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Polymer Reviews
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Development of Semiconducting Polymers for Solar Energy Harvesting

Yongye Liang & Luping Yu
a a a

Department of Chemistry and James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, IL, 60637 Version of record first published: 06 Nov 2010

To cite this article: Yongye Liang & Luping Yu (2010): Development of Semiconducting Polymers for Solar Energy Harvesting, Polymer Reviews, 50:4, 454-473 To link to this article: http://dx.doi.org/10.1080/15583724.2010.515765

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Polymer Reviews, 50:454473, 2010 Copyright Taylor & Francis Group, LLC ISSN: 1558-3724 print / 1558-3716 online DOI: 10.1080/15583724.2010.515765

Development of Semiconducting Polymers for Solar Energy Harvesting

YONGYE LIANG AND LUPING YU
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Department of Chemistry and James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, IL 60637
Semiconducting polymer solar cells are an attracting class of devices for low-cost solar energy harvesting. The bulk hetero-junction structure based on composite materials of semiconducting polymer donor and fullerene acceptor is an effective form of active layers for polymer solar cells. So far, the limiting factors for widespread, practical applications in polymers solar cell is their low power conversion efciency (PCE) and potential instability under light exposure. Thus new polymeric materials with desired properties and stability are crucial for improving the solar cell performance. Numerous conjugated polymers, such as poly[phenylene vinylene]s (PPVs) and polythiophenes, have been explored for this purpose, which lead to PCE as high as 5%. To improve the performance, low bandgap polymers and polymers with low lying HOMO energy levels have been the subject of recent focus. Efciencies close to 8% have been achieved in the polymer system composed of thieno[3,4-b]thiophene and benzodithiophene alternating units (PTB). The high efciency is due to the synergistic combinations of desired properties in the polymer system through detailed ne-tuning of the polymer structure. The recent results reafrmed the notion that better solar cell polymers could be further developed for vital applications in real devices. Keywords semiconducting polymer, solar cell, bulk hetero-junction, ne-tuning

1. Introduction
In the recognition of energy demand increase and fossil fuel depletion, as well as the environmental pollution from fuel combustion, the search and utilization of clean and renewable energies is becoming one of the greatest challenges for our society. Solar energy is the largest renewable energy source, which can potentially provide about 124 PW (PW = 1015 Watts) energy globally, more than 8000 times of the total worldwide energy consumption in 2004 (15 TW, 1TW = 1012 Watts).1 The direct conversion of solar radiation into electricity, called photovoltaic, is a simple and clean way to harness such a vast energy source. The photovoltaic effect requires active semiconducting materials, and currently inorganic solar cell based on silicon is the dominant technology. It exhibits good performance in PCE and lifetime. However, the high production and installation cost of silicon solar cells limits its widespread use to provide a large fraction of our electricity.2,3 New photovoltaic (PV)

Received May 7, 2010; accepted August 5, 2010. Address correspondence to Professor Luping Yu, 929 E 57th Street, Chicago, IL 60637, USA. E-mail: lupingyu@uchicago.edu

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systems exhibiting low cost and high efciency for solar energy conversion are actively pursued worldwide.4 An alternative material is the semiconducting polymers. Solar cells based on organic semiconductors enjoy several unique advantages compared to their inorganic counterparts.5 First of all, polymer semiconductors are soluble in organic solvents and the composite active layer of solar cells can be fabricated from solution in a single step by a variety of simple techniques such as spin coating, inkjet printing, and roller casting, and all are cost-effective and easier than the inorganic ones. The physical properties of organic solar cells, such as absorption spectrum and charge transport property, can be tailored by chemical synthesis. Meanwhile, the thickness of active layer can be very thin (about 100 nm) due to their high absorption coefcient within their absorption range so that organic solar cell can be semitransparent and the color can be tuned. Furthermore, the lightweight and mechanical exibility of polymer materials enable some specic application of organic solar cells, such as in portable devices. The donor/acceptor concept pioneered by Tang in 19866 and bulk-heterojunction (BHJ) developed by Yu et al. in 19957 led to the active pursuit of polymer solar cells. The solution processed BHJ solar cells are easy to prepare and present a high density of heterojunction interfaces that enables the efcient exciton dissociation and charge generation over the whole active layer, which favors high PCE. These two advantages establish the solution processed BHJ solar cells as the most promising technology for organic solar cells. Gradual progress in the solar cell performance is underway based on this architecture. PCE evolved from 1% in 1995, to 5% in 2005 and close to 8% most recently.8 Despite the envisioned advantages and recent technology advances, so far polymer solar cells are still inferior to inorganic counterparts in terms of PCE and life times.9 Solar cells with PCE over 10% is necessary for widespread application.10 Theoretical calculations have shown that the polymer/fullerene BHJ solar cell in a single layer conguration can achieve more than 10% in PCE.11 After an exhaustive effort in morphology control, electrode modication, the introduction of dielectric layers, and the utilization of the plasmonic effect, it is clear that the most important limiting factor for further improvement on the photovoltaic performance is the materials in active layers, especially the polymer donor material.12,13 In this article, we will briey review research progress in the development of new semiconducting polymers for solar energy harvesting.

