported on Fig 1 at 245 GHz the loss factor (εprimeprime) of GeS2 is low but steadily increasing as the frequency increases at the same time the dielectric constant (εprime) is higher and constant The ability of a material to interact with electromagnetic energy is related to the material complex dielectric constant (εlowast) εlowast = εprime + iεprimeprime The dielectric constant εprime (the real part of εlowast) is a measure of how much energy from an external electric field is stored in the material the loss factor εprimeprime (the imaginary part of εlowast) quantifies the efficiency with which the electromagnetic energy is converted to heat Therefore a material with a high loss factor is easily heated by microwaves [26] The behavior of both εprime and εprimeprime depicted in Fig 1 indicates that for GeS2 the efficiency with which the electromagnetic energy is converted in thermal energy is very low Also GeS (Fig 2) shows a low efficiency in converting electromagnetic energy in thermal energy as previously observed [22] As a consequence using 245 GHz radiation the heating of GeS2 starting from room temperature is minimum Thus to obtain sublimation a better energy absorber as graphite is necessary The addition of graphite to GeS2 also keeps the system under strong reducing conditions avoiding oxidation reactions of both reactant and products with oxygen impurities Although reaction (I) is reported by the literature as an ldquohigh temperature reactionrdquo it seems to take place at a quite low temperature 470K leading to white sulfur vapors and black crystals with a beautiful metallic sheen of GeS which start to sublime as a brown powder as the ldquoobserved temperaturerdquo reaches 870K [2 3 10] The white material which starts to sublime at 460K observed temperature has been found to be sulfur by mass spectrometry (Fig 3) The brown powder obtained at 870K was found to be a mixture of sulfur and GeS by MS analysis (Fig 4) After repeated washing with CS2 the sublimed material was free of sulfur as indicated by the mass spectrum reported on Fig 5 Unwashed samples of the sublimed material were submitted to TEMminusEDS analysis Figure 6 shows a large dark spherical particle presenting on its left side a small agglomerate of clearer material The EDS analysis (Fig 7) indicates for the larger particle a SGe ratio very close to 1 and for the agglomerate a SGe ratio close to 2 hence the large particle is sublimed GeS while the agglomerate consists of undecomposed GeS2 in agreement with equilibrium reaction (I) The amount of sublimed GeS2 is very small despite according to the literature it starts to sublime at a temperature somewhat higher than 870K [27] In fact the disulfide has not been detected by both MS (Figs 3ndash5) and
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 151
Raman which shows for both CS2 washed and unwashed samples the same scattering peaks displayed by commercial 9999 GeS (Aldrich) at 268 237 212 112 and 94 cmminus1 in good agreement with the literature data [28] The presence of considerable amounts of sulfur from reaction (I) can also be observed from the EDS analysis of the particle shown on Fig 8 The particle has been collected on the walls of the glass reactor close to the crucible containing GeS2 and graphite The particle consists of an agglomerate containing carbon sulfur and a very small amount of germanium (Fig 9) Figures 10 and 11 are SEM pictures of materials obtained at a He flow rate of 06 and 20 liters per minute respectively In both cases the material consists in spherical particles with diameter ranging from lt 01 to about 3 microm On both pictures the particle size distribution has been calculated For the particles obtained al 06 Lmin the distribution (Fig 12) shows a maximum in the 05minus07 microm range whereas the size distribution of the particles obtained at 20 Lmin shows a maximum in the 03minus05 microm range (Fig 13) Moreover the entire particle size distribution is shifted to smaller size as the He flow increases and the particle sizes are smaller than in the case of sublimation of GeS in Ar flow [22] The thermal conductivity of He is more than eight time larger than that of Argon leading to a faster cooling of the subliming particles [27] The increase of the flow rate of the carrier gas leads to a more rapid removal of the particles from the hot subliming system Both the above conditions are in good agreement with the requirements that the hot primary particles should rapidly be cooled by the carrier gas and as the carrier gas flows faster should rapidly be removed from the hot subliming zone moreover rapid cooling rate and minimum time at high temperature prevent agglomeration [29 30] TEM observation (Fig 14) shows that spherical particles with diameters as small as 10minus20 nm can be obtained The interference fringes exhibited by the particle in the bottom right corner of Fig 14 do not fit with the reticular