2012-Small Molecule Semiconductors For High-Efficiency Organic Photovoltaics

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Downloaded by Universitat Erlangen Nurnberg on 24 July 2012 Published on 28 March 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15313K
Volume 41 | Number 11 | 7 June 2012 | Pages 40894380
ISSN 0306-0012
CRITICAL REVIEW Yuze Lin, Yongfang Li and Xiaowei Zhan Small molecule semiconductors for high-efficiency organic photovoltaics
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CRITICAL REVIEW
Small molecule semiconductors for high-eciency organic photovoltaics

Yuze Lin,ab Yongfang Lia and Xiaowei Zhan*a
Received 18th November 2011 DOI: 10.1039/c2cs15313k
Organic photovoltaic cells (OPVs) are a promising cost-eective alternative to silicon-based solar cells, and possess light-weight, low-cost, and exibility advantages. Signicant 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-dened molecular structure, denite molecular weight, and high purity without batch to batch variations. The highest power conversion eciencies 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 donoracceptor 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 structureproperty 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
a
Beijing National Laboratory for Molecular Sciences and Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. E-mail: xwzhan@iccas.ac.cn b Graduate University of Chinese Academy of Sciences, Beijing 100049, China
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-eective alternative to silicon-based solar cells, and possess low-cost, lightweight, and exibility advantages. Contemporary OPVs are based
Yuze Lin received a BS degree in chemistry from Beijing Institute of Technology in 2009. Now he is a PhD student at the Institute of Chemistry, Chinese Academy of Sciences. His research interests include synthesis of conjugated small molecules and polymers and their application in solar cells.
Yuze Lin
Xiaowei Zhan obtained a PhD degree in chemistry from Zhejiang University in 1998. He was then a postdoctoral researcher at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS) from 1998 to 2000, and in 2000 he was promoted to Associate Professor at ICCAS. Dr Zhan worked in the University of Arizona and Georgia Institute of Technology from 2002 to 2006 as Research Associate and Research Scientist. He has Xiaowei Zhan been a full professor at ICCAS since 2006. His research interests are in the development of organic and polymeric materials for organic electronics and photonics.
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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 diuse 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 dierent electrodes with dierent 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 dierence 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 eciency 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 diusion length in organic materials (typically 520 nm).4 Since the exciton dissociation process is conned to the D/A interfacial zone, only excitons produced at a distance shorter than their diusion length have a good probability to reach the interfacial zone and generate free charge carriers. So the exciton diusion 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 threelayered OPV with a codeposited interlayer of mixed pigments between the respective pigment layers, and the interlayer acted as an ecient carrier photogeneration layer.5 Actually, this type
Yongfang Li has been a professor at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS) since 1993. He obtained his PhD degree in physical chemistry in 1986 from Fudan University, then came to ICCAS as a postdoctoral fellow working on conducting polymers with Prof. Renyuan Qian (19861988). He did visiting research in Prof. Hiroo Inokuchis lab at the Institute for Molecular Science in Japan from 1988 to 1991 Yongfang Li and in Prof. Alan J. Heegers lab at UCSB from 1997 to 1998. His present research interests are polymer solar cells and related photovoltaic materials including conjugated polymer donor, solution-processable organic molecule donor and fullerene derivative acceptor materials.
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OPV device is the predecessor of hybrid planar-mixed molecular heterojunction (PMHJ) OPVs.6 And the mixed interlayer was recognized as the rst 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 ecient 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 520 nm length scale, which is within a distance less than the exciton diusion length. Compared to bilayer heterojunction, BHJ signicantly increases the D/A interfacial area, leading to enhanced eciency 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 fabricated by vacuum deposition since it is dicult to nd 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 exographic printing. In OPV devices, principal gures-of-merit include power conversion eciency (PCE), short-circuit current density (JSC), open-circuit voltage (VOC), and ll factor (FF), dening, 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 ows 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.
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The photoactive materials, including polymeric and small molecular semiconductors, play a key role in inuencing physical processes involved in energy conversion, which in turn determine the electrical characteristics of the solar cell, such as JSC, VOC, and FF, and ultimately PCE. Recently, OPVs based on a p-type conjugated polymer as a donor and a fullerene derivative [6,6]-phenyl-C61 (or C71)-butyric acid methyl ester (PC61BM or PC71BM) as an acceptor have been rapidly developing, and so far the highest reported PCEs of this type OPVs are up to 8.3%,10 but still below 10% that is often regarded as being a prerequisite for large-scale commercial applications. On the other hand, small molecular semiconductors for OPVs have attracted considerable attention, due to their advantages over their polymer counterparts, which include well-dened molecular structure, denite molecular weight, and high purity without batch to batch variations.11 An increasing number of publications on OPVs based on small molecules have appeared, the PCEs of devices based on small molecule donors and fullerene acceptors fabricated by vacuum deposition or solution processing are both in excess of 6%.1215 As for small molecule acceptors, compared to the fullerene derivatives such as PC61BM and PC71BM, the development of nonfullerene small molecular acceptors has been lagged with relatively low performance. Recently, research on nonfullerene acceptors has become more active due to their interesting potentials, such as convenient synthesis, low cost, easy tunability of energy levels, and perhaps most importantly, better absorption in the visible spectrum. A number of reviews have summarized the synthesis and application of conjugated polymeric active materials,1631 small molecular donors,3238 fullerene acceptors,3941 small molecular nonfullerene acceptors42,43 in OPVs as well as device physics.4452 In the present review, we focus on the representative small molecular donors, acceptors and donor acceptor dyads in single OPVs. Progress in the past decade has been substantial, but continued development of OPV materials will require a better understanding of the relationships between molecular structure, electronic structure, materials microstructure, charge transport and photovoltaic properties than is currently available. For these reasons, we will survey and analyze what is currently known concerning structure/property relationships of photovoltaic small molecules.
band gap, and absorption coecient, all greatly aect the performance of OPV device. In this section, some representative small molecular donors such as dyes, fused acenes, oligothiophenes, and triphenylamine-based molecules used in the active layer of OPVs are described and discussed. Dyes Of a variety of small molecular donors that have been reported in the literature, dye-based molecules are rst and common. Several famous classes of dyes are believed to be potential materials in OPVs, such as phthalocyanine (Pc), subphthalocyanine (SubPc), merocyanine (MC), squaraine (SQ), diketopyrrolopyrroles (DPP), borondipyrromethene (BODIPY), isoindigo (ID), perylene diimides (PDI), and quinacridone (QD). As several groups have demonstrated, functionalizing a dye molecule has been conrmed to be a successful approach to donor design. Table 1 provides a summary of electronic properties as well as OPV data for representative dye-based donors (Fig. 2). Pc, comprising four isoindole units connected by 1,3-aza linkages, is a planar and highly aromatic 18-p-electron macrocycle. Pc derivatives typically exhibit excellent thermal and chemical stability,54 and they also oer exibility in their optical and electronic properties through synthetic modications, such as attaching functional groups to the molecule perimeter. The optoelectronic properties and stacking in the solid state of Pc derivatives can be turned by replacing of the two protons in the molecular cavity with a metal ion. Although many metal Pc complexes have been used in OPVs, CuPc (a1) and ZnPc (a2) have been the most common choices to date for application in Pc-based OPV devices, due to longer exciton diusion length of CuPc and ZnPc as compared to the other Pcs.55 In 1986, CuPc was rst used as a donor material in bilayer heterojunction OPV by Tang, and the device showed a PCE value of 1%.1 Inspired by this pioneering contribution, Pc has been commonly applied in vacuum-deposited OPV devices, due to high absorption coecient and long exciton diusion length.5660 And Pcs are frequently paired with fullerenes in the OPV active layer. The CuPc/C60 combination is among the most common for small molecule OPV active layers at present, and devices deriving from this system exhibited high performance.6 In 2001, Forrest and Peumans demonstrated that bilayer heterojunction OPVs based on CuPc and C60 with PCE of 3.6% can be achieved under 150 mW cm2 simulated AM1.5G illumination,57 while the BHJ OPVs based on a mixture of vacuum codeposited CuPc and C60 were fabricated and the best PCE was up to 3.5% at 100 mW cm2 simulated AM1.5G illumination.59 Later, Forrest et al. fabricated an OPV structure with a planar-mixed heterojunction (PMHJ), i.e., a mixed layer consisting of CuPc and C60 sandwiched between homogeneous CuPc and C60 layers, and the device aorded a maximum PCE of 5.0%, at 120 mW cm2 under simulated AM1.5 solar illumination.6 Additionally, stacking two of these cells together in a tandem cell resulted in a ca. 15% increase in device performance and a PCE of 5.7% at 100 mW cm2 AM1.5 simulated solar illumination.60 Planar Pcs have relatively narrow absorption band and cannot eectively absorb low-energy photons, while ca. 50% of photons
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Small molecular donors