2. Materials for BHJ Organic Solar Cells

There are two components in the BHJ structure, the donor and the acceptor. The selection of the materials for both components is very important for solar cell performance. Photovoltaic properties of several representative solar cell systems with different donor/acceptor are outlined in Table 1. Owing to their strong absorbing ability, good lm-forming ability and unique electronic properties from the long pi-conjugated system, semiconducting polymers are good candidates as donor component. A potential drawback is that conjugated polymers exhibit a broad distribution in molecular weight, which is easy to cause purication difculty and poor reproducibility due to batch-to-batch difference. Small conjugated molecules offer the advantages of mono-dispersity and easy purication, so they are actively searched for solar cell applications. However, the lm forming ability from solution and the charge mobility in the blend structure of small molecules are not as good as polymers. As a result, so far, the PCE of the solution processed BHJ solar cells using small molecules donors is much lower than the polymer counterpart.14,15

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Table 1 Photovolatic properties of representative BHJ solar cell systems with different donor/ acceptor materials. Some structures are showed in Fig. 1 Type Polymer/Fulleride Small molecule/ Fulleride Polymer/Polymer Polymer/Inorganic nanocrystals Donor materials PTB7 Squaraine 1 DH6TDPP P3HT P3HT MDMOPPV Acceptor materials PC71 BM PC61 BM PC61 BM F8TBT CdSe ZnO Voc (V) 0.74 0.62 0.67 1.15 0.7 0.84 Jsc FF PCE (mA/cm2) (%) (%) Reference 14.5 5.7 8.42 3.6 5.7 2.40 69 35 45 34 40 59 7.40 1.24 2.33 1.20 1.70 1.60 74 12b 12a 14c 17 18

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Note: Voc = open-circuit voltage, Jsc = short-circuit current density, FF = ll factor.

Thus far, fullerene derivatives are found to be the best candidates as acceptor component due to their high electron afnity and superior electron mobility. Especially, the threedimensional structure of fullerene offers unique packing ability in blend, which can form the electron transport channels efciently. The original fullerenes do not have enough solubility in organic solvents, so fullerene derivatives with solublizing groups are usually used.16 Introduction of the functional group usually improves the miscibility with the donor components, but with small impact on the electronic properties of fullerene. As a result, fullerene derivatives BHJ structure can provide the advantages of efcient exciton dissociation by intermixing the donor/acceptor phases well enough and efcient extraction of the separated charges from the interface by high electron mobility. The weakness of fullerene derivatives as acceptor materials in BHJ solar cells lies in their weak absorption in visible region (like C60 ) and expensive materials cost (like C70 ). N-type polymers as acceptor materials offer the advantages of low cost and high optical absorption. The absorption of the acceptor polymers can be tuned so that both the donor and the acceptor can cover complementary parts of the solar spectrum. However, the efciency obtained from polymer acceptor solar cells is much lower than that from the fullerene derivatives.1719 It has been reported recently that the low efciency in polymer/polymer BHJ is due to the limited transport of the separated charges.20 To overcome this problem, polymers with high local electron mobility are needed. N-type semiconducting inorganic nanocrystals were also used as the acceptor components. Such nanocrystals provide high electron mobility and high optical absorption coefcient.21 CdSe nanocrystals22 and ZnO23 nanocrystals have been used to form polymer/inorganic hybrid BHJ solar cells. However, the achieved efciencies are rather low. Problems associated with the inorganic nanocrystals are their poor solubility in organic solvents and the lack of connectivity between nanocrystals due to the existence of stabilizing bulky ligands .

3. Conjugated Polymer/Fulleride based BHJ Solar Cells

The most effective composite structure in solution processed BHJ organic solar cells is based on conjugated polymer/fullerene BHJ structure, in which electron rich semiconducting polymer plays as donor and fullerene plays as acceptor. PPV/PC61 BM and P3HT/PC61 BM (Fig. 1) are two well-studied systems, which lead to the current understanding of the factors affecting the device performance of BHJ solar cells.

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Figure 1. Structures of widely used conjugated polymers and fullerene derivative and some structures mentioned in Table 1 for BHJ solar cells.

3.1 PPV/PC61 BM BHJ Solar Cells The rst BHJ solar cell was reported by Yu et al. in 1995 based on MEH-PPV//[6,6]-phenylC61 -butyric acid methyl ester (PC61 BM) composite.7 After several years of optimization, the efciency of devices based on this system was still around 1% under AM 1.5 illumination. In 2001, Shaheen et al. reported that a 2.5% efciency was obtained from a better processable composite of poly[2-methoxy-5-(3 ,7 -dimethyl- octyloxy)-1,4-phenylene vinylene] (MDMO-PPV) and PC61 BM by controlling the casting condition.24 The active layer is prepared by spincoating MDMO-PPV/PCBM in 1:4 weight ratio from chlorobenzene. The device has a Voc of 0.82 V, a Jsc of 5.25 mA/cm2, and an FF of 0.61, which leads to a PCE of 2.5%. There is about a three-fold enhancement in efciency compared to the one spincoating from toluene. The performance difference is attributed to the change of active layer morphology. PCBM has better solubility in chlorobenzene than toluene, which increases the miscibility of the two components. A more homogenous and bicontinuous composite was observed in the chlorobenzene-casting lm compared to the toluene-casting lm. Therefore, the heterojunction interface increases for excitons dissociation and more biocontinuous network forms for charge transport, which attributes to the performance enhancement. The performance of MDMO-PPV/PC61 BM system can be further optimized to about 3% by using LiF as interlayer.25 Another performance improvement was achieved by substituting PC61 BM to PC71 BM. PC71 BM has better absorption in the visible region than PC61 BM, and as a result, the MDMO-PPV//[6,6]-phenyl-C71 -butyric acid methyl ester (PC71 BM) system gives a larger Jsc, and about 3% in efciency was achieved.26 However, PPV materials can only harvest light below 600 nm due to their relatively large bandgap (2.2 eV) and they usually have low hole mobility, which limits the further improvement of such solar cells.

