Polymer Acceptors for High-Performance All-Polymer Solar Cells

All-polymer solar cells (all-PSCs) have attracted considerable attention owing to their pronounced advantages of excellent mechanical flexibility/stretchability and greatly enhanced device stability as compared to other types of organic solar cells (OSCs). Thanks to the extensive research efforts dedicated to the development of polymer acceptors, all-PSCs have achieved remarkable improvement of photovoltaic performance, recently. This review summarizes the recent progress of polymer acceptors based on the key electron-deficient building blocks, which include bithiophene imide (BTI) derivatives, boron-nitrogen coordination bond (B←N)-incorporated (hetero)arenes, cyano-functionalized (hetero)arenes, and fused-ring electron acceptors (FREAs). In addition, single-component-based all-PSCs are also briefly discussed. The structure-property correlations of polymer acceptors are elaborated in detail. Finally, we offer our insights into the development of new electron-deficient building blocks with further optimized properties and the polymers built from them for efficient all-PSCs.     

Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra

Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short‐circuit current density and open‐circuit voltage in comparison with the corresponding HD‐PDFC‐DTBT (HD)‐ and DT‐PDPPTPT (DPP)‐based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance.

     

High‐Efficiency Large‐Bandgap Material for Polymer Solar Cells

High‐molecular‐weight conjugated polymer HD‐PDFC‐DTBT with N‐(2‐hexyldecyl)‐3,6‐difluorocarbazole as the donor unit, 5,6‐bis(octyloxy)benzothiadiazole as the acceptor unit, and thiophene as the spacer is synthesized by Suzuki polycondensation. HD‐PDFC‐DTBT shows a large bandgap of 1.96 eV and a high hole mobility of 0.16 cm² V⁻¹ s⁻¹. HD‐PDFC‐DTBT:PC₇₁BM‐based inverted polymer solar cells (PSCs) give a power conversion efficiency (PCE) of 7.39% with a V_oc of 0.93 V, a J_sc of 14.11 mA cm⁻², and an FF of 0.56.

     

The Influence of Substituent Orientation on the Photovoltaic Performance of Phthalocyanine‐Sensitized Solar Cells

Phthalocyanines (Pcs) are used as sensitizers in dye‐sensitized solar cells (DSSCs) because of their stability and intense absorption in the red and near‐IR regions. Impressive progress has been made in photovoltaic efficiencies by introduction of bulky peripheral substituents to help suppress macrocycle aggregation. To reach benchmark efficiencies reported for other related dyes, new designs need to be explored. Single carboxy‐ZnPc regioisomers substituted at the non‐peripheral positions by rigid aryl groups have now been studied, which has shed light on the influence of steric hindrance and/or orientation of the substituent around the anchoring group on the photovoltaic response. The regioisomer bearing the aryl group far away from the anchoring group produces a more effective sensitization of the TiO₂ films and higher short‐circuit photocurrent density (J_sc). Taking advantage of the good photovoltaic performance in the near‐IR region of this ZnPc, it was combined with another appropriate dye for panchromatic sensitization of the mesoporous photoelectrode and an increase of the overall device efficiency.     

Benzotriazole Based 2D-conjugated Polymer Donors for High Performance Polymer Solar Cells

To design high efficiency polymer solar cells(PSCs), it is of great importance to develop suitable polymer donors that work well with the low bandgap acceptors, providing complementary absorption, forming interpenetrating networks in the active layers and minimizing energy loss. Recently, we developed a series of two-dimension-conjugated polymers based on bithienylbenzodithiophene-alt-benzotriazole backbone bearing different conjugated side chains, generally called J-series polymers. They are medium energy bandgap(Eg) polymers(Eg of ca. 1.80 eV)with strong absorptions in the range of 400-650 nm, and exhibit ordered crystalline structures, high hole mobilities, and more interestingly,tunable energy levels depending on the structure variations. In this feature article, we highlight our recent efforts on the design and synthesis of those J-series polymer donors, including an introduction on the polymer design strategy and emphasis on the crucial function of differential conjugated side chain. Finally, the future opportunities and challenges of the J-series polymers in PSCs are discussed.     

