Large open-circuit voltage polymer solar cells by poly(3-hexylthiophene) with multi-adducts fullerenes

Polymer solar cells (PSCs) made by poly(3-hexylthiophene) (P3HT) with multi-adducts fullerenes, [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), PC61BM-bisadduct (bisPC61BM) and PC61BM-trisadduct (trisPC61BM), were reported. Electrochemistry studies indicated that PC61BM, bisPC61BM and trisPC61BM had step-up distributional lowest unoccupied molecular orbital (LUMO) energy. PSCs made by P3HT with above PC61BMs show a trend of enlarged open-circuit voltages, which is in good agreement with the energy difference between the LUMO of PC61BMs and the HOMO of P3HT. On the contrary, reduced short-circuit currents (Jsc) were observed. The investigation of photo responsibility, dynamics analysis based on photo-induced absorption of composite films, P3HT:PC61BMs and n-channel thin film field-effect transistors of PC61BMs suggested that the short polaron lifetimes and low carrier mobilities were response for reduced Jsc. All these results demonstrated that it was important to develop an electron acceptor which has both high carrier mobility, and good compatibility with the electron donor conjugated polymer for approaching high performance PSCs.     

Fullerene derivative acceptors for high performance polymer solar cells

Polymer solar cells (PSCs) are composed of a blend film of a conjugated polymer donor and a soluble fullerene derivative acceptor sandwiched between a PEDOT?:?PSS coated ITO positive electrode and a low workfunction metal negative electrode. The conjugated polymer donor and the fullerene derivative acceptor are the key photovoltaic materials for high performance PSCs. For the acceptors, although [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) and its corresponding C(70) derivative PC(70)BM are dominantly used as the acceptors in PSC at present, several series of new fullerene derivatives with higher-lying LUMO energy level and better solubility were reported in recent years for further improving the power conversion efficiency of the PSCs. In this perspective paper, we reviewed the recent research progress on the new fullerene derivative acceptors, including various PC(60)BM-like C(60) derivatives, PC(60)BM bisadduct, PC(70)BM bisadduct, indene-C(60) bisadduct and indene-C(70) bisadduct, trimetallic nitride endohedral fullerenes and other C(60) derivatives with multi side chains. The synthesis and physicochemical properties of PC(60)BM and PC(70)BM were also introduced considering the importance of the two fullerene acceptors.     

聚合物:富勒烯薄膜光伏电池的反常高温热稳定性研究

聚合物太阳能电池光电转换效率已接近商业化要求,但稳定性差却成为其实用化瓶颈因素.高温暴晒是聚合物太阳能电池实用化必须面临的环境,因此提高聚合物太阳能电池的热稳定性至关重要.本文以典型的Poly(3-hexylthiophene-2,5-diyl(P3HT):[6,6]-Phenyl-C61-butyric acid methyl ester(PC61BM)基聚合物太阳能电池为研究模型,考察其在不同加热温度下(50~110℃)持续工作时的器件效率变化行为,结果发现电池在高温下表现出一种非常规的性能衰减再回升的行为,具体表现为高温下电池首先表现指数式急速衰减(20%~25%),随后发生反常的性能快速恢复至接近初始效率,之后电池保持超长的高温稳定性.光学显微镜和激光光束诱导电流成像结果证明,顶电极覆盖可以有效抑制活性层中PC61BM的聚集结晶,因而电池的反常热诱导稳定性提升与PC61BM的大量聚集结晶无关.活性层薄膜的紫外可见吸收光谱和器件外量子效率的表征结果证明,持续高温加热没有促进PC61BM二聚体的形成,反而有利于PC61BM二聚体的解离.综合实验分析结果,推测PC61BM在光照下的快速二聚反应及其高温解离是导致电池表现出反常热稳定性提升行为的主要原因.实验结果揭示了初期制备的聚合物太阳能电池实际处于一种亚稳态,对器件进行短暂的前期热退火有利于稳定活性层结构,消除亚稳态,有效提升器件稳定性.本研究工作不仅对富勒烯基聚合物太阳能电池的热诱导反常稳定性提升机理机制给出了解释,而且提供了一种提高聚合物太阳能电池稳定性的新策略.     