Small molecular semiconductors can be generally classied as hole or electron transporting (p-type or n-type) materials according to the type of orderly transferring charge carriers, under a given set of conditions, stemming from removal of electrons from the lled molecular orbitals or from the addition of electrons to empty orbitals, respectively. Many small molecular p-type semiconductors have been studied for decades.53 Among these molecules, only a small fraction has been applied successfully as electron donors in OPV devices due to the various optical, electrical, and stability requirements demanded of the chosen materials. The properties of materials, such as hole mobility (i.e., the distance over which holes are transported per second under the unit electric eld), exciton diusion length, thin lm morphology, frontier energy level alignment,
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Optical and electronic properties, mobilities, and OPV performance of dye-based donors Egopt/eV mhb/cm2 V1 s1 HOMOc/LUMO/eV Active layerd a1/f1 a1/C60 a1:C60 (1 : 1 vac) a1/a1:C60 (1 : 1 vac)/C60 a3/C60 a4/C60 a6/C60 a7(sol)/C60 a7(vac)/C60 a8:PC61BM (1 : 3) a9:PC61BM (3 : 7) a10:PC61BM (9 : 11) a10:C60 (1 : 1 vac) a10:C60 (9 : 11 vac) a11:PC71BM (9 : 11) a12:PC61BM (1 : 3) a13:PC71BM (1 : 3) a14:PC71BM (3 : 2) a15/C60 a15(sol)/C60 a15:PC71BM (1 : 6) a16(sol)/C60 a17:PC61BM (1 : 2) a18:PC61BM (1 : 2) a17:a18:PC61BM (1 : 1 : 2) a19:PC61BM (1 : 2) a20:PC61BM (7 : 3) a21:PC71BM (1 : 1) a22:PC71BM (3 : 2) a23:PC61BM (1 : 1) a24:PC71BM (2 : 1) a25:PC61BM (3 : 2) a26:PC61BM (1 : 1) a27:PC61BM (1 : 2) a28:PC71BM (1 : 2) JSC /mA cm2 VOC/V FF 2.3 18.8 15.4 15.0 15.1 3.36 5.6 6.1 5.3 6.3 8.24 11.5 12.6 10.2 5.70 9.32 12.6 6.89 9.71 12.0 10.0 4.43 4.14 4.70 7.00 8.42 9.2 10 4.9 8.3 11.27 6.3 5.94 8.87 0.45 0.58 0.50 0.54 0.68 0.57 0.97 0.55 0.79 0.90 0.76 0.94 0.80 0.96 1.0 0.62 0.57 0.31 0.83 0.78 0.92 0.90 0.80 0.75 0.87 0.75 0.67 0.75 0.92 0.77 0.76 0.84 0.76 0.78 0.72 0.65 0.52 0.46 0.61 0.50 0.53 0.57 0.49 0.49 0.32 0.36 0.34 0.48 0.47 0.44 0.35 0.37 0.47 0.55 0.54 0.5 0.64 0.34 0.44 0.42 0.45 0.44 0.48 0.41 0.58 0.42 0.38 0.31 0.35 PCEe (%) Ref. 0.95f 3.6g 3.5 5.0h 2.1i 4.2 2.1 1.5 2.5 1.54 1.74 2.59 4.9j 6.1 4.5 1.24 1.99 1.79 3.2 4.1 5.5 5.7 1.17 1.34 1.70 2.17k 2.33 3.0 4.4 1.53 3.7 4.06 1.76 1.42 2.22 1 57 59 6 61 63 67 69 70 72 72 73 74 12 75 79 80 81 82 83 84 86 88 88 89 90 91 92 93 94 95 96 97 99 100
Table 1
lmaxa/nm a1
a3 a4 a6 a7
755 850 590 688 1.7
2 105 (S, N) 1 105 (O, N) 5 105 (O, N) 7 106 (O, N) 105104 (O) 1.2 104 (O, N) 1.3 103 (O, N)
5.4(U)/ 5.2(U)/ 5.6/3.6 5.4/3.6 5.80/3.76 5.59/3.68 5.75/3.59 5.69/3.54 5.0/3.3 5.0/3.3 5.14/3.37 5.3/3.4 5.3/3.7 5.69/3.66 5.56/3.75 5.03/3.0 5.2(U)/3.7 5.2(U)/3.4 5.46/3.46
a8 607 a9 649 a10 616
a11 a12 a13 a14 a15
595 760 770 820 700
a16 710 a17 588 a18 675 a19 a20 a21 a22 a23 a24 a25 a26 a27 a28 672 742 720 660 695 676 660 550
1.95 1.70 1.70 2.01 1.7 1.73 1.72 1.67 1.94
5.1 105 (S, N) 9.7 105 (S, N) 5 107 (S, B) 1.0 104 (S, N) 3 105 (S, B) 4 105 (O, N) 2.5 103 (S, N) 7.18 103 (O, N) 3.64 10 5.25 105
5
5.40/3.68 5.5/3.9 (S, B) 5.27/3.54 (S, N) 5.55/3.42
a In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. c From electrochemistry unless stated otherwise, U: from UPS. d Donor/acceptor: bilayer by vacuum deposition unless stated otherwise; donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum deposition; sol: solution process. e AM1.5, 100 mW cm2 unless stated otherwise. f AM2, 75 mW cm2. g 150 mW cm2. h 120 mW cm2. i 119 mW cm2. j 88 mW cm2. k 90 mW cm2.
in the solar spectrum have energies corresponding to wavelength of 6001000 nm. Nonplanar Pc molecules, such as chloroaluminum phthalocyanine (AlClPc, a3), exhibited an absorption peak in the near-infrared around 755 nm and harvested a greater percentage of infrared photons.61 The out-of-plane Cl atom bonded to the central Al atom with square-pyramidal geometry strongly inuences the molecular packing, inducing an interleaved slip-stack arrangement and signicant red shift in absorption compared to CuPc (maximum absorption wavelength of ca. 630 nm). Additionally, ultraviolet photoelectron spectroscopy (UPS) measurements indicate that the highest occupied molecular orbital (HOMO) energy of a3 is shifted to 5.4 eV, ca. 0.1 eV farther from vacuum than that of a1, which is benecial for an increased VOC. The optimized a3/C60 bilayer devices exhibit an overall improvement in PCE from 1.8% of a1/C60 bilayer devices to 2.1%.61 Oxo-titanium phthalocyanine (a4) has also been applied in the OPV devices as donor materials leading to both a higher absorbance at long wavelengths and an increased VOC in a4/C60 bilayer OPV devices as compared to a1.62,63 The studies of a4 lms have determined that vapor deposition results in the formation of at least two distinct phases with dierent absorption spectrum. In 2009, Armstrong et al. reported that
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polymorph a4 lm has changed to crystalline form that absorbs light at the longest wavelengths by exposure of the as-deposited thin lm to concentrated solvent vapors (solvent annealing). The optimized OPVs based on a4 showed a relatively high PCE of 4.2%, with JSC of 15.1 mA cm2, VOC of 0.57 V, and FF of 0.53.63 A metal-free Pc (a5) with aliphatic side chains was one of the earliest small molecule donors in solution-processed BHJ OPVs.64 The reported a5-based devices were prepared by spincasting a mixed solution of a5 and PDI derivative (f3, Fig. 7) in chloroform. These very rst reported devices exhibited poor device performance, but recent work has shown that Pc derivatives are viable donors for application in solution-processed BHJ OPVs. Signicantly improved performance was realized by using a combination of three ZnPc-based donors and a fullerene acceptor to give PCE of 0.12%, with a JSC of 1.24 mA cm2, VOC of 0.41 V, and FF of 0.24.65 The OPVs based on Pcs showed relatively low VOC (generally less than 0.6 V), which was one of factors limiting the PCEs of OPVs. The VOC value generally depends on the energy dierence between the lowest unoccupied molecular orbital energy (LUMO) of the acceptor and HOMO energy of the donor.66 Thus, one way to increase the VOC is to lower the HOMO level
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Fig. 2 Chemical structure of dye-based donors.
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of donor materials. In 2006, Thompson and coworkers reported a subphthalocyanine (a6)/C60-based bilayer heterojunction OPV.67 Due to the deep HOMO level of a6, the devices exhibited much higher VOC (0.97 V) as compared to conventional devices based on CuPc/C60 bilayer heterojunction (0.42 V), without a concomitant reduction in JSC, resulting in enhancement in PCE from 0.9% to 2.1%. Gommans et al. reported a higher JSC (5.4 mA cm2) and higher PCE (3.0%) from this device architecture.68 In 2009, solution processing of subnaphthalocyanine (SubNc, a7) was carried out for the rst time to form a donor layer in ecient bilayer heterojunction OPVs.69 Due to its unique properties, such as good solubility, low tendency to aggregate, and strong light absorption in the visible region, amorphous a7 lms with good charge transporting and light-harvesting properties can be prepared via simple solution casting. The a7/C60 bilayer device based on solution processed a7 donor layer demonstrated a PCE of 1.5%, with a JSC of 5.6 mA cm2, VOC of 0.55 V, and FF of 0.49 after thermal annealing at 120 1C for 40 min. At the same time, Verreet et al. reported that the a7/C60 bilayer OPVs based on vacuum deposited a7 donor layer produced a higher PCE of 2.5%, with JSC of 6.1 mA cm2, VOC of 0.79 V, and FF of 0.49.70 The decreased VOC as compared to that of a6-based devices results from greater conjugation imparted by the additional benzene rings in a7, which raises the HOMO energy level.71 However, the benzene rings are also responsible for the shift in absorption to longer wavelengths and a resultant improvement of JSC, compared to a6-based OPVs. Merocyanine (MC) dye-based molecules oer high absorption coecients (usually over 1 105 M1 cm1) and suciently large variability in the position of the HOMO and LUMO levels.72,73 In 2008, Wurthner, Meerholz and coworkers have successfully applied MC dyes in solution-processed BHJ OPVs for the rst time. The optimized PCEs were up to 1.54% or 1.74% for blends of MC dyes (a8 or a9):PC61BM.72 Later, they modied the push pull dye a8 with a exible alkyl chain to achieve more ecient photovoltaic molecules by bridging the electron donating unit with a propylene group in a10 to diminish the exibility of the structure and to ensure a more planar geometry.73 a10 exhibited relatively high hole mobility of 5 105 cm2 V1 s1, ve times of that for a8. Solution-processed devices based on a a10:PC61BM blend showed a JSC of 8.24 mA cm2, larger than that of a8:PC61BM (5.30 mA cm2), resulting in a remarkably improved PCE of 2.59%. Moreover, vacuum processed BHJ OPVs based on a10 and C60 were also fabricated, and the best vacuum processed device showed a promising PCE of 4.9%.74 More recently, a PCE of 6.1% was achieved by introducing MoO3 instead of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as hole-collecting contact sandwiched between the active layer and anode after solvent annealing in CH2Cl2 for 10 min.12 They developed a new dye a11 for application in solution-processed OPVs, the optimized device showed a PCE of 4.5% with a VOC of 1.0 V.75 They reported a parallel-BHJ cell that forms in situ driven by dipolar intermolecular forces when mixing two merocyanine dyes with complementary absorption as double-donors with C60 acceptor. By optimizing the ratio of the two donor components and the thickness of the active layer, the PCE (3.2%) of the blend donor cells was higher than either (2.62.7%) of the reference devices based on
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the individual dyes only. This synergetic eect is attributed to a more ecient photon harvesting eciency of the mixed donor cells compared to either of the single donor devices.76 MC dyes show a great potential for the application in highly ecient tandem solar cells. Very recently, a dye a8 and C60-based novel tandem-cell device architecture, combining bilayer and bulk heterojunctions, was fabricated by fully vacuum depositing, consisting of only four organic layers.77 The optimized PCE was up to 4.8%, with a strikingly high VOC of 2.1 V, which is the highest VOC value reported for small molecule tandem solar cells. Wurthner et al. also investigated the charge dissociation at the D/A heterointerface of thermally evaporated bilayer heterojunction MC dye (an analog with propyl replacing butyl in a8)/C60 OPVs, where they found that the FF value can be improved by evaporating the dye lm on a heated substrate or postannealing the completed devices above the glass transition temperature (Tg) of this MC donor. The optimized bilayer device showed PCE up to 3.9% with very high FF of 0.70.78 Squaraine (SQ) has been eectively applied to small molecule OPV devices.7986 The SQ dye-based molecules showed broad absorption from 500 to 900 nm in the lm, high absorption coecients (over 1 105 M1 cm1), good photochemical and thermal stability.87 In 2008, Marks and coworkers reported that a series of SQ-based molecules exhibited promising performance in solution processed BHJ OPV, and the optimized a12-based device processed in air exhibited a PCE of 1.24%.79 Subsequently, the structure modication by using hexenyl groups (a13) instead of 2-ethylhexyl side chains improved the device PCE up to 1.99% after thermal annealing at 50 1C for 30 min.80 Wurthner, Meerholz and coworkers replaced the ketone on the SQ moiety with dicyanovinyl group (a14), leading to increased crystallinity and relatively high hole mobility (1.3 103 cm2 V1 s1 after annealing).81 The BHJ device based on a14 and PC61BM (annealing at 110 1C for 5 min) showed a PCE of 1.79%, with an unusually high JSC of up to 12.6 mA cm2, a high FF of 0.47, but a rather low VOC of 0.31 V. Thompson, Forrest and coworkers also recently reported a SQ-based molecule (a15) as donor in OPVs.8284 Initially, a15 was used to fabricate bilayer heterojunction OPVs by vacuum deposition, which exhibited a PCE of 3.2% under 1 sun, AM1.5G simulated solar irradiation.82 Later, bilayer devices using solution processed a15 layers with evaporated C60 layers were found to have a higher PCE of 4.1%, while the BHJ device achieved a PCE of 2.9%.83 Recently, they found that post-annealing through additional extended exposure of the blend to dichloromethane can lead to control of the nanoscale phase separation of a15:PC71BM (1 : 6) blend lms and an optimized morphology reduces series resistance.84 By optimizing morphology and molecular ordering of the a15:PC71BM BHJ OPVs, a peak PCE of 5.5% has been achieved, with a maximum cell performance achieved when the exciton diusion length is approximately equal to the mean a15 crystallite size. This result suggests that the high BHJ OPV performance could be achieved by the precise structural control of phase separation. Furthermore, they developed a series of new SQ-based dyes;85,86 the optimized a16/C60 bilayer device with using solution processed a16 layer with evaporated C60 layer showed the best OPV performance after thermal annealing at 90 1C: PCE of 5.7%, JSC of 10.0 mA cm2, VOC of 0.90 V, and FF of 0.64.86
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Crystallographic data suggest that the intermolecular stacking of a16 molecules is closer than that of a15, thereby reducing the device series resistance and increasing its ll factor. Roncali and coworkers rstly reported borondipyrromethene (BODIPY) derivatives as photovoltaic materials.8890 This type of dyes can be used as a platform for the design of donor materials owing to a unique combination of facile synthesis, good stability, and high absorption coecients. Additionally, based on the presence of a tetrahedral boron atom in the structure, BODIPY appears as an interesting potential of isotropic active materials for OPVs. In a rst exploration of BODIPY-based donors, the dyes a17 and a18 were synthesized and applied in BHJ OPVs blending with PC61BM acceptor. The absorption spectra of a17 and a18 show a maximum at 572 and 646 nm, respectively, with high molecular extinction coecients (1.01.3 105 M1 cm1). The OPV cells based on a17 or a18:PC61BM (1 : 2) delivered PCE of 1.17% or 1.34%.88 Combining these two dyes with complementary absorption characteristics and blending with PC61BM, the devices were fabricated showing broad IPCE (the incident photon-to-current conversion eciency, i.e., the current obtained outside the photovoltaic device per incoming photon) spectrum from 350 to 700 nm, yielding a PCE of 1.7%, with a JSC of 4.7 mA cm2, VOC of 0.87 V, and FF of 0.42.89 Bithiophene was incorporated into a18 to build the new molecule a19, leading to improved hole mobility of 9.7 105 cm2 V1 s1 from 5 105 cm2 V1 s1 for a18, while retaining the broad and strong absorption of BODIPY. The BHJ OPV based on a19 and PC61BM showed an improved JSC of 7.0 mA cm2 and PCE of 2.2%.90 Due to several attractive properties of diketopyrrolopyrrole (DPP) dyes for photovoltaic applications, such as strong light absorption, good photochemical stability, and facile synthetic modication, Nguyen et al. have applied a series of DPP-based materials in solution processable BHJ OPVs.9193 In 2008, they explored the rst soluble DPP-based molecule (a20) with terthiophene arms as a donor blending with PC61BM; the BHJ device exhibited a JSC of 8.42 mA cm2, VOC of 0.67 V, FF of 0.45, and an overall PCE of 2.3%.91 However, inherent aspects of this material limit the device performance, including high HOMO energy level, potential morphological instability from the thermally labile alkyl group, and imbalance of carrier mobilities (hole mobility of 5 107 cm2 V1 s1 and electron mobility (i.e., the distance over which electrons are transported per second under the unit electric eld) of 3 104 cm2 V1 s1 as measured using single-carrier diodes). By using 2-ethylhexyl group instead of t-Boc substituent in a20, the new DPPbased molecule (a21) showed deeper HOMO level (5.2 eV), improved morphological and thermal stability, and balanced carrier mobilities when blending with PC71BM (hole mobility of 1.0 104 cm2 V1 s1 and electron mobility of 4.8 104 cm2 V1 s1). Owing to these improvements, the OPVs based on a21:PC71BM (1 : 1) exhibited a PCE of 3.0%, with JSC of 9.2 mA cm2, VOC of 0.75 V, and FF of 0.44.92 The OPV performance of DPP-based materials was further improved by replacing hexylbithiophene end groups with benzofuran (a22). Blending a22 with PC71BM, very little phase separation was apparent in the as-cast lm. However, thermal annealing leads to suitable phase separation so that eective BHJ morphologies are obtained. The degree of phase separation
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can be controlled by adjusting annealing temperature; 110 1C yielded optimum device properties: JSC of 10 mA cm2, VOC of 0.9 V, FF of 0.48, and PCE of 4.4%.93 In 2010, Luscombe et al. incorporated selenophene into DPP-based molecules as the donor material in BHJ OPVs;94 the optimized devices based on an a23:PC61BM (1 : 1) blend showed a PCE of 1.53%, with a JSC of 4.9 mA cm2, VOC of 0.77 V, and FF of 0.41. Recently Frechet and coworkers reported a series of DPP-based donors with dierent end groups, and demonstrated that ecient OPV materials can be constructed by attaching planar, symmetric end groups to electroactive small molecules.95 pp interaction of molecule a24 dictated tight, aligned crystal packing, favorable morphology, and promoted intermolecular connectivity, so OPV devices based on blend of a24:PC71BM (2 : 1) exhibited a maximum PCE of 4.1% with a FF approaching 0.6. Marks and coworkers rst implemented naphtho[2,3-b : 6,7-b 0 ]dithiophene (NDT) in donor materials for BHJ OPVs.96 The molecule (a25) with NDT as core and DPP as arms was synthesized and showed high absorption coecient of 1.1 105 M1 cm1 at maximum absorption of 624 nm, appropriate HOMO energy level (5.4 eV), and relatively high hole mobility of up to 7.18 103 cm2 V1 s1. Combined with the electron acceptor PC61BM, a high PCE of 4.06% was achieved, with a JSC of 11.27 mA cm2, VOC of 0.84 V, and FF of 0.42, by annealing at 110 1C for 10 min. Similar to DPP structure, isoindigo (ID) and perylene diimide (PDI) both have symmetrical lactam structure with strong electron withdrawing property. Reynolds et al. reported synthesis of a26 based on ID as core and bithiophene as arms and application in solution processed BHJ OPVs as donor material.97 After annealing at 110 1C, the device based on a26:PC61BM (1 : 1) gave a PCE of 1.76%; the PCE was increased to 2.15% by adding a polydimethylsiloxane additive, due to more favorable morphology.98 Ko and coworkers reported annulated thiophene PDI linked with triphenylamine through a bithiophene bridge (a27),99 and BHJ OPV based on a27:PC61BM (1 : 2) showed JSC of 5.94 mA cm2, VOC of 0.776 V, FF of 0.308 and PCE of 1.42%. Frechet and coworkers reported a series of multifunctional linear quinacridone (QD)-based molecules which showed intense absorption in the visible spectral region, and the absorption range and intensity were well-tuned by the interaction between the QD core and the incorporated thiophene arms.100 A solution processed thin lm of a28:PC71BM (1 : 2) showed bicontinuous nanophase separated morphology, which was feasible for exciton dissociation and charge transport. a28-based device gave a PCE of 2.22%, under an AM1.5 simulated solar illumination. In dyes, Pc, MC, and DPP-based molecules have exhibited very high performance in OPVs with PCE values over 6%, which can be partially attributed to the strong absorption of these materials. Interestingly, some dyes (e.g., BODIPY and MC) with very similar structures can show very dierent and complementary absorption spectra while retain compatibility of other properties. Thus, multicomponent devices can be fabricated by mixing two dyes as double-donors with fullerene acceptor, and better device performance can be achieved, which may deserve further attention.
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Fused acenes In organic eld-eect transistors (OFETs), fused acenes, such as pentacene and tetracene, have been extensively studied as a p-type semiconductor, and especially, pentacene is well known to exhibit extremely high hole mobility (over 1 cm2 V1 s1).101,102 The high mobility is a key factor to enhance the PCEs of OPV devices. This type of materials has been successfully applied in vacuum deposited bilayer or solution processed BHJ OPVs, due to their high hole mobility, broad absorption and good thermal stability. Table 2 provides a summary of electronic properties as well as OPV data for representative fused acene donors (Fig. 3). In 2004, Kippelen et al. rst fabricated an ecient OPV based on a bilayer heterojunction of polycrystalline pentacene (b1) and C60.103 Under illumination of broadband light 100 mW cm2, the device exhibited a JSC of 15 mA cm2, VOC of 0.36 V, FF of 0.50, and PCE of 2.7%. Obviously, in this device the most limiting factor is the low VOC. JSC and PCE were projected to be around 8.2 mA cm2 and 1.5% under AM1.5, 100 mW cm2. In 2005, Yang et al. fabricated bilayer heterojunction OPVs with tetracene (b2)/C60 as the photoactive layer.104 The PCEs of the devices were 2.3% under AM1.5 solar illumination at 100 mW cm2. Researchers have tried to use the fused acenes for applications in solution processable BHJ OPVs by properly functionalizing with solubilizing groups such as triisopropylsilylethynyl (b3).105 Unsubstituted pentacene adopts a herringbone motif in solid state, while 6,13-bis(triisopropylsilylethynyl)pentacene exhibits a structural improvement in solid state, promoting face-to-face instead of face-to-edge (herringbone) packing, leading to close cofacial p-stacking.36,106 Such modication oers tunability of the p-orbital overlap and therefore control of intrinsic charge carrier mobility, an important parameter for OPV applications. b3 can be crystallized in lm and absorb farther into the red than pentacene, theoretically leading to higher photocurrent and PCE. Unfortunately, b3 rapidly undergoes a DielsAlder reaction with fullerene derivatives in solution, and b3-fullerene adduct ineectively supports photoinduced charge transfer. Hereby, Anthony, Malliaras and coworkers fabricated a bilayer device (spin-coated b3 layer and vacuum-deposited C60 layer),
Table 2
where adduct formation can be minimized. After optimization of photoactive layer thickness, incorporation of exciton-blocking layer, and thermal annealing, PCE reached a peak value of 0.5%.105 Triethylsilylethynyl-substituted anthradithiophene (b4) exhibited an absorption cuto of 575 nm in lm and a high hole mobility of 0.11 cm2 V1 s1.107 As-cast b4:PC61BM (7 : 3) lm was fairly amorphous and did not generate large photocurrent. Solvent (dichloromethane) vapor annealing of these blends led to the formation of spherulites, which is consisted of a network of b4 crystallites dispersed in an amorphous matrix composed primarily of PC61BM. The spherulite covered fraction of the lm appeared rough with submicrometer, needle-like crystals, which led to a marked improvement in photocurrent generating capacity. The generated photocurrent was proportional to the area covered by spherulites. Devices with 82% spherulite coverage gave the best PCE of 1.0%, with a JSC of 2.96 mA cm2, VOC of 0.84 V and FF of 0.40.107 Thompson et al. synthesized triethylsilylethynyl-substituted tetracene monomer (b5) and dimer (b6).108 The PCE of bilayer OPV device based on b5 and C60 was 0.5%, with VOC of 1.06 V, JSC of 1.48 mA cm2, and FF of 0.34. The VOC (0.31 V) for the dimer (b6) based device was substantially lower than that for the monomer based device, leading to lower PCE (0.2%), and the main reason might be that b6 has higher HOMO energy level (5.16 eV) than that (5.36 eV) of b5. In 2008, Marrocchi and coworkers reported BHJ OPV devices based on an anthracene derivative (b7):PC61BM (1 : 1.17) blend with a PCE of 1.12%.109 They found that an acetylenic spacer yielded signicantly better OPV performance than an olenic spacer in this system.110 The optimized OPV device based on b7:PC61BM (2 : 1) showed a JSC of 3.1 mA cm2, VOC of 0.89 V, FF of 0.45, and overall improved PCE of 1.27% upon thermal annealing at 60 1C.111 In 2010, Chung et al. reported triisopropylsilylethynyl anthracene derivative substituted with bithiophene (b8).112 The BHJ OPVs were fabricated by blending b8 with PC61BM (1 : 14). As varying the blending ratio, the blend lm morphology changed from obvious phasesegregated crystalline domains at 1 : 1 ratio to homogeneous, nearly amorphous phases at 1 : 4 ratio. At the ratio of 1 : 4, BHJ OPVs yielded a PCE of 1.4%, higher than that for other ratios, revealing that well-mixed homogeneous phases,
Optical and electronic properties, mobilities, and OPV performance of fused-acene-based donors Egopt/eV 1.77 2.14 1.65 2.16 2.25 2.19 2.0 1.90 2.87 2.51 mhb/cm2 V1 s1 HOMOc/LUMO/eV Active layerd b1/C60 b2/C60 b3(sol)/C60 b4:PC61BM (7 : 3) b5/C60 b6/C60 b7:PC61BM (1 : 1.17) b8:PC61BM (1 : 4) b9:PC61BM (1 : 1) b10:PC71BM (1 : 1) b11:f3 (2 : 3) b12:PC61BM (1 : 2) b13:PC71BM (1 : 2) JSC/mA cm2 15 7.0 1.9 2.96 1.48 1.73 1.37 4.55 6.55 5.41 3.35 102 2.68 6.37 VOC/V 0.363 0.58 0.47 0.84 1.06 0.31 0.762 0.78 0.83 0.80 0.69 0.90 1.0 FF 0.50 0.57 0.52 0.40 0.34 0.37 0.44 0.40 0.41 0.45 0.4 0.61 0.38 PCEe (%) 2.7 2.3 0.5 1.0 0.5 0.2 1.12g 1.40 2.25 1.95 1.95h 1.46 2.5
f
lmaxa/nm b1 b2 b3 b4 b5 b6 b7 b8 b9 b10 b11 b12 b13 520 535 612 503 537 620 368 375
Ref. 103 104 105 107 108 108 109 112 113 114 115 116 117
0.11 (O, N) 0.07 (O, N) 104105 (S, B)
2.3103 (O, N)
5.15/2.98 5.36/2.76 5.16/3.00 5.51/3.00 5.3/2.8 5.1/3.0 5.46/3.60 5.25/2.64 5.03/2.6 5.28/2.77
a In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. c From electrochemistry. d Donor/acceptor: bilayer by vacuum deposition unless stated otherwise; donor:acceptor: blend by solution process; sol: solution process. e AM1.5, 100 mW cm2 unless stated otherwise. f Broad band light 100 mW cm2. g 41 mW cm2. h At 490 nm, 0.47 mW cm2.
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Fig. 3
Chemical structure of fused acene donors.
rather than highly crystalline phases, resulted in improved PCE by allowing for ecient charge separation. In 2009, Watkins and coworkers reported a new class of organic semiconductors based on dibenzo[b,def]chrysene (DBC).113 In contrast to well-studied pentacenes, DBC derivatives did not undergo cycloaddition reactions with fullerenes. In the BHJ OPVs, one successful result was obtained by using a mixture of triethylsilylethynyl-substituted DBC (b9) and PC61BM spincasted from chloroform solution. Casting solvents played an important role in determining crystallinity and morphology. High boiling point solvent such as chlorobenzene led to larger scale of phase separation, and reduced interfacial area, resulting in very low device eciency. Spin-casted BHJ lms from low boiling point solvent such as chloroform showed phase separation at the nanoscale, which beneted more ecient dissociation
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of the photogenerated excitons and collection of separated charges. At high concentration and high spin speed, the BHJ lms from chloroform have been well modied to enhance the PCE of OPV devices. Hereby the optimized device showed a JSC of 6.55 mA cm2, VOC of 0.83 V, FF of 0.41 and PCE of 2.25%. Very recently, triisopropylsilylethynyl-functionalized dibenzo[def,mno]chrysene (b10) with similar structure to b9 was synthesized and applied to fabricate OPV devices.114 The primary BHJ OPVs based on b10:PC71BM exhibited a PCE of 1.95%, lower than that of b9. In 2001 Friend and coworkers used a discotic liquid crystalline hexaperihexabenzocoronene (HBC) derivative (b11) in combination with a PDI acceptor (f3, Fig. 7) to fabricate solution-processed OPVs with a PCE of 1.95% at 490 nm (0.47 mW cm2).115 Recently, Holmes and coworkers reported
