ISSN 0306-0012 CRITICAL REVIEW Yuze Lin, Yongfang Li and Xiaowei Zhan Small molecule semiconductors for high-efficiency organic photovoltaics www.rsc.org/chemsocrev Volume 41 | Number 11 | 7 June 2012 | Pages 4089–4380 Chemical Society Reviews Downloaded by Universitat Erlangen Nurnberg on 24 July 2012 Published on 28 March 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15313K View Online / Journal Homepage / Table of Contents for this issue
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ISSN 0306-0012
CRITICAL REVIEWYuze Lin, Yongfang Li and Xiaowei ZhanSmall molecule semiconductors for high-effi ciency organic photovoltaics
www.rsc.org/chemsocrev Volume 41 | Number 11 | 7 June 2012 | Pages 4089–4380
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This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 4245–4272 4245
Cite this: Chem. Soc. Rev., 2012, 41, 4245–4272
Small molecule semiconductors for high-efficiency organic photovoltaics
Yuze Lin,ab
Yongfang Liaand Xiaowei Zhan*
a
Received 18th November 2011
DOI: 10.1039/c2cs15313k
Organic photovoltaic cells (OPVs) are a promising cost-effective alternative to silicon-based solar
cells, and possess light-weight, low-cost, and flexibility advantages. Significant progress has been
achieved in the development of novel photovoltaic materials and device structures in the last
decade. Nowadays small molecular semiconductors for OPVs have attracted considerable
attention, due to their advantages over their polymer counterparts, including well-defined
molecular structure, definite molecular weight, and high purity without batch to batch variations.
The highest power conversion efficiencies of OPVs based on small molecular donor/fullerene
acceptors or polymeric donor/fullerene acceptors are up to 6.7% and 8.3%, respectively, and
meanwhile nonfullerene acceptors have also exhibited some promising results. In this review we
summarize the developments in small molecular donors, acceptors (fullerene derivatives and
nonfullerene molecules), and donor–acceptor dyad systems for high-performance multilayer,
bulk heterojunction, and single-component OPVs. We focus on correlations of molecular chemical
structures with properties, such as absorption, energy levels, charge mobilities, and photovoltaic
performances. This structure–property relationship analysis may guide rational structural design
and evaluation of photovoltaic materials (253 references).
Introduction
Nowadays, fossil fuel (such as coal, oil, and gas) production and
use gives rise to a mass of environmental problems, and also their
stocks are diminishing. The need to develop renewable energy
sources has become urgent. The development of photovoltaic
cells (PVs), which transform inexhaustible solar energy into
electricity, is therefore one of the most promising long-term
solutions for clean, renewable energy. Currently, the main
barrier that prevents PV technology from providing a large
fraction of energy is the high cost of silicon-based PVs.
Organic photovoltaic cells (OPVs) are a promising cost-effective
alternative to silicon-based solar cells, and possess low-cost, light-
weight, and flexibility advantages. Contemporary OPVs are based
a Beijing National Laboratory for Molecular Sciences and KeyLaboratory of Organic Solids, Institute of Chemistry,Chinese Academy of Sciences, Beijing 100190, China.E-mail: [email protected]
bGraduate University of Chinese Academy of Sciences,Beijing 100049, China
Yuze Lin
Yuze Lin received a BS degreein chemistry from BeijingInstitute of Technology in2009. Now he is a PhD studentat the Institute of Chemistry,Chinese Academy of Sciences.His research interests includesynthesis of conjugated smallmolecules and polymers andtheir application in solar cells.
Xiaowei Zhan
Xiaowei Zhan obtained a PhDdegree in chemistry fromZhejiang University in 1998.He was then a postdoctoralresearcher at the Institute ofChemistry, Chinese Academyof Sciences (ICCAS) from1998 to 2000, and in 2000 hewas promoted to AssociateProfessor at ICCAS. Dr Zhanworked in the University ofArizona and Georgia Instituteof Technology from 2002 to2006 as Research Associateand Research Scientist. He hasbeen a full professor at ICCAS
since 2006. His research interests are in the development of organicand polymeric materials for organic electronics and photonics.
4246 Chem. Soc. Rev., 2012, 41, 4245–4272 This journal is c The Royal Society of Chemistry 2012
on a heterojunction resulting from the contact of an electron
donor (D) and an electron acceptor (A) material. Absorption
of solar photons creates excitons, which diffuse to the D/A
interface, where they are dissociated into free holes and
electrons, and opposite polarity carriers (holes and electrons)
transport through the donor and acceptor channels to anodes
and cathodes respectively, subsequently charges are collected at
the electrodes, resulting in the generation of electrical power.
D/A heterojunctions can be created with two main types of
architectures, bilayer heterojunction1 and bulk heterojunction
(BHJ).2
Before the mid 1980s, in conventional OPVs, a single layer
of single component organic material was sandwiched between
two different electrodes with different work functions.3 In
these single-layer and single-component cells, the built-in
potential is derived from either a Schottky-type potential
barrier at one of the metal/organic contacts or the difference in
work function of the electrodes, and the photovoltaic properties
are strongly dependent on the nature of the electrodes. These
early OPVs showed very poor performance.