planes of GeS or graphite and are considered as moireacute interference fringes Though according to the XRD spectrum of CS2 washed samples reported in Fig 15 and to the absence of interference fringes on TEM photograph of Fig 14 the material is amorphous and it appears to be metastable In facts after 10 months aging at room temperature the compound becomes crystalline as shown by the XRD spectrum reported on Fig 16 CONCLUSIONS Microwave assisted sublimation of GeS has already been demonstrated to be a useful method for the preparation of crystal spherical particles of GeS [22] A similar preparation method is proposed for the preparation of GeS amorphous though metastable spherical small particles by microwave assisted sublimationminusdecomposition of GeS2 At the proposed conditions some contamination from GeS2 and S could be present nevertheless the amount of GeS2 is negligible being detectable only by TEMminusEDS analysis and the material can be easily purified from sulfur by repeated CS2 washing ACKNOWLEDGEMENTS This work received the financial support of MIUR (Progetti di Rilevante Interesse Nazionale 2001 ldquoSintesi di nanoparticelle assistita da microonderdquo)
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
Man
ey P
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(c)
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Man
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Lim
ited
Materials Research Innovations Online 152
REFERENCES
1 OrsquoHare PAG (1995) Thermochimica Acta 2671 2 Schaumlfer H Trenkel M (1979) Z Anorg Allg Chem 458234 3 OrsquoHare PAG (1987) J Chem Thermodynamics 19675 4 Chandrasekhar HR Humphreys RG Cardona M (1977) Phys Rev B 162981 5 Drummond G Barrow RF (1953) Proc Phys Soc 65A277 6 Feltz A (1993) Amorphous Inorganic Materials and Glasses VCH Weinheim Basel
Cambridge New York 223 7 Nemanich RJ (1977) Phys Rev B 16165 8 Stanić V Etsell TH Pierre AC Mikula RJ (1997) J Mater Chem 7105 9 Vollath D Szabo DV Taylor RD Willis JO (1997) J Mater Res 122175 10 OrsquoHare PAG Volin KJ Susman S (1995) J Chem Thermodynamics 2799 11 Tomaszkiewicz I OrsquoHare PAG (1994) J Chem Thermodynamics 26727 12 Drahokoupil J Smotlacha O Fendrych F Klokočniacutekovaacute H Koslov MA (1986) J
nonminusCryst Solids 8843 13 Yabumoto T (1958) J Phys Soc of Japan 13559 14 MacLachlan MJ Petrov S Bedard RL Manners I Ozin GA (1998) Angew Chem Int 372076 15 Martinez B Roig A Molins E GonzalezminusCarrentildeo T Serna CJ (1998) J Appl Phys
833256 16 Kammler HK Maumldler L Pratsinis SE (2001) Chem Eng Technol 24583 17 Ford Q (1998) Ceram Ind 31 18 Pratsinis SE Vemury S (1996) Powder Technol 88267 19 Sutherland JT Poling SA Belin RC Martin SW (2004) Chem Mater 161226 20 Friesen M Junker M Schnoumlckel H (1999) Heteroatom Chem 10658 21 Černošek Z Černoškovaacute E Beneš L (1997) J Mol Structure 435193 22 Agostino A Bonometti E Castiglioni M Michelin Lausarot P (2004) Mat Res Innovat 841 23 Inorganic Syntheses (1946) Vol II Conrad Fernelius W Ed 102 24 Perakis A Kotsalas IP Pavlatou EA Raptis C (1999) Phys Stat Sol 211421 25 Microwave Processing of Materials (1994) Publication NMABminus473 National
Academy Press Washington DC 3068 26 Mingos DMP Baghurst DR (1991) Chem Soc Rev 201 27 Handbook of Chemistry and Physics (1992minus93) 73rd Ed CRC Press Bminus103 E12 E13 28 Hsueh HC Warren MC Vass H Ackland GJ Clark SJ Crain J (1996) Phys Rev 5314806 29 Flagan RC Luden MM (1995) Mater Sci Eng A204113 30 Haggerty JS (1987) Design of New Materials Cocke DL and Clearfield A (ed) Plenum Press New York 95
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
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(c)
WS
Man
ey amp
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Lim
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Materials Research Innovations Online 153
1 2 3 4 5 60
1
2
3
4
5
6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
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Man
ey amp
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Lim
ited
Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 8 TEM image of a composite particle collected near the sublimation crucible
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
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Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
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0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