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synthesis of diuorenyl-substituted HBC (b12) and its use in OPVs. Devices based on a blend of b12:PC61BM (1 : 2) after thermal annealing at 150 1C generated JSC of 2.68 mA cm2 and PCE of 1.46%.116 Later, they attached oligothiophene to b12 to yield b13.117 Relative to b12, b13 has extended conjugation and broader absorption. The BHJ OPVs based on b13:PC71BM (1 : 2) exhibited higher JSC (5.71 mA cm2) and higher PCE (2.64%) relative to the devices based on b12:PC71BM (1 : 2) (JSC of 2.53 mA cm2 and PCE of 1.0%). Most fused acenes possess high crystallinity and relatively high mobility, and these materials show moderate photovoltaic performance in vacuum deposited bilayer devices. For solution-processed BHJ devices, high crystallinity of fused acenes leads to large phase separation scale when blending with fullerene acceptor, which causes decreased device performance. Thus, tuning the crystallinity of fused acenes by modifying their substituent groups is necessary to achieve high performance BHJ devices based on fused acenes. Oligothiophenes Oligothiophenes, including one-dimensional, two-dimensional and three-dimensional conjugated systems, are one of the largest families of organic semiconductors, and have been widely used in OPVs due to their high charge-carrier mobility and facile synthesis to tune energy levels.118 Table 3 summarizes electronic properties as well as OPV data for representative one, two and three dimensional oligothiophenes (Fig. 4). BHJ OPVs based on blend of a-sexithiophene (c1) and C70 were fabricated by the vacuum coevaporation method.119 Since c1 was easy to aggregate and crystallize, it was dicult to mix homogeneously c1 and C70 at a blend ratio of 1 : 1 (w/w), leading to insucient formation of carrier transport network and charge separation. When c1:C70 ratio was 1 : 5 (w/w), excessive C70 prevented c1 from crystallization, leading to
Table 3
formation of amorphous structure, so that charge separation eciency was improved and desirable carrier transport interpenetrating network was formed. After thermal annealing at 140 1C for 20 min, the OPV devices exhibited a PCE of 2.38%. However, narrow absorption and relatively high HOMO level of c1 limited JSC and VOC of OPVs, respectively. To achieve high-eciency OPVs, conjugated oligothiophenes with low band gap, broad absorption and appropriate energy levels are required. One successful approach is to introduce electron withdrawing units into the conjugated backbone to form DA oligothiophenes with highly polarizable p-electron systems, which can extend the absorption spectrum of the donor toward longer wavelengths by an intramolecular charge transfer and thus have a good match with the solar spectrum. The dicyanovinyl (DCV) group has strong electron-withdrawing properties leading to ecient intramolecular charge transfer. Some DCV-substituted oligothiophenes have been synthesized and applied in vacuum-deposited and solution-processed OPVs.120126 In 2006, Bauerle, Leo and coworkers fabricated bilayer heterojunction OPVs based on terminally DCV-substituted oligothiophenes bearing butyl side chains (c2) as donor and C60 as acceptor.120 Due to low HOMO level and red-shifted absorption of c2, these OPVs aorded PCEs of up to 3.4%, with high VOC of 0.98 V, JSC of 10.6 mA cm2 at 118 mW cm2 simulated sunlight. Later, they used selenophene instead of thiophene in c2 to synthesize a series of c2 analogs. Selenophene-containing oligomers showed slightly lower performance due to lower degree of donor/acceptor phase separation compared to c2 in BHJ OPVs, but PCE was still in a good range of 2.53.1%.123 Recently, they synthesized a series of terminally DCV-substituted oligothiophenes without solubilizing side chains via a novel convergent approach and used them as electron donors in vacuum-processed bilayer heterojunction and BHJ OPVs.124 OPV devices incorporating c3 and C60 showed PCEs of up to 2.8% for bilayer heterojunction
Optical and electronic properties, mobilities, and OPV performance of oligothiophene-based donors Egopt/eV 1.77 1.68 1.68 1.74 1.69 1.83 1.73 2.00 1.87 1.9 1.51 1.5 2.13 2.1 2.06 1.74 2.28 2.65 mhb/cm2 V1 s1 HOMOc/LUMO/eV 5.3(U)/3.1 5.6(U)/ 5.43/3.87 5.13/3.42 5.13/3.29 5.21/3.68 5.11/3.54 4.95/3.26 5.50/3.34 5.65/3.64 5.28/3.38 5.16/3.60 5.2/3.6 5.26/2.66 5.29/3.16 5.4/3.3 5.1/3.2 5.28/3.07 Active layerd c1:C70 (1 : 5) (vac.) c2/C60 c3:C60 (2 : 1) (vac.) c4:PC61BM (1 : 1.4) c5:PC61BM (2 : 1) c6:PC61BM (2 : 1) c7:PC61BM (2 : 1) c8:PC61BM (1 : 0.8) c9/C60 c10/C60 c11:PC71BM (1 : 4) c12:PC71BM (3 : 2) c13:PC71BM (7 : 3) c14:PC61BM (1 : 1.2) c15:PC71BM (1 : 2) c16:PC61BM (1 : 4) c17:PC61BM (1 : 4) c18:PC71BM (1 : 4) c19:PC61BM (1 : 2) c20:PC61BM (1 : 3) c21:PC61BM (1 : 3) JSC/mA cm2 9.2 10.6 11.1 12.4 10.74 13.98 9.77 11.51 3.1 4.7 8.45 10.9 14.4 3.65 4.61 3.35 2.5 4.79 4.19 1.13 1.33 VOC/V 0.58 0.98 0.97 0.88 0.86 0.92 0.93 0.80 0.98 1.00 0.82 0.7 0.78 0.85 0.94 0.94 0.93 0.93 0.97 0.85 0.51 FF 0.45 0.49 0.49 0.34 0.55 0.47 0.60 0.64 0.57 0.67 0.43 0.42 0.59 0.26 0.36 0.40 0.47 0.37 0.42 0.24 0.27 PCEe (%) 2.38 3.4f 5.2 3.7 5.08 6.10 5.44 5.84 1.73 3.15 3.0 3.2 6.7 0.80 1.54 1.3 1.12 1.64 1.72 0.29g 0.20h Ref. 119 120 124 126 127 14 128 129 133 133 134 135 15 136 137 138 140 145 147 148 149
lmaxa/nm c1 c2 c3 c4 c5 c6 c7 c8 c9 c10 c11 c12 c13 c14 c15 c16 c17 c18 c19 c20 c21
a d e
573 579 614 580 618 563 650 503 548 415 720 720 390 426 450 535 495 400 390 399
1.5 104 (S, N) 3.3 104 (S, N) 1.5 104 (S, N) 4.5 104 (S, N) 1.8 104 (S, N) 2.5 104 (S, N) 0.12 (O, N) 1.1 104 (O, N)
In lm. b O and S: measured by OFET or SCLC method, N: in neat lm. c From electrochemistry unless stated otherwise, U: from UPS. Donor/acceptor: bilayer by vacuum deposition; donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum deposition. AM1.5, 100 mW cm2 unless stated otherwise. f 118 mW cm2. g 80 mW cm2. h 99 mW cm2.
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Fig. 4
Chemical structure of oligothiophene donors.
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and 5.2% for BHJs under simulated AM1.5 100 mW cm2 illumination. In 2010, Chen and coworkers reported the synthesis of a DCV-substituted oligothiophene with six solubilizing side chains (c4) and application in solution-processed BHJ OPVs.125,126 Absorption spectra of c4 lms showed good solar spectral coverage. Hole mobility of pristine c4 was 1.5 104 cm2 V1 s1 measured by the space charge limited current (SCLC) model.125 Under illumination of 100 mW cm2, the devices based on c4:PC61BM blend (1 : 1.4) displayed a PCE of 3.7%, with JSC of 12.4 mA cm2, VOC of 0.88 V, and FF of 0.34.126 Carefully designing and controlling the position and density of dierent alkyl side or end chains can not only increase solubility of materials in organic solvents for spin-casting devices but also improve their packing structure and solid-state miscibility with fullerenes. Recently, Chen and coworkers designed and synthesized a series of oligothiophenes end-capped with electronwithdrawing alkyl cyanoacetate groups instead of DCV and investigated the correlation between these dierent end groups and their BHJ device performance.127 OPVs based on c5:PC61BM (2 : 1) exhibited a PCE of 5.08%, with a JSC of 10.74 mA cm2 VOC of 0.86 V and FF of 0.55. Compared to c4 with DCV end group, c5 with alkyl cyanoacetate end group gave higher PCEs. The better PCEs beneted from improved FF (over 50%), which came from better lm quality and morphology. Later, 3-ethylrhodanine was introduced as an end acceptor group to synthesize oligothiophene c6.14 c6 showed stronger solar absorption than c5, which is benecial to improving the JSC. A very high PCE of 6.10% was obtained by using a blend of c6:PC61BM as the active layer, with a remarkable JSC of 13.98 mA cm2 and VOC of 0.92 V. Meanwhile, they replaced the central thiophene unit in c5 with a more electron-rich and planar structure such as benzodithiophene and dithienosilole to synthesize c7 and c8. Improved mobility and absorption of c7 and c8 led to enhanced PCEs (5.44% for c7128 and 5.84% for c8129). The high PCE values 5.086.10% of c5c8 based devices suggest that the oligothiophenes with electron-withdrawing end groups are very promising donor materials for solution processed BHJ OPVs. In addition, Roncali et al. synthesized a series of symmetrical and unsymmetrical septithiophenes end-capped with DCV and thiobarbituric (TB) electron-withdrawing groups, and investigated their photovoltaic properties in bilayer OPVs based on spin-coated donor layer and vacuum-deposited C60 acceptor layer.130 They found an interesting phenomenon that breaking the symmetry of the donor structure can lead to a signicant increase of VOC, which may be attributed to the intermolecular interactions and molecular orientation. Other electron withdrawing units such as benzothiadiazole (BT), thiadiazolopyridine (TP) and triuoroacetyl (TFA) were also introduced into oligothiophene systems.131135 Bauerle and coworkers reported two linear oligothiophenes c9 and c10 endcapped with BT and TP acceptor units, respectively.133 Bilayer heterojunction OPVs based on c10 and C60 showed a higher PCE (3.15%) with a very high FF (0.67) compared to that of c9-based devices (1.73%). The excellent FF, which is among the highest values reported for small molecule-based OPVs, might be due to better stacking in thin lm caused by intermolecular hydrogenbonding interactions by the nitrogen atom of the pyridine ring.
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In 2010, Frechet and coworkers reported a series of platinumacetylide linear oligothiophenes containing a thienyl-BT-thienyl core, and various oligothiophenes were connected to control the molecular packing by changing the number of thiophene units from two to four.134 The best device based on the oligomer with terthiophene (c11) blending with PC71BM (1 : 4) after annealing at 70 1C for 30 min exhibited a JSC of 8.45 mA cm2, VOC of 0.82 V, FF of 0.43, and PCE of 3.0%. Recently, Bazan and coworkers introduced dithienosilole (DTS) in oligothiophenes.135 The DTS-containing oligothiophenes showed broad absorption extending beyond 700 nm, due to intramolecular charge transfer. After annealing at 110 1C for 2 min, BHJ OPVs based on c12:PC71BM (3 : 2) showed a JSC of 10.9 mA cm2 and PCE of 3.2%. Later, Heeger, Bazan and coworkers synthesized one novel isomeric compound (c13) of c12, and used it to fabricate solution processed BHJ OPVs.15 Compound c13 exhibited strong optical absorption, especially from 600 to 800 nm, and a high hole mobility of ca. 0.1 cm2 V1 s1 measured by organic eld-eect transistor (OFET). Under AM1.5 irradiation (100 mW cm2), a record PCE of 6.7% was achieved for small-molecule donor based BHJ devices from c13:PC71BM (7 : 3, w/w). This high eciency was obtained by adding remarkably low percentage of solvent additive (0.25% v/v of 1,8-diiodooctane) during the lm-forming process, which led to decreased domain sizes in the BHJ layer. Additionally, the low fraction of fullerene in BHJ layer is surprising and interesting. The high performance at such a low fullerene concentration indicated that the crystalline donor may render the fullerene acceptor to form percolated pathways to the electrode. Moreover, it seems that lower fullerene concentration has some connection with the small amount of additive required to achieve optimized BHJ morphologies. Aside from linear oligothiophenes, two-dimensional oligothiophene systems have also been reported. Early in 2006, Liu, Tian and coworkers reported X-shaped conjugated systems with four linear oligothiophene arms connected to a central thiophene core.136 c14 with the longest arms had the lowest bandgap with an absorption onset of 520 nm; the blend of c14 and PC61BM exhibited the smallest feature size in AFM images. BHJ OPVs based on c14:PC61BM gave a PCE of 0.80% under simulated solar illumination. Recently, Zhan and coworkers reported a new X-shaped oligothiophene (c15) with four longer arms than c14.137 Owing to the longer conjugation, c15 exhibited red shifted absorption with the maximum at 426 nm and the onset of 582 nm in lm relative to c14. BHJ OPVs based on the blend of c15:PC61BM (1 : 2) gave a VOC of 0.93 V, JSC of 2.71 mA cm2, FF of 0.40, and PCE of 1.02%. Replacing PC61BM with PC71BM led to an improved JSC of 4.61 mA cm2 and a higher PCE of 1.54%. In 2006, Kopidakis et al. investigated 1,3,5 and 1,2,4,5substituted phenyl-cored thiophene dendrimers as donor materials in photovoltaic application.138 Once again, the oligomers with the longest oligothiophene arms exhibited the best performance. Although three-armed dendrimers had superior mobility, four-armed dendrimers enabled solution-cast lm formation and yielded smaller optical bandgap. The best material (c16) consisted of a 1,2,4,5-substituted phenyl core with each arm containing six thiophenes. Solution processed BHJ devices based on c16:PC61BM (1 : 4) exhibited PCE of 1.3%,
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with a JSC of 3.35 mA cm2, VOC of 0.94 V and FF of 0.40. However, due to high bandgaps (over 2.3 eV) and poor morphology, 1,3,5-substituted phenyl-cored thiophene dendrimers did not show promising photovoltaic performance, which was similar to the work from Roncali et al.139 In an eort to improve overlap with the solar spectrum, they reported a thiophene dendrimer that was modied with an electron-withdrawing group in order to lower the bandgap.140 The dendrimer c17 had an electron-withdrawing tricyanobenzene core and three oligothiophene arms to create a pushpull structure that lowers LUMO level. Compared to its counterpart without cyano groups and other 1,3,5-substituted phenylcored thiophene dendrimers, the optical absorption onset of c17 was down to 2.1 eV, attributed to lowering of the LUMO level. The density functional theory calculations showed that the optimized geometry of c17 is totally planar and therefore p-stacking should be favored in lms.141 Planarized structure led to improved morphology both in neat lms and in blends with PC61BM. The BHJ OPVs based on c17:PC61BM showed an improved FF, from 0.28 for that without cyano groups to 0.47, leading to an overall PCE enhancement from 0.40% to 1.12%.140 The authors attributed the higher FF to the improved morphology and reduced carrier recombination of the c17:PC61BM blend. Extended pushpull oligothiophenes with DCV groups exhibited narrow optical energy gap, strong absorption and favorable intermolecular pp interactions in the solid state and were promising donors for high-eciency photovoltaic applications.142144 Wong and coworkers synthesized a series of dendritic oligothiophenes with carbazole and DCV, the optical bandgap of these molecules in thin lms greatly reduced to 1.74 eV with strong spectral broadening and a high ionization potential at ca. 5.5 eV as determined by UPS. The BHJ OPVs fabricated from dendrimer c18 blended with PC71BM (1 : 4) showed a PCE of 1.64% with a Voc of 0.93 V after annealing at 100 1C for 10 min.145 In 2008, Bauerle and coworkers reported promising OPV results with large, highly branched oligothiophene dendrimers blended with PC61BM.146,147 The largest dendrimer showed absorption cuto up to 600 nm. Oligothiophene c19 showed the best result in BHJ OPV blending with PC61BM, and the optimized device produced a PCE of 1.72%, with JSC of 4.19 mA cm2, VOC of 0.97 V, and FF of 0.42.147 One issue with many OPV materials, such as fused acenes and low dimensional oligomers, is molecular and crystal orientation. High anisotropy in light absorption and charge transport is an important concern for the future of OPV materials, especially the solution processable BHJ materials. In 2006, Roncali and coworkers sought to overcome the low dimensionality of planar small molecules via synthesis of three dimensional oligothiophenes with a tetrahedral silicon core.148 Absorption spectra of these compounds are identical in thin lm and solution state, indicating an absence of aggregation or intermolecular p-interactions in the solid state. Within a BHJ, these molecules are likely to form amorphous hole-transporting networks that may hinder charge collection. The PCE of device based on c20:PC61BM (1 : 3) under white light irradiation at 80 mW cm2 is 0.3%, a relatively high value considering the charge transport limitation and the 440 nm light absorption onset.
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However, the insucient robustness of the silicon-thiophene bond was identied as a problem, and in some cases degradation of the molecules was observed during vacuum sublimation. In order to solve this problem, they have developed a dierent approach based on the use of a bithiophene twisted by steric eect as a core for building three dimensional oligothiophenes. The steric interactions associated with the xation of bulky groups at the 3,3 0 -positions of bithiophene produced a dihedral angle between the thiophene rings, thus generating a tetrahedral starting unit for the construction of three dimensional systems.149 BHJ OPVs based on c21 and PC61BM in a 1 : 3 (w/w) ratio under white light irradiation at 99 mW cm2 gave a JSC of 1.33 mA cm2, VOC of 0.51 V, and PCE of 0.20%. The low PCE was considered in relation with the poor absorption of c21, the maximum peak was only 399 nm. One-dimensional oligothiophenes with pullpush structure exhibited promising OPV performance. Especially, oligothiophenes with electron-withdrawing end groups yielded very high PCEs up to 6.10% when blending with PC61BM. Meanwhile, oligothiophenes with fused rings (such as benzodithiophene and dithienosilole) showed better performance in BHJ devices. On the other hand, the issue mentioned above in low dimensional oligomers is molecular and crystal orientation. High anisotropy in light absorption and charge transport is critical concern for OPV materials, especially for the solution processable BHJ materials. Thus, introducing the electron-withdrawing units and fused rings into three-dimensional oligothiophenes may produce surprising and superb results in BHJ OPVs. Triphenylamine derivatives Triphenylamine (TPA) has been regarded as a promising unit for organic semiconductor materials due to its good holetransporting and electron-donating capabilities.53,150 TPAbased small molecules, including pushpull molecules with TPA as the terminal group and star-shaped molecules with TPA as core have been widely investigated for application in OPVs, and they have exhibited good photovoltaic performance. Table 4 provides a summary of electronic properties as well as OPV data for representative linear and star-shaped TPA-based donors (Fig. 5). Li and coworkers reported a series of TPA-based linear pushpull chromophores with benzothiadiazole (BT) pull moieties.151,152 Early in 2006, they synthesized a DAD molecule d1 with TPA as the donor, BT as the acceptor and vinylthiophene as the bridge, and the solution-processed BHJ OPVs based on d1:PC61BM (1 : 1) blend showed a PCE of 0.26%.151 Replacing thiophene in d1 with 4-hexylthiophene (d2) or 4-hexylthieno[3,2-b]thiophene (d3) led to higher PCEs (1.44%) due to better lm formation caused by alkyl chains.152 Zhan and coworkers synthesized d4, similar to d2 but without a vinyl group.153 BHJ OPVs based on d4:PC71BM (1 : 3) gave a higher Voc (0.93 V) and higher PCE (2.21%) relative to d2:PC71BM (1 : 3).154 They used 1% 1,8-octanedithiol (ODT) as additive to further improve PCE to 2.86%. This 30% PCE enhancement was attributed to aggregated domain formation, enhanced absorption, improved hole mobility, and more balanced charge transport. Later, they replaced benzothiadiazole in d4 with thiazolothiazole to synthesize d5; BHJ OPVs
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Optical and electronic properties, mobilities, and OPV performance of TPA-based donors HOMOc/LUMO/eV Active layerd JSC/mA cm2 VOC/V FF 0.76 0.79 0.74 0.93 0.91 0.92 0.71 0.79 0.97 0.83 0.79 0.95 0.67 0.48 0.66 0.72 0.89 1.15 0.67 0.87 1.07 0.87 0.84 0.88 0.89 0.81 0.85 0.33 0.375 0.34 0.41 0.437 0.41 0.38 0.44 0.33 0.48 0.50 0.56 0.29 0.41 0.30 0.34 0.36 0.28 0.3 0.39 0.31 0.52 0.308 0.439 0.41 0.39 0.327 PCEe (%) Ref. 0.26f 1.44 1.44 2.86 3.73 1.8 1.40 2.06 1.08g 3.82 5.81 6.4 1.23 0.46 0.81 0.49 1.17 1.85h 0.32 1.80i 2.02i 4.3 1.4 3.0 0.61 1.33 2.39 151 152 152 154 155 156 159 159 160 161 162 13 163 165 165 165 165 167 168 169 169 170 171 171 172 173 174
Table 4
lmaxa/nm Egopt/eV mhb/cm2 V1 s1 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 d11 d12 d13 d14 d15 d16 d17 d18 d19 d20 d21 d22 d23 d24 d25 d26 d27 560 569 581 534 436 508 498 536 592 542 684 550 587 435 544 540 538 1.8 1.73 1.64 2.03 2.31 2.09 1.88 1.79 1.7 1.91 1.86 2.38 1.91 1.84 1.78 1.78 1.78 1.9 1.83 1.65 2.14 1.86 1.96 1.04 104 (S, N) 1.48 104 (S, N) 3.5 107 (S, B) 1.3 106 (S, B) 1.19 106
5.1/3.3 5.14/3.37 5.10/3.42 5.16/2.99 5.39/2.91 5.4(U)/ (S, N) 5.14/2.76 5.16/3.37 5.4(U)/ 5.15/3.71 5.46(U)/ 5.43/3.57
538 563 585 486 541 529
2.9 105 (S, N) 0.011 (O, N) 3.9 105 (S, N) 5.6 105 (S, N) 4.9 104 (O, N)
4.7 105 (S, N)
6.02/ 5.50/ 5.72/ 5.78/ 5.28/3.11 5.22/3.34 5.03/3.42 5.41/3.37 5.3/3.27 5.19/3.08
0.867 d1:PC61BM (1 : 1) d2:PC71BM (1 : 3) 4.84 d3:PC71BM (1 : 3) 5.71 d4:PC71BM (1 : 3) 7.49 d5:PC71BM (1 : 4) 9.39 4.9 d6:PC71BM (1 : 3) d7:PC71BM (1 : 3) 5.07 5.94 d8:PC71BM (1 : 3) 3.06 d9/C60 9.53 d10:C70 (1 : 1) (vac) d11/d11:C70 (1 : 1)/C70 14.68 d12/d12:C70 (1 : 1)/C70 12.1 6.32 d13:PC61BM (1 : 2) 2.33 d14/C60 4.10 d15:PC61BM (1 : 3) 1.97 d16/C60 3.65 d17/C60 d18/C60 4.59 1.7 d19/C60 d20:PC61BM (1 : 2) 5.30 d21:PC61BM (1 : 2) 5.83 d22:PC71BM (1 : 3) 9.51 5.21 d23:PC71BM (1 : 2) 7.66 d24:PC71BM (1 : 2) 1.66 d25:PC61BM (1 : 3) d26:PC61BM (1 : 3) 4.18 8.58 d27:PC71BM (1 : 3)
a In lm. b O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. 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 cm2 unless stated otherwise. f 85 mW cm2. g 90 mW cm2. h 80 mW cm2. i 95 mW cm2.
based on d5:PC71BM (1 : 4) after thermal annealing at 110 1C for 10 min aorded JSC of 9.39 mA cm2, VOC of 0.91 V, FF of 0.44, and PCE of 3.73%.155 Bo and coworkers reported a series of X-shaped TPA-based molecules with BT as core.156 Interestingly, the X-shaped molecules exhibited deeper HOMO levels and wider bandgaps than corresponding linear molecules. The best X-shaped molecule (d6) blending with PC71BM showed a JSC of 4.9 mA cm2,VOC of 0.92 V, FF of 0.41, and PCE of 1.8%, similar to that for its linear counterpart. Cyano-containing electron withdrawing units, such as dicyanomethylenepyran (DCP),157159 DCV13,160162 and cyanoacetic acid,163 were also combined with TPA to build pushpull molecules. In 2007, Li and coworkers designed and synthesized a DAD molecule (d7) with TPA as the donor, DCP as the acceptor, and divinylbenzene as the bridge.157 The VOC, JSC, FF, and PCE of the optimized device based on d7:PC61BM (1 : 3) reached 0.9 V, 2.14 mA cm2, 0.41, and 0.79%, respectively. Replacing benzene bridge in d7 with thiophene (d8) led to broader absorption, benecial to generating excitons and improving the JSC of OPVs.159 The OPV devices based on d8:PC71BM (1 : 3) blend showed a JSC of 5.94 mA cm2 and PCE of 2.06%, higher than that (1.40%) of devices based on d7. In 2011, Roncali and coworkers reported a series of molecules with TPA as the end group, a DCV dimer as the core and thiophene as the bridge.160 These compounds showed interesting light-harvesting properties (absorption onset at ca. 700 nm) and low-lying HOMO levels. The symmetrical molecule d9 with one thiophene as bridge showed promising performance in d9/C60 bilayer heterojunction OPVs: JSC of 3.06 mA cm2,
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VOC of 0.97 V, FF of 0.33, and PCE of 1.08%. Lin, Wong and coworkers reported a molecule (d10) adopting coplanar diphenylsubstituted dithienosilole as a central p-bridge between TPA and DCV, with a cuto absorption wavelength of 650 nm; vacuum deposited planar-mixed heterojunction (PMHJ) OPVs incorporating C60 or C70 as an acceptor showed an appreciable PCE of 2.69 or 3.82%, respectively.161 More recently, they reported a novel DAA molecule (d11) with ditolylaminothienyl as the donor and BT and DCV as acceptors for vacuum-deposited OPV devices;162 PMHJ OPVs using C70 acceptor delivered very high Jsc of 14.68 mA cm2 and PCE of 5.81%, which was attributed to the solar spectral response extending to the near-IR region and the ultracompact absorption dipole stacking of the thin lm. Later, they further developed DAA molecule (d12) where the pyrimidine acceptor was employed to replace the BT block in d11.13 The PMHJ device based on d12 and C70 exhibited a markedly high spectra-mismatch-corrected PCE of 6.4% with a JSC of 12.1 mA cm2, VOC of 0.95 V, and FF of 0.56. The high VOC value for d12 is attributed to its low-lying HOMO level (5.46 eV) acquired by using UPS, which is deeper than that of d11 (5.30 eV measured by UPS). Compared to d11, the JSC is slightly lower possibly due to the blue-shifted absorption of d12. The PCE value of 6.4% is among the highest ever obtained for organic vacuum-deposited single cells. Pei and coworkers reported a DAA molecule (d13) with TPA as donor and BT and cyanoacetic acid as acceptors, which exhibited broad absorption (300800 nm) in thin lm.164 Solution-processed BHJ OPVs based on d13:PC61BM (1 : 2) blend gave a moderate PCE of 1.23%.163
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Fig. 5
Chemical structure of triphenylamine-based donors.
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Beneting from its special propeller starburst molecular structure, three-dimensional, amorphous materials with isotropic optical and charge-transporting properties could be expected when combining TPA core with linear p-conjugated arms. Early in 2006, a series of three-dimensional, star-shaped molecules with TPA as core for OPVs were rstly reported by Roncali and coworkers.165168 They synthesized a series of star-shaped molecules based on a triphenylamine core modied by various combinations of thienylenevinylene conjugated branches and electron-withdrawing indanedione or dicyanovinyl groups (d14d18).165 Compared to d14, d15d18 with electronwithdrawing end groups showed broadening and red shift of absorption and IPCE spectra as well as down-shifting of HOMO levels. Under the same conditions, the PCE of vacuumdeposited bilayer OPVs increased from 0.46% (d14) to 1.17% (d17). Optimized devices based on d18 exhibited a PCE of 1.85% with a very high VOC of 1.15 V.167 In 2006, they synthesized a star-shaped molecule with TPA as core and terthiophene as arms (d19).168 d19 exhibited high mobility (0.011 cm2 V1 s1) but narrow absorption (lmax = 429 nm), leading to a low PCE (0.32%). Replacing terminal bithiophene in d19 with one (d20) or two (d21) dicyanovinyl groups extended absorption bands and lowered HOMO levels as a result of intramolecular charge transfer,169 resulting in a large improvement of VOC and JSC. The BHJ OPV devices based on d20 or d21:PC61BM (1 : 2) showed PCEs of 1.80 and 2.02%, respectively. Recently, Zhan and coworkers reported a new threedimensional, star-shaped, DAD small molecule (d22) with TPA as the core, BT as the bridge and terthiophene as the arms.170 Relative to its counterpart d19 without BT, d22 exhibited broader absorption as a result of intramolecular charge transfer. The d22:PC71BM (1 : 2) blend lm exhibited nanoscale aggregated domains, which are benecial to charge separation and enhanced eciency of the OPVs. Without any post-treatment, the BHJ OPV devices exhibited a JSC of 9.51 mA cm2, VOC of 0.87 V, FF of 0.52 and PCE of 4.3%. The PCE value of 4.3% is among the highest reported for solution processed BHJ OPVs based on TPA-containing small molecules, indicating that d22 is a promising three dimensional donor molecule for OPVs. To improve absorption and solution processability of d18, Li and coworkers replaced thiophene with 4,4 0 -dihexyl-2,2 0 bithiophene to give d23.171 Solution-processed BHJ OPVs based on d23:PC71BM (1 : 2) showed a PCE of 1.4%. To further extend absorption, they incorporated vinylene bridge between TPA and bithiophene units in d23 to give d24. The absorption spectrum of the d24 lm covered a broad wavelength range in the visible region from 380 to 750 nm, which red-shifted by ca. 40 nm relative to that of the d23 lm. BHJ OPVs based on d24:PC71BM (1 : 2) showed a JSC of 7.76 mA cm2, VOC of 0.88 V, FF of 0.439 and PCE of 3.0%, better than that of d23. In 2008, Li and coworkers synthesized a star-shaped, DA molecule (d25) with TPA as core, BT as arm and vinylene as bridge.172 The optimized BHJ device based on d25:PC61BM (1 : 3) produced a PCE of 0.61%. Attaching vinyl-TPA to d25 as end groups (d26) extended the absorption and the absorption maximum red shifted from 486 to 541 nm.173 The PCE of BHJ devices based on d26:PC61BM (1 : 3) reached 1.33%,
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higher than that of the devices based on d25 or the corresponding linear molecule. The result indicates that the three dimensional, star-shaped structure may be benecial to improving the photovoltaic performance compared to its linear counterpart. Subsequently, PCE of the devices was further improved to 2.39% by using PC71BM as an electron acceptor and replacing the terminal group of vinyl-TPA in d26 with 4-hexylthiophene (d27).174 In materials based on TPA and its analogs, the DAA structure (e.g., d11 and d12) showed amazing results in PMHJ OPVs, with PCEs up to 6.4%. Meanwhile, the three-dimensional pullpush materials based on TPA as core (e.g., d22) also gave high performance in solution-processed BHJ OPVs with PCEs up to 4.3%. These results suggest that combining multi electron-withdrawing units with TPA core to form threedimensional DAA structure may be one good direction for developing high performance OPV materials.
Small molecular acceptors