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3.2 Poly(3-alkylthiophene)/PC61 BM BHJ Solar Cells Poly(3-alkylthiophenes) are good alternatives to PPV for photovoltaic application. They have a bandgap around 1.9 eV, which can harvest sunlight from 350 nm to about 650 nm in lm. The alkyl side chains make them very soluble in organic solvents. The regioregular poly(3-alkylthiophenes) have good interchain packing ability, offering hole mobility up to 0.1 cm2/Vs.27 Poly (3-hexylthiophene) (P3HT) is a generally used polymer in poly(3alkylthiophenes). However, low efciency was obtained from P3HT/PC61 BM simple solar cells without any post-treatment in the early years. In 2003, Padinger et al. reported that about 3.5% can be achieved by P3HT/PC61 BM system by post thermal annealing with external bias, which is about ten fold increase in efciency compared to the untreated system (0.4%).28 This thermal annealing effect attracted great attention and raised further extensive studies on thermal annealing for optimization of the P3HT/PC61 BM system, and about 45% device efciencies were obtained in subsequent years.29,30,31 Generally, the optimized ratio of P3HT/PC61 BM is about 1:1 by weight and chlorobenzene or dichlorobenzene is used as solvent. Thermal annealing is usually taken at between 100 to 150C for about 560 mins. The detailed conditions on thermal annealing of P3HT/PCBM solar cells vary from report to report, which may be due to other different experimental parameters used. Similar changes on device characteristics upon annealing are observed: Voc decreases slightly to about 0.6 V, while Jsc and FF signicantly increases to about 10 mA/cm2 and over 0.6, respectively. The better device performance of the annealed P3HT/PC61 BM is attributed to the increase of P3HT crystallinity in blend. When P3HT/PC61 BM active layer lm forms from solution, both components are intimately mixed32 and the conguration and planarity of the P3HT chain are distorted by PC61 BM. Thermal annealing allows the growth of P3HT crystalline, which leads to the enhancement of long wavelength absorption and hole mobility. The growth of P3HT crystalline is accompanied by the aggregation of PC61 BM, and to a certain extent, a better bicontinuous interpenetrating network is formed for the charge transport.33 Such morphology change enhances Jsc and FF, which accounts for the efciency increase. Besides thermal annealing, other methods have been developed to control the morphology of P3HT/PC61 BM in order to improve the efciency. Li et al. proposed a solventannealing method.34 Through controlling the solvent evaporation time during lm forming of the P3HT/PC61 BM, the ordering of P3HT is controlled.35 The performance of the device prepared from slow drying without thermal annealing is comparable to the device prepared from thermal annealing. Complying both the solvent annealing and thermal annealing, an efciency of 4.4% can be achieved in P3HT/PC61 BM systems. Moule and Meerholz proposed a solvent mixing method.36 By adding a small ratio of dipolar solvent (nitrobenzene) in the P3HT/PC61 BM solution in chlorobenzne, the aggregation of P3HT increases in solution and it can be brought to lm. The P3HT/PC61 BM devices made from such mixed solvents can achieve up to 4% efciency without thermal annealing. Other methods, like the addition of PC61 BM soluble addictive37,38 or the growth of P3HT nanobers,39 are also reported to improve P3HT/PC61 BM efciency by controlling the morphology. P3HT/PC61 BM device performance is highly dependent on the processing condition, an external factor. In another side, internal factors, like P3HT regioregularity (RR), molecular weight, also have great inuence. RR is dened by the percentage of head-to-tail linkages in the polymer chain. Kim et al. reported the study of P3HT/PC61 BM solar cells with different P3HT RR and showed that increasing the RR of P3HT results in device performance improvement due to the higher crystalline in polymer with higher RR.40 Sivula et al. reported that certain degree of regioirregularity in P3HT can improve the stability of solar

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Developing Semiconductor Polymers for Solar Energy Harvesting Table 2 Photovoltaic properties of some PPV/fulleride or P3HT/fulleride BHJ solar cells Entry 1 2 3 4 5 6 7 8 9 Materials PPV/PC61 BM PPV/PC71 BM P3HT/PC61 BM P3HT/PC61 BM P3HT/PC61 BM P3HT/PC61 BM P3HT/PC61 BM P3HT/PC61 BM (TiO2 ) P3HT/PC61 BM (NiO)

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Voc (V) Jsc (mA/cm2) FF (%) PCE (%) Reference 0.82 0.77 0.55 0.61 0.63 0.65 0.61 0.61 0.64 5.25 7.6 8.5 10.6 9.5 11.1 10.6 11.1 11.3 61 51 60 62 68 54 67 66 69 2.5 3.0 3.5 4.0 5.0 4.9 4.4 5.0 5.0 19 21 23 24 (a) 24 (b) 24 (c) 27 35 36