Dihydronaphthyl-based [60]fullerene bisadducts for efficient and stable polymer solar cells

Dihydronaphthyl-based [60]fullerene bisadduct derivative, NC(60)BA, was synthesized at mild temperature in high yield. NC(60)BA not only possesses a LUMO energy level 0.16 eV higher than PC(61)BM but also has amorphous nature that can overcome thermal-driven crystallization. The fabricated P3HT:NC(60)BA-based polymer solar cells exhibit superior photovoltaic performance and thermal stability compared to PC(61)BM-based devices under the same conditions.     

Crystalline low band-gap alternating indolocarbazole and benzothiadiazole-cored oligothiophene copolymer for organic solar cell applications

A low band-gap alternating copolymer of indolocarbazole and benzothiadiazole-cored oligothiophene demonstrated balanced crystallinity and solubility; a solar cell combining this polymer with PC(61)BM in a preliminary test demonstrated power conversion efficiencies of 3.6%.     

窄带系聚合物APFO3的激发态光物理特性

化学计算证实了光致激发窄带系聚合物APFO3后,会发生链内电荷转移（ICT）过程,同时这一特性还影响了吸收光谱中的第一吸收带. 瞬态吸收结果再一次表明了当聚合物在单分散体系中确实存在ICT特性,而且这种特性会同振动弛豫竞争. 在聚集态中,受链间相互作用的影响,ICT特性会消失,而且激子弛豫过程将在光致激发后的弛豫过程中占据主导地位. 混有PC61BM的APFO3薄膜的光致激发动力学显示,当PC61BM 的含量超过50%时,激子解离已经达到饱和. 基于此异质节的光伏器件性能显示PC61BM的含量高于50％以后,光电流的增幅也很小．     

Charge trapping and storage by composite P3HT/PC60BM nanoparticles investigated by fluorescence-voltage/single particle spectroscopy

Fluorescence-voltage/single particle spectroscopy (F-V/SPS) was employed to study exciton-hole polaron interactions and interfacial charge transfer processes for pure poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) and composite P3HT/PC(60)BM NPs in functioning hole-injection devices. F-V/SPS data collected on a particle-by-particle basis reveal an apparent bistability in the fluorescence-voltage modulation curves for composite NPs of P3HT and [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) that is absent for pure P3HT NPs. A pronounced deep trapping of free electrons photogenerated from the composite P3HT/PC(60)BM NPs at the NP/dielectric interface and hole trapping by fullerene anions in composite P3HT/PC(60)BM NPs under photoexcitation lies at the basis of this finding. The deep electron trapping effect reported here for composite conjugated polymer/fullerene NPs presents an opportunity for future application of these NPs in nanoscale memory and imaging devices.     

Facile synthesis of a 56π-electron 1,2-dihydromethano-[60]PCBM and its application for thermally stable polymer solar cells

A facile synthesis was employed to make a 56π-electron methano-PC(61)BM with a very small 1,2-dihydromethano (CH(2)) group. This new fullerene derivative possesses high electron mobility (0.014 cm(2) V(-1) s(-1)) and higher LUMO energy level (0.15 eV) than PC(61)BM. Bulk hetero-junction devices based on using poly(3-hexylthiophene) and methano-PC(61)BM as active layer exhibited better performance and thermal stability than those using the PC(61)BM analogue.     

Fullerenes and derivatives as electron transport materials in perovskite solar cells

In this study, two fullerenes (C60, C70) and their methano-substitutions (PC61BM, PC71BM), as electron transport materials (ETMs) in perovskite solar cells (Pero-SCs), were systematically studied. As being used as ETMs, methanofullerenes, though with lower electron mobility compared to the counterpart pristine fullerenes, lead to higher power conversion efficiencies (PCEs) of Pero-SCs. The difference is likely caused by the fill-out vacancies and smoother morphology of the interfaces between ETM and perovskite layers, as they were prepared by different methods. In addition, compared to C60 and PC61BM, C70 and PC71BM showed priority in terms of short-circuit current density, which should be attributed to fast free charge extraction abilities.     