As the rapid development of donor materials, including polymers and small molecules, PCEs of the OPVs have reached over 8%. The acceptors are of the same importance as the donors for high performance OPVs. However, research eorts devoted to the acceptors are much less than those on the donors. So far, fullerenes and their derivatives still dominate the acceptors although nonfullerene-based acceptors have attracted increasing attention in recent years. Fullerenes and their derivatives Fullerenes and their derivatives have been widely used in bilayer heterojunction and BHJ OPVs largely due to their strong tendency to accept electrons from donor semiconducting materials and high electron mobilities in the lms even in composite form.39,40 Additionally, fullerene derivatives readily form favorable nanoscale morphological network with donors, which could improve BHJ OPV performance. Table 5 provides a summary of electronic properties as well as OPV data for representative fullerene derivatives (Fig. 6). Generally, C60 (e1) and C70 (e2) were mainly used in vacuum deposited OPVs as acceptors, while their soluble derivatives PC61BM (e3) and PC71BM (e4) were mainly used in solution processed OPVs. C60 was discovered by Kroto et al. in 1985.175 The spherical shape of C60 renders it a good acceptor in any direction, and this isotropy toward electron transfer is advantageous versus planar molecular structures because it greatly increases the chance for a benecial alignment with the donor p-system. Leo and coworkers obtained an over 25% improvement in device performance in ZnPc:C70 BHJ devices over that using ZnPc:C60.176 The PCE enhancement from 2.27 to 2.87% was attributed to an increase in photocurrent (from 7.52 to 9.88 mA cm2), due to stronger long-wavelength absorption of C70 as compared to C60, caused by a relaxation of symmetryforbidden transitions in C70. PC61BM was rstly synthesized by Hummelen et al. for the application in photophysical studies toward improvement of photoinduced electron transfer eciencies in the fabrication of photodetectors and photodiodes.177 PC61BM has much better solubility in organic solvents than its parent compound C60.
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Optical and electronic properties, mobilities, and OPV performance of fullerene-based acceptors mea/cm2 V1 s1 e1 e2 e5 e6 e7 e8 e9 e10 e11 e12 e13 1.3 103 (O, N) 7 104 (S, N) 9.0 105 (S, B) 2.0 104 (S, B) 4.0 104 (S, N) 1.1 103 (S, B) LUMOb/eV 3.9 3.9 3.7 3.74 3.72 3.85 3.66 3.63 3.74 3.75 Active layerc ZnPc:e1 (vac, 1 : 2) ZnPc:e2 (vac, 1 : 2) P3HT:e5 (1 : 1.2) P3HT:e6 (1 : 1) P3HT:e7 (1 : 1) P3HT:e8 (1 : 1.2) P3HT:e9 (1 : 0.6) P3HT:e10 (1 : 1) BP/BP:e11/e11 P3HT:e12 (1 : 1) P3HT:e13 (55 : 45) JSC/mA cm2 7.52 9.88 9.14 10.61 10.79 9.05 10.3 8.64 10.5 10.3 11.3 VOC/V 0.56 0.56 0.724 0.84 0.86 0.87 0.83 0.81 0.75 0.81 0.65 FF 0.543 0.522 0.68 0.727 0.721 0.655 0.62 0.61 0.65 0.63 0.57 PCEd (%) 2.27 2.87 4.5 6.48 6.69 5.2 5.3 4.2 5.2 5.25 4.2 Ref. 176 176 188 190 192 193 195 199 200 201 202
Table 5
a O and S: measured by OFET or SCLC method, N and B: in neat or blend lm. b From electrochemistry. c donor:acceptor: blend by solution process unless stated otherwise; vac: vacuum deposition. d AM1.5, 100 mW cm2.
Fig. 6 Chemical structure of fullerene derivative acceptors.
In 1995, Yu et al. invented the BHJ structure for the OPVs using soluble PC61BM as acceptor blended with conjugated polymer donor.2 A deciency of PC61BM as a photovoltaic material is its very weak absorption in the visible region, due to the high degree of symmetry of C60 which causes the lowestenergy transition formally dipole forbidden. To improve the visible absorption of PC61BM, Wienk et al. synthesized the corresponding C70 derivative PC71BM possessing stronger
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absorption from 400 to 700 nm than PC61BM.178 Since then, PC61BM and PC71BM have been widely used in the fabrication of BHJ OPVs. So far the BHJ OPVs based on polymer donors and PC61BM or PC71BM acceptors have PCE values of over 7%.10,179185 In recent years, some other promising fullerene derivatives have also been reported.39 PC61BM analogues with the phenyl ring replaced by thiophene,186 uorene, or triphenylamine187 units have been synthesized successfully
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and exhibited PCEs of 4% in solution processed BHJ OPV devices in combination with regioregular poly(3-hexylthiophene) (P3HT) donor. Relatively deep LUMO levels of the PC61BM analogues lead to VOC loss in OPV devices, and further limit increase in PCEs. In 2008, Blom and coworkers introduced bisPC61BM (e5), the bisadduct analogue of PC61BM, as a new fullerene-based acceptor material in OPVs.188 The cyclic voltammetry measurements showed the LUMO energy level of bisPC61BM was 0.1 V higher than that of PC61BM, so that the device based on P3HT:bisPC61BM (1 : 1.2) showed a higher VOC of 0.73 V (0.58 V for PC61BM), ultimately a higher PCE of up to 4.5% (3.8% for PC61BM). Li and coworkers developed indeneC60 bisadduct (IC60BA, e6)189,190 and indene-C70 bisadduct (IC70BA, e7)191,192 which exhibited 0.17 and 0.19 eV LUMO up-shift, respectively, relative to PC61BM and PC71BM. Meanwhile, IC60BA and IC70BA were easier to synthesize and more soluble in common solvents than PC61BM and PC71BM. The photovoltaic properties of the fullerene derivatives were studied by fabricating BHJ OPVs with P3HT as donor and the fullerene derivatives as acceptor. Thanks to the LUMO up-shift, the VOC of the devices with IC60BA and IC70BA reached 0.84 V, which was 0.26 V higher than that (0.58 V) of the devices with PC61BM as acceptor, and the PCE values of the devices were up to 5.44 and 5.64%, respectively, which were over 40% enhancement in comparison with that (3.88%) of the BHJ OPVs based on P3HT and PC61BM.189,191 After thermal annealing at 150 1C for 10 min, BHJ OPVs based on P3HT and IC60BA provided a PCE of 6.48%.190 By additive (3-hexylthiophene) processing, BHJ OPVs based on P3HT and IC70BA showed a PCE of up to 6.69%,192 which is the highest value in the OPVs based on P3HT reported in the literature so far. Cheng and coworkers reported a new class of diphenylmethano-based C60 bisadduct.193 The plane of the phenyl groups lying parallel to the fullerene surface sterically protects and shields the core C60 structure from severe intermolecular aggregation, rendering it intrinsically soluble, morphologically amorphous, and thermally stable. The double functionalization raises the LUMO energy level (3.85 eV) by ca. 0.1 eV, compared to that of PC61BM (3.95 eV). The BHJ devices based on P3HT:e8 (1 : 1.2) blend after thermal annealing at 140 1C for 10 min exhibited a JSC of 9.05 mA cm2, VOC of 0.87 V, FF of 0.655, and a high PCE of 5.2%. Voroshazi et al.,194 Kim et al.195 and Wang et al.196 independently reported novel o-xylenyl C60 bisadduct e9 with a higher LUMO level (3.66 eV) relative to PC61BM. e9 was successfully used as an electron acceptor with P3HT in BHJ OPVs, showing a high PCE of 5.31% with a high VOC of 0.83 V.195 Endohedral fullerenes were also conrmed to have much higher LUMO levels than their corresponding empty-cage fullerenes in theory197 and experiment.198 Ross et al. synthesized a series of soluble PCBM-like Lu3N@C80 derivatives, and the LUMO energy level of Lu3N@C80-PCBH (e10) is 0.28 eV higher than that of PC61BM.199 The BHJ devices based on P3HT:e10 (1 : 1) after thermal annealing at 110 1C for 10 min displayed high VOC of 0.89 V and PCE of 4.2%. This result indicates that this series of endohedral fullerene derivatives might be another type of high VOC acceptor for application in OPVs.
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Matsuo et al. synthesized a new fullerene derivative with Si-containing side chains (e11), which has good thermal stability and LUMO up-shift relative to PC61BM.200 They fabricated OPVs with a three-layer structure: an interdigitated BHJ layer of tetrabenzoporphyin (BP):e11 sandwiched by BP donor and e11 acceptor layers. The JSC, VOC, FF and PCE of the best device reached 10.5 mA cm2, 0.75 V, 0.65 and 5.2%, respectively. Recently, Sharma and coworkers synthesized a new fullerene derivative (e12) from PC61BM; e12 displayed better solubility in common solvents and stronger absorption in the lm than PC61BM.201 After optimizing mixed solvents and subsequent thermal annealing, the best device with P3HT and e12 showed a JSC of 10.3 mA cm2, VOC of 0.81 V, FF of 0.63, and PCE of 5.25%. Frechet and coworkers synthesized a dihydronaphthyl fullerene benzyl alcohol benzoic acid ester (e13);202 the best BHJ OPV based on P3HT:e13 (55 : 45) after thermal annealing at 150 1C for 30 min exhibited a JSC of 11.3 mA cm2, VOC of 0.65 V, FF of 0.57, and PCE of 4.2%. Without question, fullerene derivatives are the most successful acceptors in the OPVs so far. During the last decade, signicant advances have been made in fullerene-based acceptors, appropriate chemical modications have up-shifted their inherent LUMO energy levels, and the cost of fullerene production has also decreased along with an increase in synthetic yields and material purity. Nevertheless, there remain incentives to develop nonfullerene acceptors that will not only retain the favorable electron accepting and transporting properties of fullerenes, but also overcome their insuciencies such as the limited spectral breadth and bandgap variability. Rylene diimides On the basis of recent developments in high-performance electron transporting materials for OFETs, some research groups have begun investigating nonfullerene acceptors for use in OPVs. Rylene diimides have attracted interest as alternative acceptor materials since they exhibit excellent photostability, easy alteration of HOMO and LUMO energies, large absorption coecients, high electron mobilities, electron anities similar to those of fullerenes and each of these properties can be readily tailored through either variation of substituents on the imide nitrogen atoms or on the rylene core.203206 Table 6 provides a summary of electronic properties as well as OPV data for representative rylene diimide related acceptors (Fig. 7). Perylene diimides (PDIs) are among the earliest and most common nonfullerene acceptors investigated in OPVs. Many early studies of OPVs incorporating PDIs consisted of layered structures fabricated by vacuum deposition. The rst bilayer heterojunction OPV was reported by Tang where a PDI-based small molecule (f1) was used as the acceptor along with CuPc as the donor.1 When ZnPc was employed as a donor in place of CuPc in a simple bilayer device, the PCE was improved from 0.95% to 1.3%.207 Later, the cis-isomer f2 was prepared, and a bilayer heterojunction device based on CuPc/f2 showed a PCE of 0.93%, slightly lower than that of f1 (1.1%).208 The lower eciency was attributed to less ecient packing in acceptor f2, leading to shorter exciton diusion lengths in the system.
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Optical and electronic properties, mobilities, and OPV performance of rylene diimide-based acceptors Egopt/eV meb/cm2 V1 s1 HOMOc/LUMO/eV Active layerd ZnPc/f1 CuPc/f2 P3HT:f3 (1 : 4) P3HT:f4 (1 : 4) P3HT:f5 (1 : 1) X:f6 (1 : 1) Y:f7(1 : 3.5) Z:f8 (1 : 1) ZnPc/f9 P3HT/P3HT:f10 (1 : 1)/f10
d
Table 6
lmaxa/nm f1 f2 f3 530 f4 542 f5 f6 f7 f8 455 f9 f10
JSC/mA cm2 VOC/V FF 3.66 1.65 1.32 1.74 6.8 6.3 8.30 2.11 3.51
PCEe(%) Ref. 1.3 0.93f 0.25 0.182 0.50 2.85 3.17 3.88 0.54 1.50 207 208 209 211 212 213 214 215 216 217
2.13 8.8 104 5.6 104 4.6 104
5.8/3.8 5.82/3.69 6.0/3.85 5.9/3.8 5.90/3.95 5.78/3.87 5.5/4.1
2.13
0.45 0.36 0.75 0.88 0.95 0.90 0.50 0.82
0.34 0.38 0.38 0.47 0.53 0.52 0.51 0.52
a In lm. b Measured by SCLC method in blend lm. c From electrochemistry. blend by solution process. e AM1.5, 100 mW cm2. f 94 mW cm2.
Donor/acceptor: bilayer by vacuum deposition; donor:acceptor:
Fig. 7 Chemical structure of rylene diimide acceptors.
BHJ OPVs based on solution processed blends of PDI-based materials with appropriate donor materials are attracting increasing attention. Solution processable PDI-based acceptors can be prepared by introducing solubilizing groups, such as alkyl, on the imide nitrogen atoms. 3-Pentyl substituted PDI (f3) was prepared and blended with a variety of donors such as P3HT209 and polycarbazole210 to fabricate OPVs by spin coating. By careful control over the solvent, substrate temperature during deposition, and annealing temperature and time, the devices based on P3HT:f3 (1 : 4) lm showed a JSC of 1.65 mA cm2, VOC of 0.45 V, FF of 0.34, and PCE of 0.25%.209 Nonetheless the tendency for f3 to form crystalline domains within polymer matrices limited the eciencies of BHJ devices since the crystalline domains acted as electron traps to decrease photocurrents. PDIs with longer alkyl substituents on the imide nitrogen atoms have also been prepared, and when blended with P3HT
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gave low eciencies. For instance, a maximum PCE of 0.18% was achieved with a P3HT:f4 weight ratio of 1 : 4 after annealing at 80 1C for 1 h.211 Along with varying substituents on the imide nitrogen atoms, recent studies have also examined the impact of substituents in the bay regions of the PDIs on thinlm morphology and device performance.211,212 Although the PDIs with electron donating or withdrawing substituents have tuned the LUMO energy level over a range of nearly 0.7 eV and impacted on device VOC, none of these PDI bay-substituted derivatives yielded higher performance than simple PDIs without bay-region substituents.211 Very recently, Laquai et al. demonstrated that the photovoltaic characteristics of blend lms of P3HT and PDIs are improved upon using a core-alkylated PDI derivative (f5) instead of the often used N-alkylated.212 The alkyl-substitution pattern aected the packing of the PDI and improved the blend aggregation.
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The optimized device based on P3HT:f5 exhibited a PCE of 0.5%, with JSC of 1.74 mA cm2, VOC of 0.75 V, and FF of 0.38. PDI-based small molecular acceptors had no promising results in OPVs, until Sharma and coworkers developed a series of high-performance acceptors by attaching tert-butylphenoxy groups to the bay-region of PDIs and varying the imide substituent.213215 The acceptors f6f8 with dierent fusedring substituents on the imide exhibited electron mobilities (Measured by SCLC) of 49 104 cm2 V1 s1 when blended with small molecular donors X, Y, or Z (Fig. 7). The devices based on X:f6, Y:f7, and Z:f8 blends gave PCEs of 2.85%,213 3.17%,214 and 3.88%,215 respectively, after annealing and/or inserting a ZnO layer between the active layer and the cathode. The PCE of 3.88% is the highest ever reported for nonfullerenebased BHJ OPVs. Compared to the PDI-based molecules, the smaller fusedring unit naphthalene diimide (NDI) derivatives were less successful as acceptors in OPVs, because they possess a larger bandgap and thus absorb poorly in the visible spectrum (generally at onset less than 400 nm). For example, bilayer OPVs based on ZnPc/f9 exhibited a PCE of 0.54%, lower than that (1.3%) of its analog, f1.216 Recently, Jenekhe and coworkers reported a new nonfullerene acceptor (f10) with NDI as core and oligothiophene as arms used in BHJ OPVs. After annealing at 100 1C for 10 min and adding 0.2% diiodooctane additive, the optimized P3HT:f10 based device showed a PCE of 1.5%.217,218 Although rylene diimides have strong absorption and high electron mobility, the performance of OPVs using rylene diimides as acceptors do not yet rival those of fullerene-based systems. The planar shapes of rylene diimides may result in enhanced p-stacking and more quasi one-dimensional electron transport, compared to the spherical/ellipsoidal molecular
Table 7
shapes of fullerenes. So when rylene diimide-rich phases do not have high degrees of long-range order, there can be multiple orientations of p-stacked phases, which may decrease long-range mobilities and therefore act as recombination centers. In this system, introducing bulky side chains can decrease the molecular planarity and may be helpful to improve the photovoltaic performance. Other nonfullerene acceptors Apart from the rylene-based acceptors, some other n-type molecules have been reported as the nonfullerene acceptors for OPVs. Table 7 provides a summary of electronic properties as well as OPV data for representative other nonfullerene small molecular acceptors (Fig. 8). One method of increasing the n-type character of molecules is to introduce electronwithdrawing units, such as uorine and cyano, to the periphery of the aromatic rings.219 For example, hexadecauorinated CuPc g1 showed electron mobilities of up to 5 103 cm2 V1 s1 in OFETs.220,221 When incorporating g1 in bilayer heterojunction OPVs as an acceptor and sexiphenyl (p-6P) as a donor, a PCE of 0.18% was obtained.222 Using subphthalocyanine (SubPc) instead of p-6P led to improved PCE of 0.56%.223 Torres and coworkers synthesized a series of uorinated SubPc as acceptors in OPVs.224 Bilayer OPV devices of the acceptors with a variety of donors, such as pentacene, CuPc, AlClPc, SubPc and SubNc, were prepared by vacuum evaporation. In these devices, the SubPc/g2-based device showed the highest PCE of 0.96%, with JSC of 2.1 mA cm2, VOC of 0.94 V, and FF of 0.49. However, the PCE value of 0.96% was obviously lower than that (3.0%) of SubPc/C60-based control device. The moderate eciencies could be limited by the low electron mobility of the amorphous uorinated SubPc as well as series resistance eects in the active layer. Jones and coworkers found that replacing uorinated SubPc (g2) with chlorinated SubPc (g3) led to
Optical and electronic properties, mobilities, and OPV performance of other nonfullerene-based acceptors Egopt/eV 1.5 6.4/4.9 meb/cm2 V1 s1 HOMOc/LUMO/eV Active layerd p-6P/g1 SubPc/g1 SubPc/g2 SubPc/g3 SubPc/g4 P3HT:g5 (1 : 1) P3HT:g6 (1 : 1) P3HT:g7 (1 : 1) P3HT:g8 (1 : 1) P3HT:g9 (5 : 3) P3HT:g10 (1 : 1) P3HT:g11 (1 : 1) P3HT:g12 (1 : 1) P3HT:g13 (1 : 1) P3HT:g14 (1 : 2) P3HT:g15 (1 : 1) P3HT:g16 (1 : 1) POPT:g16 (1 : 1) P3HT:g17 (1 : 1.4) P3HT:g18 (1 : 2) P3HT:g19 (1 : 1) P3HT:g20 (1 : 2) P3HT:g21 (1.5 : 1) JSC/mA cm2 0.96 2.54 2.1 3.53 7.8 3.72 1.93 2.44 3.17 1.93 0.24 0.66 5.72 2.36 1.79 3.00 5.50 4.7 2.36 1.93 4.40 3.9
d
lmaxa/nm g1 g2 g3 g4 g5 g6 g7 g8 g9 g10 g11 g12 g13 g14 g15 g16 g17 g18 g19 g20 g21
a
VOC/V 0.42 0.40 0.94 1.31 0.95 0.84 0.54 0.95 0.80 1.05 0.93 0.78 0.48 0.62 0.67 0.76 0.62 0.96 0.71 0.52 0.76 1.1
FF 0.55 0.49 0.58 0.54 0.41 0.41 0.43 0.50 0.39 0.21 0.27 0.57 0.50 0.37 0.48 0.40 0.56 0.52 0.31 0.56 0.4
PCEe (%) 0.18 0.56 0.96 2.68 4.0 1.29 0.43 1.00 1.26 0.80 0.06f 0.30.4f 0.14 1.57 0.73 0.45 1.10 1.40 2.54 1.00 0.31 1.86 1.7
Ref. 222 223 224 225 226 228 227 228 228 229 232 233 235 236 237 240 241 241 244 245 246 247 248
780
710 1.82 700 620 490 640 475 1.15 105 (S) 1.14 104 (S)
5.7/3.95 5.29/3.50 5.47/3.64 5.34/3.21 6.27/3.92 5.47/3.42 5.9/4.1 6.2/3.6 6.02/3.50 6.0/3.6 5.77/3.35 5.26/3.52 5.9/4.09 6.1/3.5 5.17/3.24
1.8 2.40 2.34 1.81 1.81 2.18
580 410 517
3 10
(O)
In lm. b O and S: measured by OFET or SCLC method in neat lm. c From electrochemistry. donor:acceptor: blend by solution process. e AM1.5, 100 mW cm2. f 80 mW cm2.
Donor/acceptor: bilayer by vacuum deposition;
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Fig. 8 Chemical structure of other nonfullerene acceptors.
improved performance; SubPc/g3-based device showed promising PCEs of 2.68% with very high VOC of 1.31 V.225 After selective halogenation to tune the energy levels of SubPc, g3 provided sucient interfacial HOMO and LUMO osets for ecient exciton dissociation, whilst maximizing the interface gap. Recently, Verreet et al. reported uorinated fused SubPc
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dimer (g4, mixture of two isomers) with strong and complementary absorption to the donor material SubPc.226 The optimized SubPc/g4-based bilayer device exhibited a high PCE of 4%, with JSC of 7.8 mA cm2, VOC of 0.95 V, and FF of 0.54. The PCE of 4% is the highest ever reported for nonfullerene-based bilayer OPVs.
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Although pentacene and its derivatives belong to a promising class of donors in OPVs, Anthony and coworkers demonstrated that it is possible to switch them from donors to acceptors in OPVs by lowering their LUMO energy levels through cyanation.227 Cyanopentacenes g5 and g6 with tricyclopentylsilyl groups have been synthesized;227,228 the energy levels can be tuned by varying the number of cyano groups, while the trialkylsilyl groups control crystal packing and lm morphology. They found that the HOMO and LUMO energy levels downshifted by ca. 0.14 eV for every cyano group that was introduced to the pentacene core, and a particularly strongly one-dimensional sandwich herringbone crystal packing motif yielded devices with the highest photocurrent. In the initial devices, blended with P3HT donor, dicyanopentacene g6 exhibited a best PCE of 0.43%, with JSC of 1.93 mA cm2, VOC of 0.54 V, and FF of 0.41. Reducing the number of cyano from 2 (g6) to 1 (g5) led to a higher performance: JSC of 3.72 mA cm2, VOC of 0.84 V, FF of 0.41, and PCE of up to 1.29%.228 The 0.3 V improvement in VOC was attributed to an up-shift of LUMO energy level caused by a decrease in cyano number. Subsequently, several other pentacene derivatives with a single electron withdrawing group were investigated, and the better acceptors were found to be chloropentacene g7 and triuoromethylpentacene g8 with PCE of 1.00% and 1.26%, respectively, when blending with P3HT.228 Recently, anthradithiophene was also converted into acceptor for OPVs, through the introduction of amide groups.229 In most literature work, anthradithiophene derivatives were studied as a mixture of syn and anti isomers due to the great challenge in the preparation of isomerically pure materials. However, amide groups caused dierent self-assembly of the syn- and anti-isomers that allowed for the rst time separation and property evaluation of isomerically pure anthradithiophenes. Anthony and coworkers evaluated the acceptor properties of two pure isomers and their mixture in BHJ OPVs with P3HT as donor; syn-isomer g9 yielded much better PCE (0.8%) than that of anti-isomer (0.008%) or their mixture (0.09%) after annealing at 120 1C for 1 min. For anti-isomer, larger scale aggregation was observed in the blend lm, while syn-isomer:P3HT blend showed a more uniform coverage textured with small grains of the acceptor. The dierence in blend lm morphology is responsible for the dierence in OPV performance. As same as CuPc and pentacene, oligothiophenes have also been widely employed as donors in OPVs. However, thienylS,S-dioxide caused a signicant increase in electron anity of the oligothiophene system.230234 Barbarella et al. developed a series of linear and branched thiophene-S,S-dioxide-containing oligothiophene acceptors for OPVs.232,233 In these studies, due to the propensity for linear oligothiophene acceptors to crystallize and form aggregates leading to reduced D/A interfacial area, BHJ OPVs based on all linear acceptors blending with P3HT showed very low PCEs, and the asymmetric molecule g10 gave a PCE of 0.06%, higher than the others.232 To suppress crystallization, V-shaped acceptors were synthesized. Owing to the branched structure lacking any symmetry elements, these V-shaped acceptors displayed a low tendency to crystallization and better lm forming properties than their linear counterparts.233 Thus for the acceptor g11, devices fabricated from a blend of P3HT yielded estimated PCE of 0.30.4% by thermal annealing.233
4266 Chem. Soc. Rev., 2012, 41, 42454272
Cyano is an excellent electron-withdrawing unit in design of donor and acceptor materials for OPVs. As with the systems described above, carbazole has also been modied as an acceptor through cyanation.235 The molecule g12 substituted with two DCV groups showed broad absorption with the onset of about 600 nm. By controlling blend ratio, solvent and annealing conditions, the optimized devices with P3HT:g12 showed a PCE of 0.14%. The relatively low PCE of OPVs based on g12 is due to its low electron mobility of 1.15 105 cm2 V1 s1 estimated by the SCLC method. Wang and coworkers developed DCV substituted quinacridone derivatives as acceptors for BHJ OPVs.236 These molecules exhibited remarkable absorption in the region from 650 to 700 nm. In particular, molecule g13 exhibited a LUMO energy level of 4.1 eV, small bandgap (1.8 eV) and moderate electron mobility (1.14 102 cm2 V s1 by SCLC). A device based on P3HT:g13 exhibited a PCE of 1.57%, with JSC of 5.72 mA cm2, VOC of 0.48 V, and FF of 0.57. However, the relatively deep LUMO energy level of g13 led to a signicant loss of photovoltage. Meredith et al. combined uorene, BT and DCV together to synthesize a new nonfullerene acceptor (g14), which can be processed by vacuum deposition or solution processing to give amorphous thin lms and can be annealed at a modest temperature to give lms with better order and enhanced charge transport properties.237 The P3HT:g14 BHJ device spun cast from dichlorobenzene showed a low PCE of 0.04%, and after annealing at 65 1C for 20 min, the PCE was improved to 0.73%, which can be attributed to an increase in electron mobility in the acceptor phase and improvement in the charge percolation network to the contacts. Recently, a series of substituted dicyanoimidazole derivatives known as Vinazene have received focused attention as acceptors in BHJ OPVs.238243 The series of Vinazene-based molecules displayed a wide range of electronic properties, with LUMO energy levels ranging from 2.76 to 3.60 eV.238,239 Of these molecules, g15 and g16 containing BT core gave the most ecient devices when blended with P3HT in BHJ OPVs.238241 After thermal annealing, g15 and g16 based devices showed a PCE of 0.45%240 and 1.1%,241 respectively. For g16, a further improvement in eciency can be achieved by employing an octylphenyl-substituted polythiophene (POPT) as the donor. The optimized device at a 1 : 1 blend weight ratio of POPT:g16 yielded a JSC of 5.5 mA cm2, VOC of 0.62 V, FF of 0.4, and PCE of 1.4%.241 The higher performance of POPT could be explained by the ability of the conjugated phenyl substituent to twist out of planarity, resulting in a high dissociation eciency. Very recently, Sellinger et al. synthesized a series of electron-decient molecules based on a central BT moiety anked with vinylimides and used for solution processed BHJ OPVs as acceptors.244 Of these acceptors, phthalimide-BT based molecule (g17) showed promising photovoltaic performance. BHJ OPVs based on P3HT:g17 (1 : 1.4) yielded a high VOC of 0.96 V and a maximum PCE of 2.54%, whereas naphthalimide-BT analog only aorded 0.1% PCE. The high VOC is attributed to the high LUMO level (3.3 eV) of g17. DPP-based materials have been proven promising donors for OPVs; blended with PC71BM acceptors, they yielded PCEs
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up to 4.4%.93 Interestingly, a variety of DPP derivatives with electron withdrawing end capping groups (such as aldehyde, triuoromethylphenyl and triuorophenyl) were tested as acceptors in OPVs.245,246 The inherent electron anity of DPP moiety was further improved through the introduction of electron withdrawing groups. Among these compounds, g18 provided the highest PCE of 1.0%, when blended with P3HT donor in a BHJ device,245 while aldehyde substituted DPP g19 showed a lower PCE of 0.31%.246 Very recently, Pei et al. modied the uoranthene-fused imide scaold to develop a new electron acceptor g20 by combining with a cyano substituent group.247 The investigation of the photophysical and electrochemical properties indicates that LUMO level (ca. 3.5 eV) of g20 both matches the work function of the LiF/Al cathode and increases VOC of OPV devices. The preliminary results showed that by thermal annealing at 100 1C, the solution-processed BHJ OPVs based on P3HT:g20 (1 : 2) gave a PCE of 1.86%, with relatively high VOC of 0.76 V, compared to that (0.58 V) of the control device based on P3HT:PC61BM blend. Wudl and coworkers reported the use of a 9,9 0 -biuorenylidene polycycle for small molecule acceptors.248,249 The 9,90 -biuorenylidene structures are particularly eective at stabilizing a negative charge, due to both steric and electronic eects. But the steric eect is relieved when the molecule receives an electron and gains aromaticity. Meanwhile, the LUMO energy level of this system is easily tuned by substitution on the aromatic periphery. When blended with P3HT, the asymmetric molecule g21 showed a decent PCE of 1.7% and a high VOC of 1.10 V.248 Chemical functionalization allows control over absorption prole and energy levels of nonfullerene acceptors. However, compared to fullerenes and their derivatives, nonfullerene acceptors showed lower performance in OPV devices, especially solution processed BHJ OPVs. The hurdles that remain arise from active layer morphology and charge transport issues. While many of these materials showed good electron mobilities when measured in neat lms, the mobilities in blends with
the donors were generally not as high. The next step in the development of new nonfullerene acceptors may involve developing multi-dimensional structures.
Donoracceptor dyad molecules for single-component OPVs