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cell devices.41 As far as molecular weight is concerned, a good system requires a rather broad polydispersity with a proper combination of low molecular weight and high molecular weight portion, so that a highly crystalline region formed by low molecular weight can be interconnected by the high molecular weight polymer chains.42 Some device techniques have also been explored to improve the performance of P3HT/PC61 BM systems. Kim et al. introduced a solution processed TiO2 layer between the active layer and aluminum electrode.43 Such TiO2 can act as an optical spacer, which increases the absorption of reective light from Al electrode in the active layer, and at the same time act as a hole-block layer, which facilitates the electron injection to the Al electrode. About 5% can be achieved in this system. Irwin et al. reported the replacement of PEDOT:PSS layer into a thin NiO layer. Such replacement improves the Voc and Jsc of the P3HT/PC61 BM device, leading to a PCE of about 5.0% .44 The P3HT/PC61 BM system was the dominant system for BHJ organic solar cells in the last 6 years. After an exhaustive research effort, the maximum EQE of P3HT/PC61 BM solar cells can reach to over 70%, which is comparable to inorganic counterparts. However, the highest overall power conversion efciencies reported so far based on this system is just around 5%, still low for commercial application. The low efciency is mainly due to the limited spectral absorption range of polymer active layer (up to 650 nm) and too large energy offset between P3HT and PC61 BM LUMO energy level, which can cause energy waste. As a result, new materials exhibiting better performances are needed in order to achieve the desired performance in polymersolar cells for practical application.12,13

4. Development of New Polymer Materials for High Performance Polymer/Fullerene Solar Cells
There are many factors limiting the performance of the BHJ solar cells. Among them, materials of active layer is the most determining factor in the overall solar cell performance as most of the fundamental processes, like light harvesting, charge generation and charge transport happen in the active layer. Based on the lessons learned from PPV/PC61 BM and P3HT/PC61 BM systems, several approaches have been pursued to optimize the polymer materials for solar cell performance improvement.12,13

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Figure 2. Solar photon ux spectra (AM 1.5).

4.1 Low Bandgap Polymers for Polymer/fulleride BHJ Solar Cells The spectrum of solar photon ux reaching the surface of the earth is shown in Fig. 2.45 The ux distributes over a large wavelength range from 280 nm to 4000 nm with a maximum at about 700 nm. The absorption of polymer/fulleride BHJ solar cells is mainly contributed from the polymer. However, due to the relatively large bandgaps, both PPV (2.2 eV) and P3HT (1.9 eV) can only harvest a very small fraction of the solar spectrum. Theoretical calculation showed that P3HT/PC61 BM system with absorption onset at about 650 nm, can absorb, at best, 23% of the available solar photons.46 Therefore, extending the polymer absorption to a near-infrared region is attractive in improving the efciency of polymer/fullerene based BHJ solar cells by efciently harvesting the energy in the entire solar spectrum. It can be achieved by the use of low bandgap polymers in BHJ solar cells. Herein, the low bandgap polymers are dened as polymers with a bandgap less than 1.8 eV. Low bandgap polymers can be synthesized by a variety of methods. One of the most used methods is the donor-accepter approach, in which a electron-rich unit (donor, D) and a electron-poor unit (acceptor, A) are alternatively coupled in the polymer backbone. Such alternation results in a mesomerism, D-A < = > D+ = A.47 Increasing the strength of the donor and the acceptor can enhance the double bond character in the single bonds between these two units on the polymer chain, which reduces the bond-length alteration energy, leading to the reduction of the bandgap.48 Use of fused rings to enhance the quinoid character in polyaromatic system is another efcient way to lower the bandgap. It is rst illustrated in polyisothianaphthene (PITN) reported by Wudl et al. in 1984.49 (Fig. 3) As the benzene has higher resonance energy than thiophene, the fused six-membered benzene ring gains aromaticity and the thiophene ring tends to dearomatize into a quinoid structure. The quinoid structure can effectively lower the bond alternation energy and reduce the polymer bandgap. Besides these two approaches, the polymer bandgap can be reduced by

Figure 3. Aromatic and quinoid structures of PITN.

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Figure 4. Structures of benzothiadiazole based low bandgap polymers for BHJ solar cells.