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Raman which shows for both CS2 washed and unwashed samples the same scattering peaks displayed by commercial 9999 GeS (Aldrich) at 268 237 212 112 and 94 cmminus1 in good agreement with the literature data [28] The presence of considerable amounts of sulfur from reaction (I) can also be observed from the EDS analysis of the particle shown on Fig 8 The particle has been collected on the walls of the glass reactor close to the crucible containing GeS2 and graphite The particle consists of an agglomerate containing carbon sulfur and a very small amount of germanium (Fig 9) Figures 10 and 11 are SEM pictures of materials obtained at a He flow rate of 06 and 20 liters per minute respectively In both cases the material consists in spherical particles with diameter ranging from lt 01 to about 3 microm On both pictures the particle size distribution has been calculated For the particles obtained al 06 Lmin the distribution (Fig 12) shows a maximum in the 05minus07 microm range whereas the size distribution of the particles obtained at 20 Lmin shows a maximum in the 03minus05 microm range (Fig 13) Moreover the entire particle size distribution is shifted to smaller size as the He flow increases and the particle sizes are smaller than in the case of sublimation of GeS in Ar flow [22] The thermal conductivity of He is more than eight time larger than that of Argon leading to a faster cooling of the subliming particles [27] The increase of the flow rate of the carrier gas leads to a more rapid removal of the particles from the hot subliming system Both the above conditions are in good agreement with the requirements that the hot primary particles should rapidly be cooled by the carrier gas and as the carrier gas flows faster should rapidly be removed from the hot subliming zone moreover rapid cooling rate and minimum time at high temperature prevent agglomeration [29 30] TEM observation (Fig 14) shows that spherical particles with diameters as small as 10minus20 nm can be obtained The interference fringes exhibited by the particle in the bottom right corner of Fig 14 do not fit with the reticular planes of GeS or graphite and are considered as moireacute interference fringes Though according to the XRD spectrum of CS2 washed samples reported in Fig 15 and to the absence of interference fringes on TEM photograph of Fig 14 the material is amorphous and it appears to be metastable In facts after 10 months aging at room temperature the compound becomes crystalline as shown by the XRD spectrum reported on Fig 16 CONCLUSIONS Microwave assisted sublimation of GeS has already been demonstrated to be a useful method for the preparation of crystal spherical particles of GeS [22] A similar preparation method is proposed for the preparation of GeS amorphous though metastable spherical small particles by microwave assisted sublimationminusdecomposition of GeS2 At the proposed conditions some contamination from GeS2 and S could be present nevertheless the amount of GeS2 is negligible being detectable only by TEMminusEDS analysis and the material can be easily purified from sulfur by repeated CS2 washing ACKNOWLEDGEMENTS This work received the financial support of MIUR (Progetti di Rilevante Interesse Nazionale 2001 ldquoSintesi di nanoparticelle assistita da microonderdquo)
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REFERENCES
1 OrsquoHare PAG (1995) Thermochimica Acta 2671 2 Schaumlfer H Trenkel M (1979) Z Anorg Allg Chem 458234 3 OrsquoHare PAG (1987) J Chem Thermodynamics 19675 4 Chandrasekhar HR Humphreys RG Cardona M (1977) Phys Rev B 162981 5 Drummond G Barrow RF (1953) Proc Phys Soc 65A277 6 Feltz A (1993) Amorphous Inorganic Materials and Glasses VCH Weinheim Basel
Cambridge New York 223 7 Nemanich RJ (1977) Phys Rev B 16165 8 Stanić V Etsell TH Pierre AC Mikula RJ (1997) J Mater Chem 7105 9 Vollath D Szabo DV Taylor RD Willis JO (1997) J Mater Res 122175 10 OrsquoHare PAG Volin KJ Susman S (1995) J Chem Thermodynamics 2799 11 Tomaszkiewicz I OrsquoHare PAG (1994) J Chem Thermodynamics 26727 12 Drahokoupil J Smotlacha O Fendrych F Klokočniacutekovaacute H Koslov MA (1986) J
nonminusCryst Solids 8843 13 Yabumoto T (1958) J Phys Soc of Japan 13559 14 MacLachlan MJ Petrov S Bedard RL Manners I Ozin GA (1998) Angew Chem Int 372076 15 Martinez B Roig A Molins E GonzalezminusCarrentildeo T Serna CJ (1998) J Appl Phys
833256 16 Kammler HK Maumldler L Pratsinis SE (2001) Chem Eng Technol 24583 17 Ford Q (1998) Ceram Ind 31 18 Pratsinis SE Vemury S (1996) Powder Technol 88267 19 Sutherland JT Poling SA Belin RC Martin SW (2004) Chem Mater 161226 20 Friesen M Junker M Schnoumlckel H (1999) Heteroatom Chem 10658 21 Černošek Z Černoškovaacute E Beneš L (1997) J Mol Structure 435193 22 Agostino A Bonometti E Castiglioni M Michelin Lausarot P (2004) Mat Res Innovat 841 23 Inorganic Syntheses (1946) Vol II Conrad Fernelius W Ed 102 24 Perakis A Kotsalas IP Pavlatou EA Raptis C (1999) Phys Stat Sol 211421 25 Microwave Processing of Materials (1994) Publication NMABminus473 National
Academy Press Washington DC 3068 26 Mingos DMP Baghurst DR (1991) Chem Soc Rev 201 27 Handbook of Chemistry and Physics (1992minus93) 73rd Ed CRC Press Bminus103 E12 E13 28 Hsueh HC Warren MC Vass H Ackland GJ Clark SJ Crain J (1996) Phys Rev 5314806 29 Flagan RC Luden MM (1995) Mater Sci Eng A204113 30 Haggerty JS (1987) Design of New Materials Cocke DL and Clearfield A (ed) Plenum Press New York 95