For BHJ OPVs, one of the main problems is ne tuning the complicated physical interactions between donordonor, acceptoracceptor, and donoracceptor to obtain an ideal and stable morphology with a well-dened nanostructure. To solve this problem, acceptors, such as fullerene, PDI, DCV etc. were attached to donor molecules, such as oligothiophene, oligophenylenevinylene, and triphenylamine, as pendant side chains or end groups to form donoracceptor dyad molecules (Fig. 9), which can be regarded as a molecular heterojunction and used to fabricate single-component OPVs. Such a structure facilitates exciton dissociation and homogeneous distribution to prevent severe phase separation. In recent years, the donoracceptor dyad molecules showed some promising performance.250 Hashimoto and coworkers developed a series of fullerenedyad molecules for single-component OPVs. In 2009, they reported synthesis of an oligophenylenevinylene containing ve phenyl rings with C60 connected to the middle phenyl ring in the conjugated chain by a polyether linker (h1).251 After thermal annealing at 150 1C for 1 min under inert atmosphere, the h1-based single-component OPV device gave JSC of 3.30 mA cm2, VOC of 0.88 V, FF of 0.44 and PCE of 1.28% under white light irradiation at 100 mW cm2. More recently, the same group reported an oligothiophene containing 8 thiophene rings and an electron-withdrawing DPP unit in the middle with C60 connected to the DPP unit by a polyether linker (h2).252 h2 showed a low bandgap and the photocurrent response was extended to 850 nm, so that a h2-based singlecomponent OPV device gave a high JSC (4.79 mA cm2). This high JSC together with VOC of 0.51 V and FF of 0.46 led to a total PCE of 1.1%.
Fig. 9 Chemical structure of donoracceptor dyads.
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In 2009, Geng et al. synthesized a series of extended DA cooligomers in which substituted uorene-alt-bithiophene oligomer was selected as donor block and PDI as acceptor block.253 They found that solvent vapor annealing signicantly improved the order of the cooligomers with an increase of the persistent length of the lamellae. After solvent annealing, h3-based single-component OPV device showed a JSC of 4.49 mA cm2, VOC of 0.87 V, FF of 0.38 and PCE of 1.50%, which is the best value reported for a single-component OPV device so far. TPA-DCV-based star-shaped DA molecule (d17, Fig. 5) reported by Roncali et al. also exhibited promising results in single-component OPVs: JSC of 1.7 mA cm2, VOC of 0.70 V, FF of 0.30, and PCE of 0.40%.167 The fast charge recombination and inecient charge hopping and transport in single-component OPVs is probably responsible for the relatively lower PCEs of single-component OPVs compared to donor/acceptor blend or bilayer solar cells.17
Conclusions and outlook