increasing the planarity of the conjugated backbone, increasing the pi-conjugation length and the control of intermolecular interactions.50 Benzothiadiazole is often used to construct low bandgap polymers for BHJ solar cells. One of the rst low bandgap polymers designed for BHJ solar cells was reported by Dhanabalan et al. in 2001.51 The polymer PTPTB (Fig. 4) is composed of dithienylpyrrole donor block and benzothiadiazole acceptor block, synthesized by Stille coupling reaction. The optical bandgap of the polymer is about 1.46 eV1.60 eV, depending on the molecular weight. Initial results gave an efciency of about 0.34% from the polymer solar cell fabricated by PTPTB/PC61 BM in 1:1 weight ratio. After optimization, a better efciency of about 1% was achieved from PTPTB/PC61 BM in 1:3 weight ratio with a Voc of 0.72 V, a Jsc of 3.10 mA/cm2 and an FF of 0.37.52 The photocurrent of the PTPTB devices is extended to about 770 nm. However, the EQE is relatively low, almost smaller than 20% over the whole spectrum, which accounts for the low PCE. A variety of low bandgap polymers have been developed for OPV since53,54; however, few of them can exhibit comparable performance as P3HT until Muhlbacher et al. reported a copolymer of dialkyl-cyclopentabithiophene and benzothiadiazole, PCPDTBT in 2006 (Fig. 4).55 Cyclopentadithiophene is a rigid and strong electron-donating unit, which makes polymer PCPDTBT have very low bandgap and high hole mobility. PCPDTBT has an optical bandgap of about 1.40 eV, with a board absorption of about 890 nm. The primary BHJ solar cells of PCPDTBT/PC71 BM in 1:3 weight ratio showed a PCE of 3.2%, a Voc of 0.65 V, and a Jsc of 11 mA/cm2. The peak EQE value (38%) and FF (47%) are relatively low, which is due to the unoptimized morphology. In 2008 Peet and Lee et al. reported that the use of additives, like alkanedithiols or diiodoalkane, can ameliorate such a morphology problem.56,57 One of the best BHJ solar cell devices was achieved from PCPDTBT/PC71 BM (1:3.6 weight ratio) in chlorobenzene solution with 2.5% (volume ratio) diiodooctane. It delivers a Voc of 0.61 V, a Jsc of 15.3 mA/cm2 and an FF of 0.53, which results in an efciency of 5.12%. A closely related polymer, PSBTBT, was reported by Hou et al.58 (Fig. 4) Replacing the bridging carbon atom in cyclopentadithiophene to the silicone atom has a positive impact on the hole transport but a slight change on absorption. The best BHJ solar cells were achieved from PSBTBT/PC71 BM blend in 1:1 weight ratio. It gives a Voc of 0.68 V and a Jsc of 12.7 mA/cm2 together with an FF of 0.55 leading to an efciency of 5.1%. Recently, Cofn et al. optimized the polymerization condition by use of microwave heating and screening of comonomer reactant ratios to obtained a higher molecular weight polymer P2 with same backbone.59 Such high molecular weight P2 gives enhanced efciency of 5.9% in P2/PC71 BM solar cells.

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Figure 5. Structures of diketo-pyrrolo-pyrrole based low bandgap polymers and acceptor side chain polymer for BHJ solar cells.

Recently, the use of diketo-pyrrolo-pyrrole as acceptor to achieve low band polymers for BHJ solar cell was reported by Wienk et al.60 (Fig. 5) The diketo-pyrrolo-pyrrole unit is very electron poor and has strong packing ability. These types of moieties were rst incorporated into conjugated polymers as efcient light absorber in photorefractive polymers by Chan et al. in 1993.61 The polymer reported by Janssen et al.,60 PBBTDPP2, is composed of quaterthiophene and diketo pyrrolo-pyrrole and has a low optical bandgap of 1.40 eV in lm. The photovoltaic performance of PBBTDPP2 is highly related to the processing solvent. The optimized PBBTDPP2/PC71 BM solar cells were achieved in 1:2 weight ratio prepared from chloroform/o-dichlorobenzene mixed solvent. The device gives a Voc of 0.61 eV and a Jsc of 11.3 mA/cm2, as well as an FF of 0.58, yielding an efciency of 4.0%. Another interesting diketo-pyrrolo-pyrrole polymer (PDPP-BDP) is reported by Huo et al.62 The polymer is composed of benzo[2,1-b:3,4-b ]dithiophene as another building unit. It has a similar bandgap (1.34 eV) as PBBTDPP2, and PDPP-BDP/PC71BM solar cell gives an efciency of 4.4% . Another method to make a low bandgap polymer for OPV is proposed by Huang et al. through making polymers with D-pi-bridge-A side chains structure.63 The polymers are composed of uorene and triarylamine alternating units with acceptor groups connecting Table 3 Photovoltaic properties of some low bandgappolymer BHJ solar cells Materials PTPTB/PC61 BM PCPDTBT/PC71 BM PCPDTBT/PC71 BM PSBTBT/PC71 BM P2/PC71 BM PBBTDPP2/PC71 BM PDPP-BPD2/PC71 BM PFPDT/PC71 BM Polymer bandgap (eV) 1.46 1.40 1.40 1.45 1.37 1.40 1.34 1.76 Voc (V) 0.72 0.65 0.61 0.68 0.57 0.61 0.72 0.99 Jsc (mA/cm2) 3.10 11.0 15.3 12.7 17.3 11.3 10.0 9.6 FF (%) 37 47 53 55 61 58 62 50 PCE (%) 1.0 3.2 5.1 5.1 5.9 4.0 4.4 4.5 Reference 42 46 47 (b) 48 49 50 52 53