聚合物太阳电池光伏材料

聚合物太阳电池由共轭聚合物给体和可溶性富勒烯衍生物受体的共混膜夹在ITO透光电极和金属电极之间所组成,具有结构简单、成本低、重量轻和可制成柔性器件等突出优点,近年来受到广泛关注。聚合物太阳电池中的给体和受体光伏材料是决定器件性能的关键。本文综述了共轭聚合物给体和富勒烯受体光伏材料的最新研究进展,对共轭聚合物受体材料和给体-受体双缆型共轭聚合物光伏材料的研究进展也进行了简要介绍。在共轭聚合物给体材料中对聚噻吩衍生物以及含有苯并噻二唑的窄带隙D-A共聚物进行了重点介绍。     

A Non-Conjugated Polymer Acceptor for Efficient and Thermally Stable All-Polymer Solar Cells

A non-conjugated polymer acceptor PF1-TS4 was firstly synthesized by embedding a thioalkyl segment in the mainchain, which shows excellent photophysical properties on par with a fully conjugated polymer, with a low optical band gap of 1.58 eV and a high absorption coefficient >10⁵ cm⁻¹, a high LUMO level of −3.89 eV, and suitable crystallinity. Matched with the polymer donor PM6, the PF1-TS4-based all-PSC achieved a power conversion efficiency (PCE) of 8.63 %, which is ≈45 % higher than that of a device based on the small molecule acceptor counterpart IDIC16. Moreover, the PF1-TS4-based all-PSC has good thermal stability with ≈70 % of its initial PCE retained after being stored at 85 °C for 180 h, while the IDIC16-based device only retained ≈50 % of its initial PCE when stored at 85 °C for only 18 h. Our work provides a new strategy to develop efficient polymer acceptor materials by linkage of conjugated units with non-conjugated thioalkyl segments.     

Developing Wide Bandgap Polymers Based on Sole Benzodithiophene Units for Efficient Polymer Solar Cells

In this work, a series of sole benzodithiophene-based wide band gap polymer donors, namely PBDTT, PBDTS, PBDTF and PBDTCl, were developed for efficient polymer solar cells (PSCs) by varying the heteroatoms into the conjugated side chains. The effects of sulfuration, fluorination and chlorination were also investigated systematically on the overall properties of these BDT-based polymers. The HOMO levels could be lowered gradually by introducing sulfur, fluorine and chlorine atoms into the side chains, which contributed to the stepwise increased V_oc (from 0.78 V to 0.84 V) in the related PSCs using Y6 as the electron acceptor. This side-chain engineering strategy could promote the polymer chain interactions and fine-tune the phase separation of active blends, leading to enhanced absorption, ordered molecular packing and crystallinity. Among them, the chlorinated PBDTCl exhibited not only high level absorption and crystallinity, but also the most balanced hole/electron charge transport and the most optimized morphology, giving rise to the best PCE of 13.46 % with a V_oc of 0.84 V, a J_sc of 23.16 mA cm⁻² and an FF of 69.2 %. The chlorination strategy afforded PBDTCl synthetic simplicity but high efficiency, showing its promising photovoltaic applications for realizing low-cost practical PSCs in near future.     

Effect of Fluorination on the Photovoltaic Properties of Medium Bandgap Polymers for Polymer Solar Cells

Fluorination of conjugated polymers is one of the effective strategies to tune the molecular energy levels and morphology for high efficient polymer solar cells (PSCs). Herein, two novel donor‐acceptor conjugated polymers, PffBT and PBT, based on bis(3,5‐bis(hexyloxy)phenyl)benzo[1,2‐ b:4,5‐b']dithiophene and benzo[c][1,2,5]thiadiazole (BT) with or without fluorination, respectively, were synthesized, and their photovoltaic properties were compared. The polymer PffBT based on fluorinated BT showed lower frontier energy levels, improved polymer ordering, and a well‐developed fibril structure in the blend with PC₇₁BM. As a result, the PSCs based on PffBT/PC₇₁BM exhibit a superior power conversion efficiency (PCE) of 8.6% versus 4.4% for PBT‐based devices, due to a high space charge limit current (SCLC) hole mobility, mixed orientation of polymer crystals in the active layer, and low bimolecular recombination.     

基于侧链不对称喹喔啉聚合物的高效非富勒烯太阳电池

喹喔啉衍生物由于合成简单,易功能化,成本较低等特点在众多领域都有广泛应用。其自身具有平面刚性结构,也是构建光电聚合物的重要单体。基于喹喔啉单元的有机分子化学结构和电子结构可修饰性强,通过骨架、侧链和取代基等修饰,易于调控分子的能级和吸光光谱,因此,当使用喹喔啉体系的共轭给体与球形富勒烯受体(如PCBM)及弱结晶性非富勒烯受体(如ITIC)均可表现出优异的光伏性能。在本工作中,基于结晶性较强的非富勒烯受体(o-IDTBR),我们首次制备出侧链不对称喹喔啉(简称：不对称喹喔啉)基聚合物(TPQ-1)与之匹配。相比于侧链对称性喹喔啉(简称：对称喹喔啉)(HFQx-T)与o-IDTBR组合,“弱结晶给体-强结晶受体”组合能表现出更佳均匀的相分离尺度,从而获得更高的短路电流及能量转换效率。TPQ-1与o-IDTBR共混后器件效率为8.6%,加入15%的TB7-Th后,器件效率达到9.6%。     