We have reviewed some representative and promising small molecule donors, acceptors, and donoracceptor dyad systems for high-performance bilayer, BHJ, and single-component OPVs. So far a number of small molecular OPV materials have been discovered, but most of these materials give relatively low PCEs. With extensive research and accumulated practical experience that we have outlined in this review, the guidelines to pursuing and developing high-performance small molecules for OPVs are becoming legible. The basic requirements of specic intrinsic properties necessary for an ideal small molecular donor, acceptor or donoracceptor dyad materials include: (a) a low optical bandgap for broad absorption range matching with solar spectrum and high extinction coecient for capturing more solar energy; (b) long exciton diusion lengths for eective migration of excitons to D/A interface; (c) high hole or electron mobility for accelerating charge transport, which in turn allows a thicker active layer required for increased light harvesting, as well as reduces charge recombination and series resistance; (d) suitable HOMO/LUMO energy levels to ensure a large VOC and a downhill energy oset for exciton dissociation. Additionally, easy sublimation, relatively low molecular weight, excellent thermal stability are also necessary for vacuum deposited materials, while good lm-forming property and sucient solubility are also necessary for solution processed materials. Meanwhile, since the optimal OPV material itself is device application and system specic, for bilayer heterojunction OPVs, high crystallinity of the active materials may be benecial to improve the device performance. On the other hand, for BHJ OPVs, it is also critical for the active materials that formation of a bicontinuous interpenetrating network with the optimum morphology for building two distinct highways for transporting free charge carriers; moderate crystallinity of materials can improve charge carrier mobility, but high crystallinity will cause large phase separation scale and low PCE of devices. Generally, low PCEs in OPV devices may be attributed to the OPV materials violating one or some of the above criteria, or the device conguration and fabrication below optimization.
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High-eciency OPVs have been achieved as a result of innovations of small molecular materials and device fabrication technology, boding a bright future for this exciting research eld. For further improving the device performance by modifying the molecular structure of active materials, it is necessary that deeply understanding the relationships between chemical structures and optical, electronic and device properties. To summarize: (1) Enhancing and extending the absorption of active materials to match solar radiation is one of the main ways to improve JSC and eciencies of OPV devices. An OPV molecule with bandgap o 2 eV is necessary but not sucient for a high PCE. The oligomers with long conjugation length generally possess broad and strong absorption. Building the pushpull structure with electron donating and withdrawing units can create the intramolecular charge transfer and in turn improve the molecular absorption. Molecules and oligomers based on fused-ring blocks such as acenes, dithienocyclopentadiene, dithienosilole, dithienopyrrole and benzodithiophene could exhibit relatively low Eg and broad absorption. (2) Since the VOC of devices is related directly to the dierence between the HOMO level of the donor and the LUMO level of the acceptor, a lower HOMO of a donor and a higher LUMO of an acceptor would help to achieve a higher VOC. In general, a donor with a HOMO below 5.3 eV or an acceptor with a LUMO above 3.7 eV tends to give VOC 4 0.8 V. The energy levels can be tuned by changing the species and number of substituent group. In general, introducing the electron-withdrawing units, such as cyano and uorine etc., would down-shift the LUMO levels of materials. On the contrary, the electron-donating units such as TPA and thiophene help to raise the HOMO levels. (3) The high hole mobility of donors and electron mobility of acceptors (4 102 cm2 V1 s2) would help to achieve a high JSC. Molecules based on fused-ring blocks tend to exhibit relatively high mobilities. Crystal structure and pp stacking in the lm are the key factors to determining the mobility of materials. In addition, the mobilities matching of donor and acceptor benet also FF and PCE of devices. (4) For solution processing, the use of long alkyl or alkoxy side chains has been a common approach. However, the side chain nature not only aects the solubility, conguration and intermolecular interaction of the molecules, and also aects the absorption, energy levels and charge transport properties. In particular, the side chain aects morphology of blend lms and nally aects the photovoltaic performance of devices. It should be stressed that increasing the content of insulating alkyl side chains relative to the conjugated main chain in the molecule may result in deterioration in charge transport. Thereby, balanced choice of a suitable solubilizing group at an appropriate location is of crucial importance for ne-tuning the structureproperties relationship. (5) The morphology and phase separation scale in BHJ lm is not only related to the nature of materials, but also can be optimized by carefully controlling the device fabrication conditions, such as varying spin-casting solvent and speed or donor/acceptor radio and concentration, thermal annealing, exposure to solvent vapor, modifying the surface energy of the blend component and substrate. With optimal morphology
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on the nanoscale, it becomes easy to translate the microscopic intrinsic properties of the photovoltaic materials into macroscopic OPV device performance. (6) Merocyanine (MC) dye and TPA-based DAA molecule donors in combination with C60 or C70 acceptors exhibited very high performance in vacuum deposited OPVs, while onedimensional oligothiophenes with pushpull structures in combination with PC61BM or PC71BM exhibited very high performance in solution processed BHJ OPVs; the best PCEs were up to 4 6%. Fused acenes exhibited relatively low eciencies in vacuum deposited or solution processed OPVs (o 3%). Nonfullerene acceptors (PCE o 4%) do not yet rival fullerene-based systems in vacuum deposited or solution processed devices, while donoracceptor dyad molecular heterojunction (PCE o 1.5%) does not yet rival donor/acceptor bilayer or bulk heterojunction in vacuum deposited or solution processed devices. (7) It should be emphasized that the PCE is more a device parameter than an intrinsic photovoltaic material parameter. High eciency achievement is a systematic combination of material properties with judicious and careful optimization of the various device fabrication conditions. So far the best performances (4 6%) of OPVs were achieved from vacuum or solution-deposited small molecule donors with fullerene acceptors. An interdisciplinary approach such as novel photovoltaic materials and new advanced device concepts will probably bring high eciency over 10% and low cost OPVs to nal commercialization.
Acknowledgements
This work was supported by NSFC (Grants 21025418, 51011130028, 21021091), 973 Project (Grant 2011CB808400), and the Chinese Academy of Sciences.
References
1 C. W. Tang, Appl. Phys. Lett., 1986, 48, 183. 2 G. Yu, J. Gao, J. C. Hummelen, F. Wudl and A. J. Heeger, Science, 1995, 270, 1789. 3 G. A. Chamberlain, Sol. Cells, 1983, 8, 47. 4 R. R. Lunt, N. C. Giebink, A. A. Belak, J. B. Benziger and S. R. Forrest, J. Appl. Phys., 2009, 105, 053711. 5 M. Hiramoto, H. Fujiwara and M. Yokoyama, Appl. Phys. Lett., 1991, 58, 1062. 6 J. G. Xue, B. P. Rand, S. Uchida and S. R. Forrest, Adv. Mater., 2005, 17, 66. 7 N. S. Sariciftci, L. Smilowitz, A. J. Heeger and F. Wudl, Science, 1992, 258, 1474. 8 J. J. M. Halls, C. A. Walsh, N. C. Greenham, E. A. Marseglia and R. H. Friend, Nature, 1995, 376, 498. 9 C. J. Brabec, N. S. Sariciftci and J. C. Hummelen, Adv. Funct. Mater., 2001, 11, 15. 10 Z. He, C. Zhong, X. Huang, W.-Y. Wong, H. Wu, L. Chen, S. Su and Y. Cao, Adv. Mater., 2011, 23, 4636. 11 X.-H. Zhu, J. Peng, Y. Cao and J. Roncali, Chem. Soc. Rev., 2011, 40, 3509. 12 V. Steinmann, N. M. Kronenberg, M. R. Lenze, S. M. Graf, D. Hertel, K. Meerholz, H. Burckstummer, E. V. Tulyakova and F. Wurthner, Adv. Energy Mater., 2011, 1, 888. 13 S.-W. Chiu, L.-Y. Lin, H.-W. Lin, Y.-H. Liu, Z.-Y. Huang, Y.-T. Lin, F. Lin, Y.-H. Chen and K.-T. Wong, Chem. Commun., 2012, 48, 1857. 14 Z. Li, G. He, X. Wan, Y. Liu, J. Zhou, G. Long, Y. Zuo, M. Zhang and Y. Chen, Adv. Energy Mater., 2012, 2, 74.
15 Y. Sun, G. C. Welch, W. L. Leong, C. J. Takacs, G. C. Bazan and A. J. Heeger, Nat. Mater., 2012, 11, 44. 16 Y.-J. Cheng, S.-H. Yang and C.-S. Hsu, Chem. Rev., 2009, 109, 5868. 17 X. Zhan and D. Zhu, Polym. Chem., 2010, 1, 409. 18 X. Zhao and X. Zhan, Chem. Soc. Rev., 2011, 40, 3728. 19 J. Chen and Y. Cao, Acc. Chem. Res., 2009, 42, 1709. 20 S. Gunes, H. Neugebauer and N. S. Sariciftci, Chem. Rev., 2007, 107, 1324. 21 E. Bundgaard and F. C. Krebs, Sol. Energy Mater. Sol. Cells, 2007, 91, 954. 22 C. Winder and N. S. Sariciftci, J. Mater. Chem., 2004, 14, 1077. 23 J. Roncali, Chem. Soc. Rev., 2005, 34, 483. 24 K. M. Coakley and M. D. McGehee, Chem. Mater., 2004, 16, 4533. 25 L. Huo and J. Hou, Polym. Chem., 2011, 2, 2453. 26 C. J. Brabec, S. Gowrisanker, J. J. M. Halls, D. Laird, S. Jia and S. P. Williams, Adv. Mater., 2010, 22, 3839. 27 O. Inganas, F. Zhang, K. Tvingstedt, L. M. Andersson, S. Hellstrom and M. R. Andersson, Adv. Mater., 2010, 22, E100. 28 C. Li, M. Liu, N. G. Pschirer, M. Baumgarten and K. Mullen, Chem. Rev., 2010, 110, 6817. 29 N. Blouin and M. Leclerc, Acc. Chem. Res., 2008, 41, 1110. 30 O. Inganas, F. Zhang and M. R. Andersson, Acc. Chem. Res., 2009, 42, 1731. 31 Y. Liang and L. Yu, Acc. Chem. Res., 2010, 43, 1227. 32 J. Roncali, Acc. Chem. Res., 2009, 42, 1719. 33 B. Walker, C. Kim and T.-Q. Nguyen, Chem. Mater., 2011, 23, 470. 34 Y. Li, Q. Guo, Z. Li, J. Pei and W. Tian, Energy Environ. Sci., 2010, 3, 1427. 35 A. W. Hains, Z. Liang, M. A. Woodhouse and B. A. Gregg, Chem. Rev., 2010, 110, 6689. 36 M. Lloyd, J. Anthony and G. Malliaras, Mater. Today, 2007, 10, 34. 37 W. Tang, J. Hai, Y. Dai, Z. Huang, B. Lu, F. Yuan, J. Tang and F. Zhang, Sol. Energy Mater. Sol. Cells, 2010, 94, 1963. 38 F. Wurthner and K. Meerholz, Chem.Eur. J., 2010, 16, 9366. 39 Y. He and Y. Li, Phys. Chem. Chem. Phys., 2011, 13, 1970. 40 J. E. Anthony, A. Facchetti, M. Heeney, S. R. Marder and X. Zhan, Adv. Mater., 2010, 22, 3876. 41 J. L. Delgado, P.-A. Bouit, S. Filippone, M. Herranz and N. Mart n, Chem. Commun., 2010, 46, 4853. 42 P. Sonar, J. P. Fong Lim and K. L. Chan, Energy Environ. Sci., 2011, 4, 1558. 43 J. E. Anthony, Chem. Mater., 2011, 23, 583. 44 A. Pivrikas, N. S. Sariciftci, G. Juska and R. Osterbacka, Progr. Photovolt.: Res. Appl., 2007, 15, 677. 45 B. C. Thompson and J. M. J. Frechet, Angew. Chem., Int. Ed., 2008, 47, 58. 46 X. Yang and J. Loos, Macromolecules, 2007, 40, 1353. 47 P. W. M. Blom, V. D. Mihailetchi, L. J. A. Koster and D. E. Markov, Adv. Mater., 2007, 19, 1551. 48 B. Kippelen and J.-L. Bredas, Energy Environ. Sci., 2009, 2, 251. 49 L.-M. Chen, Z. Hong, G. Li and Y. Yang, Adv. Mater., 2009, 21, 1434. 50 G. Dennler, M. C. Scharber and C. J. Brabec, Adv. Mater., 2009, 21, 1323. 51 M. Jrgensen, K. Norrman and F. C. Krebs, Sol. Energy Mater. Sol. Cells, 2008, 92, 686. 52 S. R. Forrest, MRS Bull., 2005, 30, 28. 53 Y. Shirota and H. Kageyama, Chem. Rev., 2007, 107, 953. 54 M. O. Senge, M. Fazekas, E. G. A. Notaras, W. J. Blau, M. Zawadzka, O. B. Locos and E. M. Ni Mhuircheartaigh, Adv. Mater., 2007, 19, 2737. 55 Y. Terao, H. Sasabe and C. Adachi, Appl. Phys. Lett., 2007, 90, 103515. 56 T. Stubinger and W. Brutting, J. Appl. Phys., 2001, 90, 3632. 57 P. Peumans and S. R. Forrest, Appl. Phys. Lett., 2001, 79, 126. 58 J. G. Xue, S. Uchida, B. P. Rand and S. R. Forrest, Appl. Phys. Lett., 2004, 84, 3013. 59 S. Uchida, J. Xue, B. P. Rand and S. R. Forrest, Appl. Phys. Lett., 2004, 84, 4218. 60 J. G. Xue, S. Uchida, B. P. Rand and S. R. Forrest, Appl. Phys. Lett., 2004, 85, 5757.
This journal is
Chem. Soc. Rev., 2012, 41, 42454272
4269
View Online
61 R. F. Bailey-Salzman, B. P. Rand and S. R. Forrest, Appl. Phys. Lett., 2007, 91, 013508. 62 M. Brumbach, D. Placencia and N. R. Armstrong, J. Phys. Chem. C, 2008, 112, 3142. 63 D. Placencia, W. Wang, R. C. Shallcross, K. W. Nebesny, M. Brumbach and N. R. Armstrong, Adv. Funct. Mater., 2009, 19, 1913. 64 K. Petritsch, J. J. Dittmer, E. A. Marseglia, R. H. Friend, A. Lux, G. G. Rozenberg, S. C. Moratti and A. B. Holmes, Sol. Energy Mater. Sol. Cells, 2000, 61, 63. 65 A. Varotto, C.-Y. Nam, I. Radivojevic, J. P. C. Tome, J. A. S. Cavaleiro, C. T. Black and C. M. Drain, J. Am. Chem. Soc., 2010, 132, 2552. 66 C. J. Brabec, A. Cravino, D. Meissner, N. S. Sariciftci, T. Fromherz, M. T. Rispens, L. Sanchez and J. C. Hummelen, Adv. Funct. Mater., 2001, 11, 374. 67 K. L. Mutolo, E. I. Mayo, B. P. Rand, S. R. Forrest and M. E. Thompson, J. Am. Chem. Soc., 2006, 128, 8108. 68 H. Gommans, D. Cheyns, T. Aernouts, C. Girotto, J. Poortmans and P. Heremans, Adv. Funct. Mater., 2007, 17, 2653. 69 B. Ma, C. H. Woo, Y. Miyamoto and J. M. J. Frechet, Chem. Mater., 2009, 21, 1413. 70 B. Verreet, S. Schols, D. Cheyns, B. P. Rand, H. Gommans, T. Aernouts, P. Heremans and J. Genoe, J. Mater. Chem., 2009, 19, 5295. 71 G. Mart n, G. Rojo, F. Agullo-Lopez, V. R. Ferro, J. M. Garc a de la Vega, M. V. Mart nez-D az, T. Torres, I. Ledoux and J. Zyss, J. Phys. Chem. B, 2002, 106, 13139. 72 N. M. Kronenberg, M. Deppisch, F. Wurthner, H. W. A. Lademann, K. Deing and K. Meerholz, Chem. Commun., 2008, 6489. 73 H. Burckstummer, N. M. Kronenberg, M. Gsanger, M. Stolte, K. Meerholz and F. Wurthner, J. Mater. Chem., 2010, 20, 240. 74 N. M. Kronenberg, V. Steinmann, H. Burckstummer, J. Hwang, D. Hertel, F. Wurthner and K. Meerholz, Adv. Mater., 2010, 22, 4193. 75 H. Burckstummer, E. V. Tulyakova, M. Deppisch, M. R. Lenze, N. M. Kronenberg, M. Gsanger, M. Stolte, K. Meerholz and F. Wurthner, Angew. Chem., Int. Ed., 2011, 50, 11628. 76 A. Ojala, H. Burckstummer, M. Stolte, R. Sens, H. Reichelt, P. Erk, J. Hwang, D. Hertel, K. Meerholz and F. Wurthner, Adv. Mater., 2011, 23, 5398. 77 V. Steinmann, N. M. Kronenberg, M. R. Lenze, S. M. Graf, D. Hertel, H. Burckstuemmer, F. Wurthner and K. Meerholz, Appl. Phys. Lett., 2011, 99, 193306. 78 A. Ojala, A. Petersen, A. Fuchs, R. Lovrincic, C. Polking, J. Trollmann, J. Hwang, C. Lennartz, H. Reichelt, H. W. Hoken, A. Pucci, P. Erk, T. Kirchartz and F. Wurthner, Adv. Funct. Mater., 2012, 22, 86. 79 F. Silvestri, M. D. Irwin, L. Beverina, A. Facchetti, G. A. Pagani and T. J. Marks, J. Am. Chem. Soc., 2008, 130, 17640. 80 D. Bagnis, L. Beverina, H. Huang, F. Silvestri, Y. Yao, H. Yan, G. A. Pagani, T. J. Marks and A. Facchetti, J. Am. Chem. Soc., 2010, 132, 4074. 81 U. Mayerhoer, K. Deing, K. Gru, H. Braunschweig, K. Meerholz and F. Wurthner, Angew. Chem., Int. Ed., 2009, 48, 8776. 82 S. Wang, E. I. Mayo, M. D. Perez, L. Grie, G. Wei, P. I. Djurovich, S. R. Forrest and M. E. Thompson, Appl. Phys. Lett., 2009, 94, 233304. 83 G. Wei, S. Wang, K. Renshaw, M. E. Thompson and S. R. Forrest, ACS Nano, 2010, 4, 1927. 84 G. Wei, S. Wang, K. Sun, M. E. Thompson and S. R. Forrest, Adv. Energy Mater., 2011, 1, 184. 85 S. Wang, L. Hall, V. V. Diev, R. Haiges, G. Wei, X. Xiao, P. I. Djurovich, S. R. Forrest and M. E. Thompson, Chem. Mater., 2011, 23, 4789. 86 G. Wei, X. Xiao, S. Wang, J. D. Zimmerman, K. Sun, V. V. Diev, M. E. Thompson and S. R. Forrest, Nano Lett., 2011, 11, 4261. 87 K. Y. Law, J. Phys. Chem., 1987, 91, 5184. 88 T. Rousseau, A. Cravino, T. Bura, G. Ulrich, R. Ziessel and J. Roncali, Chem. Commun., 2009, 1673. 89 T. Rousseau, A. Cravino, T. Bura, G. Ulrich, R. Ziessel and J. Roncali, J. Mater. Chem., 2009, 19, 2298. 90 T. Rousseau, A. Cravino, E. Ripaud, P. Leriche, S. Rihn, A. De Nicola, R. Ziessel and J. Roncali, Chem. Commun., 2010, 46, 5082. 91 A. B. Tamayo, B. Walker and T. Q. Nguyen, J. Phys. Chem. C, 2008, 112, 11545. 92 A. B. Tamayo, X. D. Dang, B. Walker, J. Seo, T. Kent and T. Q. Nguyen, Appl. Phys. Lett., 2009, 94, 103301. 93 B. Walker, A. B. Tamayo, X.-D. Dang, P. Zalar, J. H. Seo, A. Garcia, M. Tantiwiwat and T.-Q. Nguyen, Adv. Funct. Mater., 2009, 19, 3063. 94 K. A. Mazzio, M. Yuan, K. Okamoto and C. K. Luscombe, ACS Appl. Mater. Interfaces, 2011, 3, 271. 95 O. P. Lee, A. T. Yiu, P. M. Beaujuge, C. H. Woo, T. W. Holcombe, J. E. Millstone, J. D. Douglas, M. S. Chen and J. M. J. Frechet, Adv. Mater., 2011, 23, 5359. 96 S. Loser, C. J. Bruns, H. Miyauchi, R. o. P. Ortiz, A. Facchetti, S. I. Stupp and T. J. Marks, J. Am. Chem. Soc., 2011, 133, 8142. 97 J. G. Mei, K. R. Graham, R. Stalder and J. R. Reynolds, Org. Lett., 2010, 12, 660. 98 K. R. Graham, J. Mei, R. Stalder, J. W. Shim, H. Cheun, F. Stey, F. So, B. Kippelen and J. R. Reynolds, ACS Appl. Mater. Interfaces, 2011, 3, 1210. 99 H. Choi, S. Paek, J. Song, C. Kim, N. Cho and J. Ko, Chem. Commun., 2011, 47, 5509. 