低聚合度的交替共聚物太阳能电池的形态和性能

制备了由低聚合度的聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b;3,4-b']双噻吩)-交替-4,7-(2,1,3-苯并噻二唑)](LDP-PCPDTBT)、[6,6]-苯基-C61-丁酸甲酯(PC61BM)和聚甲基丙烯酸甲酯(PMMA)组成的三组分共混薄膜,并通过加入溶剂添加剂(1,8-二溴辛烷,DBO)对体系进行了优化处理.研究发现,没有加入DBO时,LDP-PCPDTBT和PC61BM相在PMMA的基质中分别是无定形的和结晶的;加入DBO后,PMMA基质中LDP-PCPDTBT和PC61BM间的相分离过程得到优化,有机太阳能电池的能量转换效率相应提高了32.4%.     

Wide bandgap conjugated polymers based on bithiophene and benzotriazole for bulk heterojunction solar cells: Thiophene versus thieno[3,2-b]thiophene as π-conjugated spacers

Two wide bandgap (WBG) conjugated polymers, P2T-DTTTAZ and P2T-DTTAZ, with donor-π-acceptor (D-π-A) structures was designed and synthesized, utilizing thieno[3,2-b]thiophene (TT) and/or thiophene (T) units as π-bridge in conjugated polymer backbone. And, the wider optical band gap (E_g) of approximately 1.98 eV for P2T-DTTTAZ and 2.09 eV for P2T-DTTAZ were observed. Obviously, replacing T unit with larger conjugated plane TT unit as π-bridges, P2T-DTTTAZ resulted in the red shifted absorption and the reduced band gap, compared with these of P2T-DTTAZ. The polymer solar cells (PSCs) with an inverted device structure based on P2T-DTTTAZ or P2T-DTTAZ as donor and [6,6] phenyl-C₆₁ butyric acid methyl ester (PC₆₁BM) as acceptor were assembled and the photovoltaic properties were also investigated. The power conversion efficiencies (PCEs) of 1.57% for P2T-DTTTAZ and 1.25% for P2T-DTTAZ were obtained.     

Effect of 1,8-Diiodooctane Content on the Performance of P3HT:PC61BM Bulk Heterojunction Photodetectors

A series of polymer photodetectors with device configuration of ITO/PEDOT:PSS/P_3 HT:PC_(61) BM/C_(60)/Al were prepared by using P_3 HT as the donor material and PC_(61) BM as the acceptor material. By regulating the content of 1,8-diiodooctane(DIO)(V/V: 1%, 3%, 5%) as a processing additive, the morphology of the active layer can be greatly improved. With C_(60) as the hole blocking layer, the dark current density of the device can be reduced by about an order of magnitude. When employing 3% DIO(V/V) in the active layer processing, the photodetetcors present the best performance, and the detectivity of the device is 1.52×10~(12) Jones at 540 nm under a bias of-0.1 V. Moreover, it also has a wider linear dynamic range of 60 dB as well as faster response speed(τ_r/τ_f=0.53/0.71 μs) than those of devices with other content of DIO additives.     

Rare solvent annealing effective benzo(1,2-b:4,5-b')dithiophene-based low band-gap polymer for bulk heterojunction organic photovoltaics

A newly synthesized benzo(1,2-b:4,5-b')dithiophene-based low band-gap copolymer pBCN is amenable to solvent annealing in the fabrication of organic photovoltaics, of which power conversion efficiency is greatly improved to 4.2% with PC(61)BM or 4.9% with PC(71)BM.     

以C_(70)衍生物为电子受体的高效聚合物固体薄膜太阳能电池

以PC[70]BM(phenyl C71-butyric acid methyl ester)取代PC[60]BM(phenyl C61-butyric acid methyl ester)作为电子受体材料,以MEH-PPV(poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene])为电子给体材料,制成了本体异质结(bulk heterojunction,BHJ)聚合物太阳能电池.MEH-PPV/PC[70]BM器件在AM1.5G(80 mW/cm2)模拟太阳光的光照条件下得到了3.42%的能量转换效率,短路电流值达到了6.07 mA/cm2,开路电压0.85 V,填充因子为53%.通过紫外可见吸收光谱和外量子效率的研究,发现PC[70]BM作为电子受体,对扩大光谱的吸收范围和增加活性层的吸收系数有明显的作用.同时比较了不同溶剂对该体系器件性能的影响.通过原子力显微镜(AFM)、光暗导I-V曲线等研究,分析了1,2-二氯苯有利于给体相和受体相的微相分离和载流子的传输的原因.     