In 1986, Tang fabricated a bilayer heterojunction solar cell
with an efficiency approaching 1%, which was a milestone in
the development of OPVs.1 Bilayer heterojunction architecture
has been intensively investigated and still is an invaluable tool
for the evaluation of new active materials, nevertheless,
performance of OPVs based on this structure is limited by the
short exciton diffusion length in organic materials (typically
5–20 nm).4 Since the exciton dissociation process is confined to
the D/A interfacial zone, only excitons produced at a distance
shorter than their diffusion length have a good probability to
reach the interfacial zone and generate free charge carriers. So
the exciton diffusion length limits the maximum thickness of the
active layer and thus the maximum fraction of the incident light
that the cell can absorb and covert into electricity.
In 1991, Hiramoto et al. fabricated a novel type of three-
layered OPV with a codeposited interlayer of mixed pigments
between the respective pigment layers, and the interlayer acted as
an efficient carrier photogeneration layer.5 Actually, this type
OPV device is the predecessor of hybrid planar-mixed molecular
heterojunction (PMHJ) OPVs.6 And the mixed interlayer was
recognized as the first bulk heterojunction layer in small
molecule-based OPVs.
In 1992, Sariciftci et al.7 demonstrated that photoexcitation
of a mixture of a conjugated polymer and fullerene (C60)
resulted in an ultrafast, highly efficient photoinduced electron
transfer. And then Yu et al.2 and Halls et al.8 created the ‘‘bulk
heterojunction’’ (BHJ) concept, which is one of the best OPV
device architectures so far. BHJ is a blend of bicontinuous and
interpenetrating donor and acceptor components in a bulk
volume. Such a nanoscale network exhibits a D/A phase
separation in a 5–20 nm length scale, which is within a distance
less than the exciton diffusion length. Compared to bilayer
heterojunction, BHJ significantly increases the D/A interfacial
area, leading to enhanced efficiency of the OPV devices.9
Two or even more OPV cells can be stacked on top of each
other to form a tandem OPV structure, which enables one to
resolve two limiting factors existing intrinsically among organic
semiconductor molecules: poor charge carrier mobility and a
narrow light absorption range.
The bilayer heterojunction and BHJ OPV device structures
are shown in Fig. 1. In the two devices, the photoactive layers
both sandwiched between a high work function anode, typically
a transparent indium tin oxide (ITO) layer, and a relatively low
work function metal cathode, such as Ca, Al. In the bilayer
heterojunction device, the donor materials stick to the anode
and the acceptor materials stick to the cathode, while the active
layer is blend of donor and acceptor materials in BHJ device.
In principle, there are two processing techniques for the
fabrication of OPV devices, vacuum deposition and solution
processing. Generally, the bilayer heterojunction was fabri-
cated by vacuum deposition since it is difficult to find suitable
solvents for donor layer and acceptor layer without destroying
the D/A interface. And both of the two processing techniques
are suitable for the BHJ devices. Some of small molecules such
as metal phthalocyanine and C60 can be deposited under high
vacuum conditions by thermal evaporation. By coevaporation
of donor and acceptor materials, BHJ layers can be obtained.
On the other hand, soluble materials can be deposited from
solution, by spin coating, inkjet printing, gravure or flexographic
printing.
In OPV devices, principal figures-of-merit include power
conversion efficiency (PCE), short-circuit current density
(JSC), open-circuit voltage (VOC), and fill factor (FF), defining,
respectively, the ratio between the output device electrical
energy versus the input solar energy, the device current density
when no reverse bias is applied, and the device voltage when
no current flows through the cell, and the ratio between
maximum power of the device and JSC � VOC.
Fig. 1 The architecture structure of bilayer heterojunction (a) and
BHJ (b) OPV devices.
Yongfang Li
Yongfang Li has been aprofessor at the Institute ofChemistry, Chinese Academyof Sciences (ICCAS) since1993. He obtained his PhDdegree in physical chemistryin 1986 from Fudan University,then came to ICCAS as a post-doctoral fellow working onconducting polymers with Prof.Renyuan Qian (1986–1988).He did visiting research in Prof.Hiroo Inokuchi’s lab at theInstitute for Molecular Sciencein Japan from 1988 to 1991and in Prof. Alan J. Heeger’s
lab at UCSB from 1997 to 1998. His present research interestsare polymer solar cells and related photovoltaic materialsincluding conjugated polymer donor, solution-processable organicmolecule donor and fullerene derivative acceptor materials.
a In film. b O and S: measured by OFET or SCLC method, N: in neat film. c From electrochemistry unless stated otherwise, U: from UPS.d Donor/acceptor: bilayer by vacuum deposition; donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum deposition.e AM1.5, 100 mW cm�2 unless stated otherwise. f 118 mW cm�2. g 80 mW cm�2. h 99 mW cm�2.
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