100 J. J.-A. Chen, T. L. Chen, B. Kim, D. A. Poulsen, J. L. Mynar, J. M. J. Frechet and B. Ma, ACS Appl. Mater. Interfaces, 2010, 2, 2679. 101 W. P. Wu, Y. Q. Liu and D. B. Zhu, Chem. Soc. Rev., 2010, 39, 1489. 102 J. E. Anthony, Chem. Rev., 2006, 106, 5028. 103 S. Yoo, B. Domercq and B. Kippelen, Appl. Phys. Lett., 2004, 85, 5427. 104 C. W. Chu, Y. Shao, V. Shrotriya and Y. Yang, Appl. Phys. Lett., 2005, 86, 243506. 105 M. T. Lloyd, A. C. Mayer, A. S. Tayi, A. M. Bowen, T. G. Kasen, D. J. Herman, D. A. Mourey, J. E. Anthony and G. G. Malliaras, Org. Electron., 2006, 7, 243. 106 J. E. Anthony, D. L. Eaton and S. R. Parkin, Org. Lett., 2002, 4, 15. 107 M. T. Lloyd, A. C. Mayer, S. Subramanian, D. A. Mourey, D. J. Herman, A. V. Bapat, J. E. Anthony and G. G. Malliaras, J. Am. Chem. Soc., 2007, 129, 9144. 108 V. S. Barlier, C. W. Schlenker, S. W. Chin and M. E. Thompson, Chem. Commun., 2011, 47, 3754. 109 L. Valentini, D. Bagnis, A. Marrocchi, M. Seri, A. Taticchi and J. M. Kenny, Chem. Mater., 2008, 20, 32. 110 A. Marrocchi, F. Silvestri, M. Seri, A. Facchetti, A. Taticchi and T. J. Marks, Chem. Commun., 2009, 1380. 111 F. Silvestri, A. Marrocchi, M. Seri, C. Kim, T. J. Marks, A. Facchetti and A. Taticchi, J. Am. Chem. Soc., 2010, 132, 6108. 112 D. S. Chung, J. W. Park, W. M. Yun, H. Cha, Y.-H. Kim, S.-K. Kwon and C. E. Park, ChemSusChem, 2010, 3, 742. 113 K. N. Winzenberg, P. Kemppinen, G. Fanchini, M. Bown, G. E. Collis, C. M. Forsyth, K. Hegedus, T. B. Singh and S. E. Watkins, Chem. Mater., 2009, 21, 5701. 114 L. Zhang, B. Walker, F. Liu, N. S. Colella, S. C. B. Mannsfeld, J. J. Watkins, T.-Q. Nguyen and A. L. Briseno, J. Mater. Chem., 2012, 22, 4266. 115 L. Schmidt-Mende, A. Fechtenkotter, K. Mullen, E. Moons, R. H. Friend and J. D. MacKenzie, Science, 2001, 293, 1119. 116 W. W. H. Wong, T. B. Singh, D. Vak, W. Pisula, C. Yan, X. Feng, E. L. Williams, K. L. Chan, Q. Mao, D. J. Jones, C.-Q. Ma, K. Mullen, P. Bauerle and A. B. Holmes, Adv. Funct. Mater., 2010, 20, 927. 117 W. W. H. Wong, C.-Q. Ma, W. Pisula, C. Yan, X. Feng, D. J. Jones, K. Mullen, R. A. J. Janssen, P. Bauerle and A. B. Holmes, Chem. Mater., 2010, 22, 457. 118 F. Zhang, D. Wu, Y. Xu and X. Feng, J. Mater. Chem., 2011, 21, 17590. 119 J. Sakai, T. Taima, T. Yamanari and K. Saito, Sol. Energy Mater. Sol. Cells, 2009, 93, 1149. 120 K. Schulze, C. Uhrich, R. Schuppel, K. Leo, M. Pfeier, E. Brier, E. Reinold and P. Bauerle, Adv. Mater., 2006, 18, 2872. 121 K. Schulze, M. Riede, E. Brier, E. Reinold, P. Bauerle and K. Leo, J. Appl. Phys., 2008, 104, 074511. 122 A. Mishra, C. Uhrich, E. Reinold, M. Pfeier and P. Bauerle, Adv. Energy Mater., 2011, 1, 265. 123 S. Haid, A. Mishra, C. Uhrich, M. Pfeier and P. Bauerle, Chem. Mater., 2011, 23, 4435.
4270
Chem. Soc. Rev., 2012, 41, 42454272
This journal is
View Online
124 R. Fitzner, E. Reinold, A. Mishra, E. Mena-Osteritz, H. Ziehlke, C. Korner, K. Leo, M. Riede, M. Weil, O. Tsaryova, A. Wei, C. Uhrich, M. Pfeier and P. Bauerle, Adv. Funct. Mater., 2011, 21, 897. 125 Y. Liu, X. Wan, B. Yin, J. Zhou, G. Long, S. Yin and Y. Chen, J. Mater. Chem., 2010, 20, 2464. 126 B. Yin, L. Yang, Y. Liu, Y. Chen, Q. Qi, F. Zhang and S. Yin, Appl. Phys. Lett., 2010, 97, 023303. 127 Y. Liu, X. Wan, F. Wang, J. Zhou, G. Long, J. Tian, J. You, Y. Yang and Y. Chen, Adv. Energy Mater., 2011, 1, 771. 128 Y. Liu, X. Wan, F. Wang, J. Zhou, G. Long, J. Tian and Y. Chen, Adv. Mater., 2011, 23, 5387. 129 J. Zhou, X. Wan, Y. Liu, G. Long, F. Wang, Z. Li, Y. Zuo, C. Li and Y. Chen, Chem. Mater., 2011, 23, 4666. 130 D. Demeter, T. Rousseau, P. Leriche, T. Cauchy, R. Po and J. Roncali, Adv. Funct. Mater., 2011, 21, 4379. 131 J. Ah Kong, E. Lim, K. K. Lee, S. Lee and S. Hyun Kim, Sol. Energy Mater. Sol. Cells, 2010, 94, 2057. 132 S. Steinberger, A. Mishra, E. Reinold, C. M. Muller, C. Uhrich, M. Pfeier and P. Bauerle, Org. Lett., 2010, 13, 90. 133 S. Steinberger, A. Mishra, E. Reinold, J. Levichkov, C. Uhrich, M. Pfeier and P. Bauerle, Chem. Commun., 2011, 47, 1982. 134 X. Zhao, C. Piliego, B. Kim, D. A. Poulsen, B. Ma, D. A. Unruh and J. M. J. Frechet, Chem. Mater., 2010, 22, 2325. 135 G. C. Welch, L. A. Perez, C. V. Hoven, Y. Zhang, X.-D. Dang, A. Sharenko, M. F. Toney, E. J. Kramer, T.-Q. Nguyen and G. C. Bazan, J. Mater. Chem., 2011, 21, 12700. 136 X. Sun, Y. Zhou, W. Wu, Y. Liu, W. Tian, G. Yu, W. Qiu, S. Chen and D. Zhu, J. Phys. Chem. B, 2006, 110, 7702. 137 H. Shang, H. Fan, Y. Liu, W. Hu, Y. Li and X. Zhan, J. Mater. Chem., 2011, 21, 9667. 138 N. Kopidakis, W. J. Mitchell, J. van de Lagemaat, D. S. Ginley, G. Rumbles, S. E. Shaheen and W. L. Rance, Appl. Phys. Lett., 2006, 89, 103524. 139 J. Roncali, P. Frere, P. Blanchard, R. de Bettignies, M. Turbiez, S. Roquet, P. Leriche and Y. Nicolas, Thin Solid Films, 2006, 511, 567. 140 W. L. Rance, B. L. Rupert, W. J. Mitchell, M. E. Kose, D. S. Ginley, S. E. Shaheen, G. Rumbles and N. Kopidakis, J. Phys. Chem. C, 2010, 114, 22269. 141 M. E. Kose, W. J. Mitchell, N. Kopidakis, C. H. Chang, S. E. Shaheen, K. Kim and G. Rumbles, J. Am. Chem. Soc., 2007, 129, 14257. 142 P. F. Xia, X. J. Feng, J. Lu, S.-W. Tsang, R. Movileanu, Y. Tao and M. S. Wong, Adv. Mater., 2008, 20, 4810. 143 W. Zhang, S. C. Tse, J. Lu, Y. Tao and M. S. Wong, J. Mater. Chem., 2010, 20, 2182. 144 H. M. Ko, H. Choi, S. Paek, K. Kim, K. Song, J. K. Lee and J. Ko, J. Mater. Chem., 2011, 21, 7248. 145 W. Zhang, G. M. Ng, H. L. Tam, M. S. Wong and F. Zhu, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 1865. 146 C.-Q. Ma, E. Mena-Osteritz, T. Debaerdemaeker, M. M. Wienk, R. A. J. Janssen and P. Bauerle, Angew. Chem., Int. Ed., 2007, 46, 1679. 147 C.-Q. Ma, M. Fonrodona, M. C. Schikora, M. M. Wienk, R. A. J. Janssen and P. Bauerle, Adv. Funct. Mater., 2008, 18, 3323. 148 S. Roquet, R. de Bettignies, P. Leriche, A. Cravino and J. Roncali, J. Mater. Chem., 2006, 16, 3040. ` 149 S. Karpe, A. Cravino, P. Frere, M. Allain, G. Mabon and J. Roncali, Adv. Funct. Mater., 2007, 17, 1163. 150 Z. Ning and H. Tian, Chem. Commun., 2009, 5483. 151 C. He, Q. He, Y. He, Y. Li, F. Bai, C. Yang, Y. Ding, L. Wang and J. Ye, Sol. Energy Mater. Sol. Cells, 2006, 90, 1815. 152 D. Deng, Y. Yang, J. Zhang, C. He, M. Zhang, Z.-G. Zhang, Z. Zhang and Y. Li, Org. Electron., 2011, 12, 614. 153 H. Shang, H. Fan, Q. Shi, S. Li, Y. Li and X. Zhan, Sol. Energy Mater. Sol. Cells, 2010, 94, 457. 154 H. Fan, H. Shang, Y. Li and X. Zhan, Appl. Phys. Lett., 2010, 97, 133302. 155 Q. Shi, P. Cheng, Y. Li and X. Zhan, Adv. Energy Mater., 2012, 2, 63. 156 W. Li, C. Du, F. Li, Y. Zhou, M. Fahlman, Z. Bo and F. Zhang, Chem. Mater., 2009, 21, 5327. 157 C. He, Q. He, X. Yang, G. Wu, C. Yang, F. Bai, Z. Shuai, L. Wang and Y. Li, J. Phys. Chem. C, 2007, 111, 8661. 158 L. Xue, J. He, X. Gu, Z. Yang, B. Xu and W. Tian, J. Phys. Chem. C, 2009, 113, 12911. 159 J. Zhang, G. Wu, C. He, D. Deng and Y. Li, J. Mater. Chem., 2011, 21, 3768. 160 A. Leliege, P. Blanchard, T. o. Rousseau and J. Roncali, Org. Lett., 2011, 13, 3098. 161 H.-W. Lin, L.-Y. Lin, Y.-H. Chen, C.-W. Chen, Y.-T. Lin, S.-W. Chiu and K.-T. Wong, Chem. Commun., 2011, 47, 7872. 162 L.-Y. Lin, Y.-H. Chen, Z.-Y. Huang, H.-W. Lin, S.-H. Chou, F. Lin, C.-W. Chen, Y.-H. Liu and K.-T. Wong, J. Am. Chem. Soc., 2011, 133, 15822. 163 Q. Liu, K. Jiang, B. Guan, Z. Tang, J. Pei and Y. Song, Chem. Commun., 2011, 47, 740. 164 Z.-M. Tang, T. Lei, K.-J. Jiang, Y.-L. Song and J. Pei, Chem.Asian J., 2010, 5, 1911. 165 S. Roquet, A. Cravino, P. Leriche, O. Aleveque, P. Frere and J. Roncali, J. Am. Chem. Soc., 2006, 128, 3459. 166 A. Cravino, S. Roquet, P. Leriche, O. Aleveque, P. Frere and J. Roncali, Chem. Commun., 2006, 1416. 167 A. Cravino, P. Leriche, O. Aleveque, S. Roquet and J. Roncali, Adv. Mater., 2006, 18, 3033. 168 A. Cravino, S. Roquet, O. Aleveque, P. Leriche, P. Frere and J. Roncali, Chem. Mater., 2006, 18, 2584. 169 E. Ripaud, T. Rousseau, P. Leriche and J. Roncali, Adv. Energy Mater., 2011, 1, 540. 170 H. Shang, H. Fan, Y. Liu, W. Hu, Y. Li and X. Zhan, Adv. Mater., 2011, 23, 1554. 171 J. Zhang, D. Deng, C. He, Y. He, M. Zhang, Z.-G. Zhang, Z. Zhang and Y. Li, Chem. Mater., 2011, 23, 817. 172 G. Wu, G. Zhao, C. He, J. Zhang, Q. He, X. Chen and Y. Li, Sol. Energy Mater. Sol. Cells, 2009, 93, 108. 173 C. He, Q. He, Y. Yi, G. Wu, F. Bai, Z. Shuai and Y. Li, J. Mater. Chem., 2008, 18, 4085. 174 J. Zhang, Y. Yang, C. He, Y. He, G. Zhao and Y. Li, Macromolecules, 2009, 42, 7619. 175 H. W. Kroto, J. R. Heath, S. C. Obrien, R. F. Curl and R. E. Smalley, Nature, 1985, 318, 162. 176 S. Pfuetzner, J. Meiss, A. Petrich, M. Riede and K. Leo, Appl. Phys. Lett., 2009, 94, 223307. 177 J. C. Hummelen, B. W. Knight, F. Lepeq and F. Wudl, J. Org. Chem., 1995, 60, 532. 178 M. M. Wienk, J. M. Kroon, W. J. H. Verhees, J. Knol, J. C. Hummelen, P. A. van Hal and R. A. J. Janssen, Angew. Chem., Int. Ed., 2003, 42, 3371. 179 M.-S. Su, C.-Y. Kuo, M.-C. Yuan, U. S. Jeng, C.-J. Su and K.-H. Wei, Adv. Mater., 2011, 23, 3315. 180 C. M. Amb, S. Chen, K. R. Graham, J. Subbiah, C. E. Small, F. So and J. R. Reynolds, J. Am. Chem. Soc., 2011, 133, 10062. 181 S. C. Price, A. C. Stuart, L. Yang, H. Zhou and W. You, J. Am. Chem. Soc., 2011, 133, 4625. 182 L. Huo, S. Zhang, X. Guo, F. Xu, Y. Li and J. Hou, Angew. Chem., Int. Ed., 2011, 50, 9697. 183 H. Zhou, L. Yang, A. C. Stuart, S. C. Price, S. Liu and W. You, Angew. Chem., Int. Ed., 2011, 50, 2995. 184 T.-Y. Chu, J. Lu, S. Beaupre, Y. Zhang, J.-R. m. Pouliot, S. Wakim, J. Zhou, M. Leclerc, Z. Li, J. Ding and Y. Tao, J. Am. Chem. Soc., 2011, 133, 4250. 185 H. Y. Chen, J. H. Hou, S. Q. Zhang, Y. Y. Liang, G. W. Yang, Y. Yang, L. P. Yu, Y. Wu and G. Li, Nat. Photonics, 2009, 3, 649653. 186 J. H. Choi, K.-I. Son, T. Kim, K. Kim, K. Ohkubo and S. Fukuzumi, J. Mater. Chem., 2010, 20, 475. 187 Y. Zhang, H.-L. Yip, O. Acton, S. K. Hau, F. Huang and A. K. Y. Jen, Chem. Mater., 2009, 21, 2598. 188 M. Lenes, G.-J. A. H. Wetzelaer, F. B. Kooistra, S. C. Veenstra, J. C. Hummelen and P. W. M. Blom, Adv. Mater., 2008, 20, 2116. 189 Y. He, H.-Y. Chen, J. Hou and Y. Li, J. Am. Chem. Soc., 2010, 132, 1377. 190 G. Zhao, Y. He and Y. Li, Adv. Mater., 2010, 22, 4355. 191 Y. He, G. Zhao, B. Peng and Y. Li, Adv. Funct. Mater., 2010, 20, 3383. 192 Y. Sun, C. Cui, H. Wang and Y. Li, Adv. Energy Mater., 2011, 1, 1058. 193 Y.-J. Cheng, M.-H. Liao, C.-Y. Chang, W.-S. Kao, C.-E. Wu and C.-S. Hsu, Chem. Mater., 2011, 23, 4056.
This journal is
Chem. Soc. Rev., 2012, 41, 42454272
4271
View Online
194 E. Voroshazi, K. Vasseur, T. Aernouts, P. Heremans, A. Baumann, C. Deibel, X. Xue, A. J. Herring, A. J. Athans, T. A. Lada, H. Richter and B. P. Rand, J. Mater. Chem., 2011, 21, 17345. 195 K.-H. Kim, H. Kang, S. Y. Nam, J. Jung, P. S. Kim, C.-H. Cho, C. Lee, S. C. Yoon and B. J. Kim, Chem. Mater., 2011, 23, 5090. 196 X. Meng, W. Zhang, Z. a. Tan, C. Du, C. Li, Z. Bo, Y. Li, X. Yang, M. Zhen, F. Jiang, J. Zheng, T. Wang, L. Jiang, C. Shu and C. Wang, Chem. Commun., 2012, 48, 425. 197 J. M. Campanera, C. Bo, M. M. Olmstead, A. L. Balch and J. M. Poblet, J. Phys. Chem. A, 2002, 106, 12356. 198 C. M. Cardona, B. Elliott and L. Echegoyen, J. Am. Chem. Soc., 2006, 128, 6480. 199 R. B. Ross, C. M. Cardona, D. M. Guldi, S. G. Sankaranarayanan, M. O. Reese, N. Kopidakis, J. Peet, B. Walker, G. C. Bazan, E. Van Keuren, B. C. Holloway and M. Drees, Nat. Mater., 2009, 8, 208. 200 Y. Matsuo, Y. Sato, T. Niinomi, I. Soga, H. Tanaka and E. Nakamura, J. Am. Chem. Soc., 2009, 131, 16048. 201 J. A. Mikroyannidis, A. N. Kabanakis, S. S. Sharma and G. D. Sharma, Adv. Funct. Mater., 2011, 21, 746. 202 S. A. Backer, K. Sivula, D. F. Kavulak and J. M. J. Frechet, Chem. Mater., 2007, 19, 2927. 203 X. Zhan, A. Facchetti, S. Barlow, T. J. Marks, M. A. Ratner, M. R. Wasielewski and S. R. Marder, Adv. Mater., 2011, 23, 268. 204 F. Wurthner, Chem. Commun., 2004, 1564. 205 F. Wurthner and M. Stolte, Chem. Commun., 2011, 47, 5109. 206 S. V. Bhosale, C. H. Jani and S. J. Langford, Chem. Soc. Rev., 2008, 37, 331. 207 S. Erten, F. Meghdadi, S. Gunes, R. Koeppe, N. S. Sariciftci and S. Icli, Eur. Phys. J.: Appl. Phys., 2006, 36, 225. 208 S. B. Rim, R. F. Fink, J. C. Schoneboom, P. Erk and P. Peumans, Appl. Phys. Lett., 2007, 91, 173504. 209 X. Y. Guo, L. J. Bu, Y. Zhao, Z. Y. Xie, Y. H. Geng and L. X. Wang, Thin Solid Films, 2009, 517, 4654. 210 J. L. Li, F. Dierschke, J. S. Wu, A. C. Grimsdale and K. Mullen, J. Mater. Chem., 2006, 16, 96. 211 W. S. Shin, H.-H. Jeong, M.-K. Kim, S.-H. Jin, M.-R. Kim, J.-K. Lee, J. W. Lee and Y.-S. Gal, J. Mater. Chem., 2006, 16, 384. 212 V. Kamm, G. Battagliarin, I. A. Howard, W. Pisula, A. Mavrinskiy, C. Li, K. Mullen and F. Laquai, Adv. Energy Mater., 2011, 1, 297. 213 G. D. Sharma, P. Balraju, J. A. Mikroyannidis and M. M. Stylianakis, Sol. Energy Mater. Sol. Cells, 2009, 93, 2025. 214 G. D. Sharma, P. Suresh, J. A. Mikroyannidis and M. M. Stylianakis, J. Mater. Chem., 2010, 20, 561. 215 J. A. Mikroyannidis, P. Suresh and G. D. Sharma, Synth. Met., 2010, 160, 932. 216 S. Erten and S. Icli, Inorg. Chim. Acta, 2008, 361, 595. 217 G. Ren, E. Ahmed and S. A. Jenekhe, Adv. Energy Mater., 2011, 1, 946. 218 E. Ahmed, G. Ren, F. S. Kim, E. C. Hollenbeck and S. A. Jenekhe, Chem. Mater., 2011, 23, 4563. 219 M. L. Tang, J. H. Oh, A. D. Reichardt and Z. Bao, J. Am. Chem. Soc., 2009, 131, 3733. 220 Z. Bao, A. J. Lovinger and J. Brown, J. Am. Chem. Soc., 1998, 120, 207. 221 S. P. Singh, A. Sellinger and A. Dodabalapur, J. Appl. Phys., 2010, 107, 044509. 222 X. Jiang, J. Dai, H. Wang, Y. Geng and D. Yan, Chem. Phys. Lett., 2007, 446, 329. 223 J. L. Yang, S. Schumann, R. A. Hatton and T. S. Jones, Org. Electron., 2010, 11, 1399. 224 H. Gommans, T. Aernouts, B. Verreet, P. Heremans, A. Medina, C. G. Claessens and T. Torres, Adv. Funct. Mater., 2009, 19, 3435. 225 P. Sullivan, A. Duraud, l. Hancox, N. Beaumont, G. Mirri, J. H. R. Tucker, R. A. Hatton, M. Shipman and T. S. Jones, Adv. Energy Mater., 2011, 1, 352. 226 B. Verreet, B. P. Rand, D. Cheyns, A. Hadipour, T. Aernouts, P. Heremans, A. Medina, C. G. Claessens and T. Torres, Adv. Energy Mater., 2011, 1, 565. 227 Y.-F. Lim, Y. Shu, S. R. Parkin, J. E. Anthony and G. G. Malliaras, J. Mater. Chem., 2009, 19, 3049. 228 Y. Shu, Y.-F. Lim, Z. Li, B. Purushothaman, R. Hallani, J. E. Kim, S. R. Parkin, G. G. Malliaras and J. E. Anthony, Chem. Sci., 2011, 2, 363. 229 Z. Li, Y.-F. Lim, J. B. Kim, S. R. Parkin, Y.-L. Loo, G. G. Malliaras and J. E. Anthony, Chem. Commun., 2011, 47, 7617. 230 G. Barbarella, O. Pudova, C. Arbizzani, M. Mastragostino and A. Bongini, J. Org. Chem., 1998, 63, 1742. 231 G. Barbarella, L. Favaretto, G. Sotgiu, M. Zambianchi, L. Antolini, O. Pudova and A. Bongini, J. Org. Chem., 1998, 63, 5497. 232 N. Camaioni, G. Ridol, V. Fattori, L. Favaretto and G. Barbarella, Appl. Phys. Lett., 2004, 84, 1901. 233 N. Camaioni, G. Ridol, V. Fattori, L. Favaretto and G. Barbarella, J. Mater. Chem., 2005, 15, 2220. 234 G. Barbarella, L. Favaretto, A. Zanelli, G. Gigli, M. Mazzeo, M. Anni and A. Bongini, Adv. Funct. Mater., 2005, 15, 664. 235 Y. Zhou, J. Pei, Q. Dong, X. Sun, Y. Liu and W. Tian, J. Phys. Chem. C, 2009, 113, 7882. 236 T. Zhou, T. Jia, B. Kang, F. Li, M. Fahlman and Y. Wang, Adv. Energy Mater., 2011, 1, 431. 237 P. E. Schwenn, K. Gui, A. M. Nardes, K. B. Krueger, K. H. Lee, K. Mutkins, H. Rubinstein-Dunlop, P. E. Shaw, N. Kopidakis, P. L. Burn and P. Meredith, Adv. Energy Mater., 2011, 1, 73. 238 R. Y. C. Shin, T. Kietzke, S. Sudhakar, A. Dodabalapur, Z.-K. Chen and A. Sellinger, Chem. Mater., 2007, 19, 1892. 239 R. Y. C. Shin, P. Sonar, P. S. Siew, Z.-K. Chen and A. Sellinger, J. Org. Chem., 2009, 74, 3293. 240 T. Kietzke, R. Y. C. Shin, D. A. M. Egbe, Z.-K. Chen and A. Sellinger, Macromolecules, 2007, 40, 4424. 241 C. H. Woo, T. W. Holcombe, D. A. Unruh, A. Sellinger and J. M. J. Frechet, Chem. Mater., 2010, 22, 1673. 242 M. Schubert, C. H. Yin, M. Castellani, S. Bange, T. L. Tam, A. Sellinger, H. H. Horhold, T. Kietzke and D. Neher, J. Chem. Phys., 2009, 130, 094703. 243 Z. E. Ooi, T. L. Tam, R. Y. C. Shin, Z. K. Chen, T. Kietzke, A. Sellinger, M. Baumgarten, K. Mullen and J. C. deMello, J. Mater. Chem., 2008, 18, 4619. 244 J. T. Bloking, X. Han, A. T. Higgs, J. P. Kastrop, L. Pandey, J. E. Norton, C. Risko, C. E. Chen, J.-L. Bredas, M. D. McGehee and A. Sellinger, Chem. Mater., 2011, 23, 5484. 245 P. Sonar, G.-M. Ng, T. T. Lin, A. Dodabalapur and Z.-K. Chen, J. Mater. Chem., 2010, 20, 3626. 246 B. P. Karsten, J. C. Bijleveld and R. A. J. Janssen, Macromol. Rapid Commun., 2010, 31, 1554. 247 Y. Zhou, L. Ding, K. Shi, Y.-Z. Dai, N. Ai, J. Wang and J. Pei, Adv. Mater., 2012, 24, 957. 248 F. G. Brunetti, X. Gong, M. Tong, A. J. Heeger and F. Wudl, Angew. Chem., Int. Ed., 2010, 49, 532. 249 X. Gong, M. Tong, F. G. Brunetti, J. Seo, Y. Sun, D. Moses, F. Wudl and A. J. Heeger, Adv. Mater., 2011, 23, 2272. 250 J. Roncali, Adv. Energy Mater., 2011, 1, 147. 251 T. Nishizawa, H. K. Lim, K. Tajima and K. Hashimoto, Chem. Commun., 2009, 2469. 252 S. Izawa, K. Hashimoto and K. Tajima, Chem. Commun., 2011, 47, 6365. 253 L. Bu, X. Guo, B. Yu, Y. Qu, Z. Xie, D. Yan, Y. Geng and F. Wang, J. Am. Chem. Soc., 2009, 131, 13242.
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Chemical Society Reviews