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to one arm of the triarylamine as side chains. The polymer PFPDT has a bandgap of 1.76 eV. The solar cell made by PFPDT/PC71 BM gives an efciency of 4.5% with a Voc of 0.99 V, a Jsc of 9.62, and an FF of 50%. The polymer has a relative high hole mobility (1.16 103 cm2 V1S1 from the space charge limiting current (SCLC) method), which is due to better isotropic charge transport from the two-dimensional structure. 4.2 Large Bandgap Polymers with Low Lying HOMO Energy Level for BHJ Solar Cells In P3HT/PC61 BM solar cell, there is about 1 eV energy offset between P3HT LUMO level and PC61 BM LUMO level. It is reported that an energy offset of about 0.3 eV is sufcient for effective charge separation.64 There is about 0.6 eV0.7 eV energy offset wasted. The Voc is determined by the energy difference of the polymer HOMO level and the PC61 BM LUMO level. As a result, compared to the P3HT/PC61 BM system, improved performance can be achieved in large bandgap polymers by lowering the HOMO and LUMO energy levels simultaneously to provide larger Voc and less wasted LUMO offset energy.65 This concept was rst illustrated in uorine-based polymer solar cells reported by Svensson et al. 66 and Zhou et al. 67 (Fig. 6) The weak strength of the uorene donor and the benzothiadiazole acceptor results in a rather large bandgap in PFDTBT, which is about 1.9 eV. The PFDTBT/PC61 BM (1:4 weight ratio) solar cells provided a Voc of about 1.0 V, much larger than that of P3HT. Combining with a Jsc of 4.66 mA/cm2 and an FF of 0.46, it gives an efciency of 2.2%.66 Further optimization of the side-chain patterns and fabrication procedures leads to an efciency of about 4.2%, mainly by the increase of Jsc to 7.7 mA/cm2.68 Substitution of the carbon atom in 9-position of uorene to a silicon atom leads to a new polymer PSiF-DBT.69 (Fig. 6) The substitution signicantly improved the hole mobility of PSiF-DBT. Still the polymer has rather low HOMO energy level, which was measured

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Figure 6. Structures of large bandgap polymers with low lying HOMO energy levels for BHJ solar cells.

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Table 4 Photovoltaic properties of some large bandgappolymer BHJ solar cells with low large Voc Materials PFDTBT/PC61 BM PSiF-DBT/PC61 BM PCDTBT/PC61 BM PCDTBT/PC71 BM HXS-1/PC71 BM APFO-15/PC61 BM Voc (V) 1.00 0.90 0.89 0.88 0.81 1.00 Jsc (mA/cm2) 4.66 9.50 6.92 10.6 9.8 6.00 FF (%) 46 51 63 66 69 63 PCE (%) 2.2 5.4 3.6 6.1 5.4 3.7 Reference 56 59 60 61 62 63

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to be 5.39 eV. PSiF-DBT/PC61 BM solar cell showed a PCE of 5.4% under 80 mW/cm2 illumination, which is mainly due to the high Voc (0.90 V) and good Jsc (9.5 mA/cm2). Blouin et al. reported a similar polymer based on carbazole, PCDTBT.70 (Fig. 6) Carbazole has good p-type transport properties. Substitution of uorene in APGF-3 into carbazole in PCDTBT is expected to improve the hole mobility of the polymer. The polymer has an absorption onset at 660 nm, which corresponds to a bandgap of 1.88 eV. The cyclovoltametry (CV) measurement showed a low lying HOMO energy level, which is about 5.50 eV (LUMO of PC61 BM is 4.30 eV). The best device performance is about 3.6% (under 90 mW/cm2, AM 1.5) from PCDTBT/PC61 BM in 1:4 weight ratio. The good performance is attributed to the large Voc of 0.89 V (due to low lying HOMO) and the high FF of 0.63 (due to good hole mobility). Further optimization of this polymer is recently reported by Park et al.71 Three ways are used for the further improvement: 1) replacing the PC61 BM into PC71 BM to improve light harvesting; 2) inserting a TiO2 optical layer to improve absorption of reective light and electron injection to cathode; 3) searching good solvent to improve nanomorphology. The best device from PCDTBT/PC71 BM in 1:4 ratio gives an efciency of 6.1%, with Voc = 0.88 V, Jsc = 10.6 mA/cm2 and FF = 0.66. A similar polymer (HXS-1) was recently reported by Qin et al., in which two octyloxy chains were introduced to benzothiazole ring and an octyl chain was connected to carbazole instead of a branched chain.72 Such modication leads to planar conformation of the polymer chains in solid state. The polymer solar cell prepared by HXS-1/PC71BM from DCB/DIO gives a PCE of 5.4%, with Voc = 0.81 V and Jsc = 9.8 mA/cm2 and FF = 0.69. The high FF indicates the balanced change transports in the solar cell device. Solar cells with large Voc and good PCE can also be achieved in quinoxaline based polymers. Gadisa et al. reported a polymer, APFO-15 composed of quinoxaline and uorene alternating units.73 The best polymer solar cells from APFO-15/PC61 BM in 1:3 ratio gave a PCE of 3.7% with Voc = 1.0 V, Jsc = 6.0 mA/cm2, and FF = 0.63. The high PCE is related to the rather high hole mobility and balanced charge carriers transport, as well as the low lying HOMO energy level. However, similar to other large bandgap polymers, the limited absorption results in rather small Jsc . 4.3 New Polymer Structure for Enhanced Photovoltaic Performance The above discussions have emphasized the importance of control in polymer bandgap and energy level to improve the polymers photovoltaic performance. Besides, the high hole mobility and suitable miscibility with fulleride to form interpenetrating network are also required for the polymer to achieve highly efcient polymer solar cells. However, it is very

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Figure 7. Structures of thieno[3,4-b]thiophene ester based polymers.