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 153
1 2 3 4 5 60
1
2
3
4
5
6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey amp
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Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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ey amp
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey amp
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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ey amp
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey amp
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ey amp
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
WS
Man
ey amp
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ited
Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
WS
Man
ey amp
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ited
Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
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ey amp
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Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
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(c)
WS
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ey amp
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Lim
ited
Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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ey P
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(c)
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ey amp
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Lim
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ey P
ublis
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(c)
WS
Man
ey amp
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Lim
ited
Materials Research Innovations Online 152
REFERENCES
1 OrsquoHare PAG (1995) Thermochimica Acta 2671 2 Schaumlfer H Trenkel M (1979) Z Anorg Allg Chem 458234 3 OrsquoHare PAG (1987) J Chem Thermodynamics 19675 4 Chandrasekhar HR Humphreys RG Cardona M (1977) Phys Rev B 162981 5 Drummond G Barrow RF (1953) Proc Phys Soc 65A277 6 Feltz A (1993) Amorphous Inorganic Materials and Glasses VCH Weinheim Basel
Cambridge New York 223 7 Nemanich RJ (1977) Phys Rev B 16165 8 Stanić V Etsell TH Pierre AC Mikula RJ (1997) J Mater Chem 7105 9 Vollath D Szabo DV Taylor RD Willis JO (1997) J Mater Res 122175 10 OrsquoHare PAG Volin KJ Susman S (1995) J Chem Thermodynamics 2799 11 Tomaszkiewicz I OrsquoHare PAG (1994) J Chem Thermodynamics 26727 12 Drahokoupil J Smotlacha O Fendrych F Klokočniacutekovaacute H Koslov MA (1986) J
nonminusCryst Solids 8843 13 Yabumoto T (1958) J Phys Soc of Japan 13559 14 MacLachlan MJ Petrov S Bedard RL Manners I Ozin GA (1998) Angew Chem Int 372076 15 Martinez B Roig A Molins E GonzalezminusCarrentildeo T Serna CJ (1998) J Appl Phys
833256 16 Kammler HK Maumldler L Pratsinis SE (2001) Chem Eng Technol 24583 17 Ford Q (1998) Ceram Ind 31 18 Pratsinis SE Vemury S (1996) Powder Technol 88267 19 Sutherland JT Poling SA Belin RC Martin SW (2004) Chem Mater 161226 20 Friesen M Junker M Schnoumlckel H (1999) Heteroatom Chem 10658 21 Černošek Z Černoškovaacute E Beneš L (1997) J Mol Structure 435193 22 Agostino A Bonometti E Castiglioni M Michelin Lausarot P (2004) Mat Res Innovat 841 23 Inorganic Syntheses (1946) Vol II Conrad Fernelius W Ed 102 24 Perakis A Kotsalas IP Pavlatou EA Raptis C (1999) Phys Stat Sol 211421 25 Microwave Processing of Materials (1994) Publication NMABminus473 National
Academy Press Washington DC 3068 26 Mingos DMP Baghurst DR (1991) Chem Soc Rev 201 27 Handbook of Chemistry and Physics (1992minus93) 73rd Ed CRC Press Bminus103 E12 E13 28 Hsueh HC Warren MC Vass H Ackland GJ Clark SJ Crain J (1996) Phys Rev 5314806 29 Flagan RC Luden MM (1995) Mater Sci Eng A204113 30 Haggerty JS (1987) Design of New Materials Cocke DL and Clearfield A (ed) Plenum Press New York 95
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 153
1 2 3 4 5 60
1
2
3
4
5
6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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ey P
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(c)
WS
Man
ey amp
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Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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ey P
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(c)
WS
Man
ey amp
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Lim
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Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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ey P
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(c)
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Man
ey amp
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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1 2 3 4 5 60
1
2
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4