Polymer Photovoltaic Cells Based on Polymethacrylate Bearing Semiconducting Side Chains

Polymethacrylate with semiconducting side chains ( P1 ), synthesized by free radical polymerization, was used as a donor material for polymer solar cells. P1 is of high molecular weight (M _n = 82 kg mol⁻¹), good thermal stability, narrow band gap (1.87 eV), and low‐lying HOMO energy level (−5.24 eV). P1 possesses not only the good film‐forming ability of polymers but also the high purity of small organic molecules. Power conversion efficiencies (PCEs) of 0.63% and 1.22% have been obtained for solar cells with M1 :PC₇₁BM and P1 :PC₇₁BM as the active layers, respectively. With PC₆₁BM as the acceptor, PCEs of M1 and P1 based devices decrease to 0.61% and 0.76%, respectively. To the best of our knowledge, this is the first report that free radical polymerization can be used to prepare polymer donors for photovoltaic applications.     

小分子给体/高分子受体型有机太阳能电池研究进展

有机太阳能电池具有低成本、柔性和质量轻等优势,是一种有应用前景的光伏技术,受到人们的广泛关注.有机太阳能电池的光敏活性层通常由p-型有机半导体(包括小分子和高分子)与n-型有机半导体(包括小分子和高分子)共混而成.小分子给体/高分子受体型有机太阳能电池具有形貌热稳定性优异的特点,值得深入研究.本综述旨在总结小分子给体/高分子受体型有机太阳能电池的研究进展,分别介绍了基于酰亚胺基、氰基和含硼氮配位键(B←N)的高分子受体的活性层材料体系的发展状况.在器件性能方面,通过分子设计、相分离形貌调控,改善了小分子给体/高分子受体的匹配性,将该类电池的能量转换效率从最初的0.29%提升至目前的9.51%,为性能的进一步提升总结了经验;在稳定性方面,基于该体系形貌热稳定性优异的特点,开发出高温耐受型有机太阳能电池器件.最后,展望了小分子给体/高分子受体型有机太阳能电池的未来发展方向和前景.     

n‐Type Conjugated Polymer Based on Dicyanodistyrylbenzene and Naphthalene Diimide Units for All‐Polymer Solar Cells

All polymer solar cells (all‐PSCs), possessing superior mechanical strength and flexibility, offer the commercialization opportunity of the PSCs for flexible and portable devices. In this work, we designed and synthesized two copolymer acceptors based on dicyanodistyrylbenzene (DCB) and naphthalene diimide (NDI) units. The corresponding copolymer acceptors are denoted as PDCB‐NDI812 and PDCB‐NDI1014. The medium band gap copolymer PBDB‐T was selected as donor material for investigation of the photovoltaic performance. Two all‐PSCs devices showed power conversion efficiencies (PCE) of 4.26% and 3.43% for PDCB‐NDI812 and PDCB‐NDI1014, respectively. The improved PCE was ascribed to the higher short‐circuit current (J_SC), greater charge carrier mobility and higher exciton dissociation probability of the PBDB‐T:PDCB‐NDI812 blend film. These results suggest that DCB unit and NDI unit based copolymer acceptors are promising candidates for high performance all‐PSCs.     

非富勒烯聚合物太阳电池研究进展

综述了以p-型共轭聚合物为给体、n-型有机半导体为受体的非富勒烯聚合物太阳电池光伏材料最新研究进展,包括n-型共轭聚合物和可溶液加工小分子n-型有机半导体(n-OS)受体光伏材料,以及与之匹配的p-型共轭聚合物给体光伏材料.介绍的n-型共轭聚合物受体光伏材料包括基于苝酰亚胺(BDI)、萘酰亚胺(NDI)以及新型硼氮键连受体单元的D-A共聚物受体光伏材料,目前基于聚合物给体(J51)和聚合物受体(N2200)的全聚合物太阳电池的能量转换效率最高达到8.26%.n-OS小分子受体光伏材料包括基于BDI和NDI单元的有机分子、基于稠环中心给体单元的A-D-A型窄带隙有机小分子受体材料等.给体光伏材料包括基于齐聚噻吩和苯并二噻吩(BDT)给体单元的D-A共聚物,重点介绍与窄带隙A-D-A结构小分子受体吸收互补的、基于噻吩取代BDT单元的中间带隙二维共轭聚合物给体光伏材料.使用中间带隙的p-型共轭聚合物为给体、窄带隙A-D-A结构有机小分子为受体的非富勒烯聚合物太阳电池能量转换效率已经突破12%,展示了光明的前景.最后对非富勒烯聚合物太阳电池将来的发展进行了展望.     