difcult to design a polymer to fulll all these requirements so far. The power of organic synthesis enables the tailoring of polymer properties by ne-tuning its structure, which can lead to enhanced photovoltaic performance in the polymer solar cell. Examples will be given below on a series of thieno[3,4-b]thiophene polymers developed for photovoltaic applications. Thieno[3,4-b]thiophene polymer is one type of low bandgap polymer in which a fused thiophene ring can stabilize the quinoidal structure of the polymer to lower the bandgap.74 Several thieno[3,4-b]thiophene polymer derivatives have been reported; however, the high HOMO energy levels of these polymers limit their photovoltaic application.75,76 To lower the HOMO, an electron withdrawing ester group was introduced to thienothiophene ring.77 Meanwhile, the side chain on ester can also improve the polymer solubility. A polymer (PTT) composed of such thienothiophene ester and thiophene alternating units was synthesized by Stille coupling reaction (Figure 7). Although PTT shows a bandgap of 1.30 eV and wide absorption in visible and near infrared range, the PTT/PC61 BM solar cell only yields a PCE of 0.6%.77 The low PCE is due to the high HOMO energy level and relative low hole mobility caused by the bulky side chain used. To adjust the energy level of the resulting polymers, a series of regio-random copolymers based on thieno[3,4-b]thiophene and alkyl thiophene unit have been synthesized. It is found that by controlling the ratio of thieno [3,4-b]thiophene to alkyl thiophene in the copolymer composition, the electro-optic properties of the copolymers can be ne-tuned.78 When these copolymers were blended with PC61 BM to form an active layer of the solar cell, an optimized copolymer composition (PTT-C) was found to give the highest efciency of 1.9%.78 To further enhance the polymer mobility, a regioregular copolymer (PF) was made by the incorporation of well-dened oligothiophene on the polymer backbone. PCE of 2.4% has been achieved by PF/PC61 BM solar cell.79 The above thienothiophene based polymer have better light absorption than P3HT, however, the efciencies of such polymer solar cells are much lower than P3HT. One limiting factor is the rather low hole mobility in these polymers. To solve the problem, a thieno[3,4b]thiophene ester and benzo[1,2-b:4,5-b ]dithiophene alternating polymer (PTB1) was developed (Fig. 8).80 Benzo[1,2-b:4,5-b ]dithiophene has been recently reported as a building

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Figure 8. Structure of PTB1.

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Figure 9. Structures of PTB polymers. (Figure available in color online)

block for semiconducting polymers with high hole mobility.81 The dithiophene rings are fused by a benzene ring, which forms a rigid structure. The incorporation of the benzodithiophene unit is expected to improve the polymer hole mobility. Meanwhile, there are two side chains on the benzodithiophene ring, which can enable good solubility of the polymer without introducing too bulky a side chain on thienothiophene ester. The side chain pattern also provides good packing ability and space for fulleride intercalation. The optical bandgap of PTB1 is 1.58 eV with peak absorption at 690 nm, corresponding to the maximum photon ux of the solar spectrum. PTB1 has higher SCLC mobility (4.5 104 cm2 V1s1) than P3HT (2.7 104 cm2 V1s1) measured in the same condition. PTB1 has good miscibility with fulleride and ne interpenetrating networks are formed in PTB1/PC61 BM blend lm. These superior properties lead to good photovoltaic performance of PTB1 solar cells. PTB1/PC61 BM solar cell gives a PCE of 4.8% with Voc = 0.58 V, Jsc = 12.5 mA/cm2 and FF = 65.4%; while PTB1/PC71 BM solar cell gives a PCE of 5.6% with Voc = 0.56 V, Jsc = 15.8 mA/cm2 and FF = 63.3%. The enhanced efciency in PC71 BM solar cell is due to the higher absorption of PC71 BM in the visible region compared to PC61 BM. The Jsc and FF obtained from PTB1 solar cells are among the highest values reported for solar cell system based on low bandgap polymers. However, the Voc of the polymer solar cells is relatively small, just about 0.560.58 V. The encouraging results of polymer PTB1 lead us to select the polymer backbone as the structural platform to further investigate the structure/property relationship and to search for new polymers with improved solar cell performance. As mentioned before, a way to increase Voc is lowering the polymer HOMO energy level65 which can be achieved by introducing an electron withdrawing group to the polymer backbone or replacing the electron rich group on the backbone to a less electron rich group. Side chains on polymer backbone can be ne-tuned to further optimize the miscibility with fullerene. A series of new semiconducting polymers with alternating thieno[3,4-b]thiophene and benzodithiophene units have been developed.82 (Fig. 9) Two methods are applied to lower the polymer HOMO. In PTB3, the electron rich alkoxy side chains on benzodithiophene in PTB1 are replaced with a less electron rich alkyl chain. In PTB4, electron withdrawing uorine is introduced to the thienothiophene of the polymer backbone. The length and pattern of the side chains on both the thienothiophene ester and benzodithiophene are varied in these polymers to tune the polymer solubility and miscibility with fullerene. The electro-optic properties of these polymers are very similar; for example, they have similar bandgap and absorption spectra. (Fig. 10) As expected, PTB3 and PTB4 have lower HOMO energy level (0.1 eV) compared to the analogues with the same side-chain patterns. The hole mobility of these polymers varied slightly according to structures: the polymer with bulkier side chains have lower mobility and the alkyl grafted PTB3 and uorinated PTB4 exhibit larger hole mobility than other polymers.