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6
7
8
9
101 2 3 4 5 6
0
1
2
3
4
5
6
7
8
9
10
loss factor (ε)
dielectric constant (ε)
Per
mitt
ivity
Frequency GHz
Fig 1 Dielectric behavior of GeS2 in the 1-6 GHz at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
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64
36160 256
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19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
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10664
32 44
104
48
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7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
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4
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7
8
9
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32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
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Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 8 TEM image of a composite particle collected near the sublimation crucible
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
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Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
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Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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0
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0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 154
1 2 3 4 5 6-10123456789
101 2 3 4 5 6
-1012345678910
loss factor
dielectric constant
Per
mitt
ivity
Frequency GHz
Fig 2 Dielectric behavior of GeS in the 1-6 GHZ at room temperature
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
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65
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64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
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e Ab
unda
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10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
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4
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6
7
8
9
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11
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13
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ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 8 TEM image of a composite particle collected near the sublimation crucible
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
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Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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0
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0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 155
CXcaliburdatacastiglioniA_16_10_03 16102003 161707
A_16_10_03 69 RT 116 AV 1 NL 126E8T 00 + c EI det=25100 Full ms [ 3000-100000]
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400mz
0
5
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25
30
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40
45
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55
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65
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85
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ativ
e A
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ance
64
36160 256
128
96
19238 258
16213066
19443 22457 69 9826083 85 111 22616414912344 9973 196132 262236179 207 243 283 355311288 327 368341 386 395
Fig 3 Mass spectrum of material (sulfur) sublimed at 460 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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ublis
hing
(c)
WS
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Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
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55
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75
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ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
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ey P
ublis
hing
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
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Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
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Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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0
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0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
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ey P
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hing
(c)
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ey amp
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Materials Research Innovations Online 156
CXcaliburdatacastiglioniGES 16_3_04 22042004 111118
GES 16_3_04 384 RT 654 AV 1 NL 104E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190mz