Fluorinated Photovoltaic Materials for High‐Performance Organic Solar Cells

Over the past decade, organic solar cells (OSCs) have achieved a dramatic boost in their power conversion efficiencies from about 6 % to over 16 %. In addition to developments in device engineering, innovative photovoltaic materials, especially fluorinated donors and acceptors, have become the dominant factor for improved device performance. This minireview highlights fluorinated photovoltaic materials that enable efficient OSCs. Impressive OSCs have been obtained by developing some important molds of fluorinated donor and acceptor systems. The molecular design strategy and the matching principle of fluorinated donors and acceptors in OSCs are discussed. Finally, a concise summary and outlook are presented for advances in fluorinated materials to realize the practical application of OSCs.     

N-Type Quinoidal Polymers Based on Dipyrrolopyrazinedione for Application in All-Polymer Solar Cells

Conjugated molecules and polymers with intrinsic quinoidal structure are promising n-type organic semiconductors, which have been reported for application in field-effect transistors and thermoelectric devices. In principle, the molecular and electronic characteristics of quinoidal polymers can also enable their application in organic solar cells. Herein, two quinoidal polymers, named PzDP-T and PzDP-ffT, based on dipyrrolopyrazinedione were synthesized and used as electron acceptors in all-polymer solar cells (all-PSCs). Both PzDP-T and PzDP-ffT showed suitable energy levels and wide light absorption range that extended to the near-infrared region. When combined with the polymer donor PBDB-T, the resulting all-PSCs based on PzDP-T and PzDP-ffT exhibited a power conversion efficiency (PCE) of 1.33 and 2.37 %, respectively. This is the first report on the application of intrinsic quinoidal conjugated polymers in all-PSCs. The photovoltaic performance of the all-PSCs was revealed to be mainly limited by the relatively poor and imbalanced charge transport, considerable charge recombination. Detailed investigations on the structure-performance relationship suggested that synergistic optimization of light absorption, energy levels, and charge transport properties is needed to achieve more successful application of intrinsic quinoidal conjugated polymers in all-PSCs.     

Multifunctional Conjugated Polymers with Main‐Chain Donors and Side‐Chain Acceptors for Dye Sensitized Solar Cells (DSSCs) and Organic Photovoltaic Cells (OPVs)

A novel multifunctional conjugated polymer (RCP‐1) composed of an electron‐donating backbone (carbazole) and an electron‐accepting side chain (cyanoacetic acid) connected through conjugated vinylene and terthiophene has been synthesized and tested as a photosensitizer in two major molecule‐based solar cells, namely dye sensitized solar cells (DSSCs) and organic photovoltaic cells (OPVs). Promising initial results on overall power conversion efficiencies of 4.11% and 1.04% are obtained from the basic structure of DSSCs and OPVs based on RCP‐1, respectively. The well‐defined donor (D)‐acceptor (A) structure of RCP‐1 has made it possible, for the first time, to reach over 4% of power conversion efficiency in DSSCs with an organic polymer sensitizer and good operation stability.     

高效率窄带隙聚合物太阳能电池材料

太阳能电池能够将太阳能直接转化为电能,是利用太阳能资源的一种非常有效的手段。聚合物太阳能电池因成本低、重量轻、制备方便和可制成柔性器件的优点,已经成为该领域的研究热点之一。基于窄带隙共轭聚合物给体/富勒烯受体复合材料体系制得的太阳能电池的最高转换效率已经达到8.3%,而寻找性能更优异的聚合物给体材料是进一步提高光伏性能的关键因素。本文综述了近几年关于高效率窄带隙聚合物太阳能电池给体材料的研究进展,着重介绍了苯并噻二唑类共聚物、稠环噻吩类共聚物和吡嗪类共聚物等窄带隙聚合物给体材料体系及相应光伏器件的性能,分析了各种材料的优点和不足,并对今后这一领域的发展做了展望。     

Planar Conjugated Polymers Containing 9,10‐Disubstituted Phenanthrene Units for Efficient Polymer Solar Cells

Four novel conjugated polymers ( P1‐4 ) with 9,10‐disubstituted phenanthrene (PhA) as the donor unit and 5,6‐bis(octyloxy)benzothiadiazole as the acceptor unit are synthesized and characterized. These polymers are of medium bandgaps (2.0 eV), low‐lying HOMO energy levels (below −5.3 eV), and high hole mobilities (in the range of 3.6 × 10⁻³ to 0.02 cm² V⁻¹ s⁻¹). Bulk heterojunction (BHJ) polymer solar cells (PSCs) with P1‐4 :PC₇₁BM blends as the active layer and an alcohol‐soluble fullerene derivative (FN‐C60) as the interfacial layer between the active layer and cathode give the best power conversion efficiency (PCE) of 4.24%, indicating that 9,10‐disubstituted PhA are potential donor materials for high‐efficiency BHJ PSCs.