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Figure 10. (a) Absorption spectra and (b) energy levels of PTB polymers. (Figure available in color online)

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The photovoltaic performance of these polymers was studied in the PTB/PC61 BM solar cells. The alkyl substituted PTB3 and the uorinated polymer PTB4 devices showed enhanced Voc (>0.72 V). The changes in Voc are well correlated with the HOMO energy levels of polymers. In the optimized conditions, polymer solar cells from PTB3 (5.85%) and PTB4 (6.10%) showed obvious enhancement in PCE compared to PTB1 (4.76%). The PCE enhancement is due to the increase of Voc without sacricing of Jsc and FF. It shows the success of structure ne-tuning to improve the solar cell performance. Side-chain patterns also play an important role in the polymer performance. When the long dodecyl chain on PTB1 changes to a shorter 2-ethylhexyl side chain on PTB2, the PCE of PTB2 slightly increases (5.10%), which may be due to the increase of miscibility. In another side, the too bulky side chains can be detrimental to the polymer performance as they reduce the polymer miscibility with fullerides (like PTB6). The polymer photovoltaic performance is related to the morphology of composite lms, which can be affected by the lm preparation conditions. In some of the PTB polymers, the active layer needs to be prepared from mixed solvents (like dichlorobenzene/diiodooctance) to achieve optimized morphology . As it has been demonstrated in PTB1 solar cells, the use of PC71 BM instead of PC61 BM as acceptor can lead to further enhancement of the PCE. A power conversion efciency of 7.4% has been achieved from PTB7/PC71 BM solar cell devices with Voc = 0.74 V, Jsc = 14.5 mA/cm2 and FF = 69.0%.83 It is the rst polymer solar cell system showing power conversion efciency over 7%. A similar polymer with ketone replacing to ester in thieno[3,4-b]thiophene unit showed a similar PCE of 7.7%.84 Table 5 Characteristic properties of polymers and their solar cells in PTBx/PC61 BM composite Polymers PTB1 PTB2 PTB3 PTB4 PTB5 PTB6 PTB3a PTB4a PTB5a EHOMO (eV) 4.90 4.94 5.04 5.12 5.01 5.01 ELUMO (eV) 3.20 3.22 3.29 3.31 3.24 3.17 Voc (V) 0.58 0.60 0.74 0.76 0.68 0.62 0.72 0.74 0.66 Jsc (mA/cm2) 12.5 12.8 13.1 9..20 10.3 7.74 13.9 13.4 10.7 FF (%) 65.4 66.3 56.8 44.5 43.1 47.0 58.5 61.4 58.0 PCE (%) 4.76 5.10 5.53 3.10 3.02 2.26 5.85 6.10 4.10

Note: a). Devices prepared from mixed solvents dichlorobenzene/diiodooctance (97/3, v/v).

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Figure 11. Structure of thieno[3,4-c]pyrrole-4,6-dione polymers.

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Inspired by the design of PTB polymers, several similar polymers, in which thieno[3,4b]thiophene units are replaced to thieno[3,4-c]pyrrole-4,6-dione units, have been reported most recently for efcient solar cells.8587 The use of thieno[3,4-c]pyrrole-4,6-dione unit lowers the polymer HOMO energy level, which leads to a larger Voc (>0.80). However, the lowering of HOMO energy level also causes the increase of polymer bandgap (1.80 eV), resulting in a smaller Jsc. PCE of 5.5% has been demonstrated in the polymer solar cells with PC71 BM as acceptor.

5. Conclusions
Since their discovery in 1995, polymer/fullerene BHJ solar cells constitute a very popular research area, and a better understanding of the operating mechanism and factors that affect the solar cell performance have been obtained. However, the observed efciency in polymer solar cells, especially in large solar panels is still lower than the corresponding commercial inorganic systems, which limits their vital applications. It has been realized that the ideal polymer in BHJ structure should exhibit a broad absorption with a high coefcient in the solar spectrum to ensure effective harvesting of solar photons. In addition, the polymer should have high hole mobility for charge transport. To maximize the effective charge carriers extraction, the hole mobility of the polymer should be balanced with the electron mobility of the fulleride acceptor. It also requires for the polymer to have suitable energy levels matching the fulleride. The polymer should have a low-lying HOMO energy level to provide a large Voc and suitable LUMO energy level to provide enough offset for charge separation. Besides these optical and electronic properties, the polymer should have appropriate compatibility with fullerene to form effective bicontinuous interpenetrating network in nanoscale for charge separation and transport. Signicant progress has been made in developing various polymer donor materials that exhibit properties that satisfy the above requirements. A good example is the PTB polymer system with thieno[3,4-b]thiophene and benzodithiophene alternating units, based on which the BHJ solar cells with PC71 BM exhibited a PCE close to 8%. However, several challenges still exist in this area. First, new donor materials with better properties are still needed. Second, acceptor polymers that can rival fullerenes are essential to lower the cost of polymer solar cells. Third, a detailed understanding of the photochemical stability of the organic solar cells must be gained. With the current success, we believe that solutions can be found and polymer solar cells will have a bright future.

Acknowledgements
We would like to acknowledge the support from NSF, AFOSR, DOE, NSF MRSEC (University of Chicago) and Solarmer Energy Inc. for the preparation of this article and the works described here.

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