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e Ab
unda
nce
10664
32 44
104
48
102
7441108
39 7236
70
7655 9166 7745
795651 1158257 96 97 128117 13389 11960 14585 109 165152134 191171159 189178 193 198
Fig 4 Mass spectrum of material (GeS + C) sublimed at 870 K
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
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ey P
ublis
hing
(c)
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
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9
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Rel
ativ
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bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 12 Size distribution of the particles depicted in Fig 10
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Fig 13 Size distribution of the particles depicted in Fig 11
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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d by
Man
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ublis
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(c)
WS
Man
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Son
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Materials Research Innovations Online 157
CXcaliburdatacastiglioniGESPULITO 15102003 151952
GESPULITO 496 RT 846 AV 1 NL 316E6T 00 + c EI det=25100 Full ms [ 3000-100000]
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230mz
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rel
ativ
e A
bund
ance
32
106
10440 74
72102
70
10844 7634
48 6436 55 857957 20791 110 133 16997 148 189 193119 144128 165 198151 221176 183 229214159
Fig 5 Mass spectrum of the material (GeS) sublimated at 870 K after washing with CS2
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
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(c)
WS
Man
ey amp
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 158
Fig 6 TEM image showing a large GeS particle and a small agglomerate of sulfur rich material
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Man
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Son
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
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Man
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(c)
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Man
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Son
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Materials Research Innovations Online 159
Fig 7 EDS spectra of the particles in Fig 6 showing their GeS ratio
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 160
Fig 8 TEM image of a composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 161
Fig 9 EDS spectrum of the composite particle collected near the sublimation crucible
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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(c)
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Materials Research Innovations Online 162
Fig 10 SEM picture of the particle collected using He carrier flowing at 06 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Materials Research Innovations Online 164
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Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 163
Fig 11 SEM picture of the particle collected using He carrier flowing at 2 lmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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Man
ey P
ublis
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(c)
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Man
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Son
Lim
ited
Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 164
0
10
20
30
40
50
60
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 12 Size distribution of the particles depicted in Fig 10
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 165
0
5
10
15
20
25
30
35
40
45
0 - 01 01 - 03 03 - 05 05 - 07 07 - 09 09 - 11 11 - 13 13 - 15 15 - 19 25 - 3
microns
Fig 13 Size distribution of the particles depicted in Fig 11
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 166
Fig 14 TEM image of some particles obtained using he flow of 2 ltmin
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 167
Fig 15 XRD spectrum of CS2 washed GeS particles showing their amorphous state
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
Pub
lishe
d by
Man
ey P
ublis
hing
(c)
WS
Man
ey amp
Son
Lim
ited
Materials Research Innovations Online 168
GeSOTT04_1 - File GeS OTT04_1RAW - Type 2ThTh locked - Start 7000 deg - End 100000 deg - Step 0005 deg - Step time 1 s - Temp 25 degC (Room) - Time Started 0 s - 2-Theta 7000 deg - Theta
Conteggi (Cps)
2 theta
20 30 40 50 60 70 80
Fig 16 XRD spectrum of the CS2 washed GeS particles after 10 month aging
copy2006 Matrice Technology Limited Materials Research Innovations 10-2 1433-075X
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