Volume 41 | Number 11 | 7 June 2012 | Pages 40894380

Chem Soc Rev

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Small molecule semiconductors for high-eciency organic photovoltaics

The Royal Society of Chemistry 2012

The Royal Society of Chemistry 2012

Small molecular donors

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755 850 590 688 1.7

a8 607 a9 649 a10 616

a11 a12 a13 a14 a15

595 760 770 820 700

1.95 1.70 1.70 2.01 1.7 1.73 1.72 1.67 1.94

5.40/3.68 5.5/3.9 (S, B) 5.27/3.54 (S, N) 5.55/3.42

The Royal Society of Chemistry 2012

Fig. 2 Chemical structure of dye-based donors.

The Royal Society of Chemistry 2012

Chem. Soc. Rev., 2012, 41, 42454272

The Royal Society of Chemistry 2012

The Royal Society of Chemistry 2012

0.11 (O, N) 0.07 (O, N) 104105 (S, B)

Chem. Soc. Rev., 2012, 41, 42454272

The Royal Society of Chemistry 2012

Chemical structure of fused acene donors.

The Royal Society of Chemistry 2012

Chem. Soc. Rev., 2012, 41, 42454272

The Royal Society of Chemistry 2012

Chemical structure of oligothiophene donors.

The Royal Society of Chemistry 2012

Chem. Soc. Rev., 2012, 41, 42454272

The Royal Society of Chemistry 2012

The Royal Society of Chemistry 2012

538 563 585 486 541 529

4.7 105 (S, N)

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Chemical structure of triphenylamine-based donors.

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Chem. Soc. Rev., 2012, 41, 42454272

Small molecular acceptors

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Fig. 6 Chemical structure of fullerene derivative acceptors.

The Royal Society of Chemistry 2012

The Royal Society of Chemistry 2012

lmaxa/nm f1 f2 f3 530 f4 542 f5 f6 f7 f8 455 f9 f10

2.13 8.8 104 5.6 104 4.6 104

5.8/3.8 5.82/3.69 6.0/3.85 5.9/3.8 5.90/3.95 5.78/3.87 5.5/4.1

0.45 0.36 0.75 0.88 0.95 0.90 0.50 0.82

0.34 0.38 0.38 0.47 0.53 0.52 0.51 0.52

Donor/acceptor: bilayer by vacuum deposition; donor:acceptor:

Fig. 7 Chemical structure of rylene diimide acceptors.

The Royal Society of Chemistry 2012

1.8 2.40 2.34 1.81 1.81 2.18

580 410 517

Donor/acceptor: bilayer by vacuum deposition;

Chem. Soc. Rev., 2012, 41, 42454272

The Royal Society of Chemistry 2012

Fig. 8 Chemical structure of other nonfullerene acceptors.

The Royal Society of Chemistry 2012

The Royal Society of Chemistry 2012

Donoracceptor dyad molecules for single-component OPVs