Efficient ternary blend bulk heterojunction solar cells with tunable open-circuit voltage

To explore the potential of ternary blend bulk heterojunction (BHJ) photovoltaics as a general platform for increasing the attainable performance of organic solar cells, a model system based on poly(3-hexylthiophene) (P3HT) as the donor and two soluble fullerene acceptors, phenyl-C(61)-butyric acid methyl ester (PC(61)BM) and indene-C(60) bisadduct (ICBA), was examined. In all of the solar cells, the overall ratio of polymer to fullerene was maintained at 1:1, while the composition of the fullerene component (PC(61)BM:ICBA ratio) was varied. Photovoltaic devices showed high short-circuit current densities (J(sc)) and fill factors (FF) (>0.57) at all fullerene ratios, while the open-circuit voltage (V(oc)) was found to vary from 0.61 to 0.84 V as the fraction of ICBA was increased. These results indicate that the V(oc) in ternary blend BHJ solar cells is not limited to the smallest V(oc) of the corresponding binary blend solar cells but can be varied between the extreme V(oc) values without significant effect on the J(sc) or FF. By extension, this result suggests that ternary blends provide a potentially effective route toward maximizing the attainable J(sc)V(oc) product (which is directly proportional to the solar cell efficiency) in BHJ solar cells and that with judicious selection of donor and acceptor components, solar cells with efficiencies exceeding the theoretical limits for binary blend solar cells could be possible without sacrificing the simplicity of a single active-layer processing step.     

Development of a new benzo(1,2-b:4,5-b')dithiophene-based copolymer with conjugated dithienylbenzothiadiazole-vinylene side chains for efficient solar cells

A new benzodithiophene-based copolymer PTG1 with dithienylbenzothiadiazole-vinylene side chains exhibits excellent film-forming ability, a deep HOMO energy level, and a good miscibility with PC(71)BM. Bulk heterojunction polymer solar cells fabricated from PTG1 and PC(71)BM showed a promising power conversion efficiency over 4.0%.     

Thienopyrazine or dithiadiazatrindene containing low band gap conjugated polymers for polymer solar cells

Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.     

Triplet exciton generation in bulk-heterojunction solar cells based on endohedral fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu(3)N@C(80) (Lu(3)N@C(80)-PCBEH) show an open circuit voltage (V(OC)) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC(61)BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (J(SC)) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the J(SC) in blends containing the high voltage absorber Lu(3)N@C(80)-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu(3)N@C(80)-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC(61)BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu(3)N@C(80)-PCBEH are responsible for the reduced photocurrent.     

J-aggregation induced low bandgap anthracene-based conjugated molecule for solution-processed solar cells

A new anthracene-based X-shaped conjugated molecule, HBTATHT, was synthesized. Thin film transistors based on unannealed HBTATHT showed a carrier mobility of 0.15 cm(2) V(-1) s(-1) (I(on/off) = 7.9 × 10(6)). Further, a solution processed solar cell made of HBTATHT exhibited promising power conversion efficiencies of 4.84% and 4.70% with PC(61)BM (1?:?0.8 wt ratio) and PC(71)BM (1?:?0.6 wt ratio), respectively.     

Effect of side chain conjugation lengths on photovoltaic performance of two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with side chains

Two new two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with different π conjugation lengths as side chains, called PDPPMTD and PDPPBTD , were designed and synthesized for use in polymer solar cells (PSCs). The resulting copolymers in the thin film state displayed broad absorption in the visible range with an absorption edge at over 1000 nm, and both had relatively low‐lying HOMO levels, at ?5.20 and ?5.18 eV for PDPPMTD and PDPPBTD , respectively. The power conversion efficiency (PCE) of the PSC that was based on PDPPBTD /PC61BM (w/w = 1:2) reached 4.10 % with a Jsc of 14.5 mA/cm2, a Voc of 0.59 V and an FF of 48%, while PDPPMTD /PC61BM (w/w = 1:2) had a PCE of 2.96% with a Jsc of 12.6 mA/cm2, a Voc of 0.60 V, and an FF of 39%. These results indicate that subtle tuning of the chemical structure can significantly influence Jsc and FF. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2878–2889