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.     

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.     

含Ullazine结构基元的共轭聚合物的合成及其光电性能研究

将Ullazine结构基元引入到聚合物主链或侧链中,分别与吡咯并吡咯二酮(DPP)、2,5-双(三甲基锡)噻吩共聚得到了二元共聚物PB和三元共聚物PT,分别利用凝胶渗透色谱和热重分析表征了聚合物的分子量和热稳定性,并研究了聚合物的光物理、电化学和光伏性能.基于共聚物PB和PT作为电子给体材料的聚合物太阳能电池器件测试结果表明,二元共聚物PB由于具有较低的能级水平从而获得较高开路电压,而侧链含Ullazine结构基元的三元共聚物PT具有更宽的吸收光谱和更高的空穴迁移率,获得了更高的短路电流和能量转换效率.     

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.     

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.     

Low-bandgap poly(thiophene-phenylene-thiophene) derivatives with broaden absorption spectra for use in high-performance bulk-heterojunction polymer solar cells

Two low-bandgap (LGB) conjugated polymers ( P1 and P2) based on thiophene-phenylene-thiophene (TPT) with adequate energy levels have been designed and synthesized for application in bulk-heterojunction polymer solar cells (PSCs). The absorption spectral, electrochemical, field effect hole mobility and photovoltaic properties of LGB TPT derivatives are investigated and compared with poly(3-hexylthiophene) (P3HT). Photophysical studies reveal bandgaps of 1.76 eV for P1 and 1.70 eV for P2, which could effectively harvest broader solar spectrum. In addition, the thin film absorption coefficients of P1 and P2 are 1.6 x 10 (5) cm (-1) (lambda approximately 520 nm) and 1.4 x 10 (5) cm (-1) (lambda approximately 590 nm), respectively. Electrochemical studies indicate desirable HOMO/LUMO levels that enable a high open circuit voltage while blending them with fullerene derivatives as electron acceptors. Furthermore, both materials show sufficient hole mobility (3.4 x 10 (-3) cm (2)/Vs for P2) allowing efficient charge extraction and a good fill-factor for PSC application. High-performance power conversion efficiency (PCE) of 4.4% is obtained under simulated solar light AM 1.5 G (100 mW/cm (2)) from PSC device with an active layer containing 25 wt% P2 and 75 wt% [6,6]-phenyl-C71-butyric acid methyl ester (PC 71BM), which is superior to that of the analogous P3HT cell (3.9%) under the same experimental condition.     

Organic bulk heterojunction photovoltaics incorporating cyclopenteno[60]fullerene monoadducts as n-type materials display superior power conversion efficiency than with PC61BM

Organic bulk heterojunction photovoltaics, merely incorporating monoadducts of cyclopenteno[60]fullerenes (CPFs) as n-type materials and P3HT as p-type materials, display superior power conversion efficiency up to 4.6 ± 0.12%, superseding that with PC₆₁BM/P3HT (3.8 ± 0.20%) for ca. 20%, under AM 1.5G irradiation―primarily attributed to the lack of homo-conjugation on CPFs and their higher LUMO energy levels.     

Conjugated polymer‐functionalized graphite oxide sheets thin films for enhanced photovoltaic properties of polymer solar cells

In this study, the maleimide‐thiophene copolymer‐functionalized graphite oxide sheets (PTM21‐GOS) and carbon nanotubes (PTM21‐CNT) were developed for polymer solar cell (PSC) applications. The grafting of PTM21‐OH onto the CNT and GO sheets was confirmed using FTIR spectroscopy. PTM21‐CNT and PTM21‐GOS exhibited excellent dispersal behavior in organic solvents. Better thermal stability was observed for PTM21‐CNT and PTM21‐GOS as compared with that for PTM21‐OH. In addition, the optical band gaps of PTM21‐GOS and PTM21‐CNT were lower than that of PTM21‐OH. We incorporated PTM21‐GOS and PTM21‐CNT individually into poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) blends for use as photoconversion layers of PSCs. Good distributional homogeneity was observed for PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend film. The UV–vis absorption peaks of the blend films red‐shifted slightly upon increasing the content of PTM21‐GOS or PTM21‐CNT. The band gap energies and LUMO/HOMO energy levels of the P3HT/PTM21‐GOS and P3HT/PTM21‐CNT blend films were slightly lower than those of the P3HT film. The conjugated polymer‐functionalized PTM21‐GOS and PTM21‐CNT behaved as efficient electron acceptors and as charge‐transport assisters when incorporated into the photoactive layers of the PSCs. PV performance of the PSCs was enhanced after incorporating PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Free Carrier Generation in Organic Photovoltaic Bulk Heterojunctions of Conjugated Polymers with Molecular Acceptors: Planar versus Spherical Acceptors

A comparative study of the photophysical performance of the prototypical fullerene derivative PC₆₁BM with a planar small‐molecule acceptor in an organic photovoltaic device is presented. The small‐molecule planar acceptor is 2‐[{7‐(9,9‐di‐n‐propyl‐9H‐fluoren‐2‐yl)benzo[c][1,2,5]thiadiazol‐4‐yl}methylene]malononitrile, termed K12. We discuss photoinduced free charge‐carrier generation and transport in blends of PC₆₁BM or K12 with poly(3‐n‐hexylthiophene) (P3HT), surveying literature results for P3HT:PC₆₁BM and presenting new results on P3HT:K12. For both systems we also review previous work on film structure and correlate the structural and photophysical results. In both cases, a disordered mixed phase is formed between P3HT and the acceptor, although the photophysical properties of this mixed phase differ markedly for PC₆₁BM and K12. In the case of PC₆₁BM the mixed phase acts as a free carrier generation region that can efficiently shuttle carriers to the pure polymer and fullerene domains. As a result, the vast majority of excitons quenched in P3HT:PC₆₁BM blends yield free carriers detected by the contactless time‐resolved microwave conductivity (TRMC) method. In contrast, approximately 85 % of the excitons quenched in P3HT:K12 do not result in free carriers over the nanosecond timescale of the TRMC experiment. We attribute this to poor electron‐transport properties in the mixed P3HT:K12 phase. We propose that the observed differences can be traced to the respective shapes of PC₆₁BM and K12: the three‐dimensional nature of the fullerene cage facilitates coupling between PC₆₁BM molecules irrespective of their relative orientation, whereas for K12 strong electronic coupling is only expected for molecules oriented with their π systems parallel to each other. Comparison between the eutectic compositions of the P3HT:PC₆₁BM and P3HT:K12 shows that the former contains enough fullerene to form a percolation pathway for electrons, whereas the latter contains a sub‐percolating volume fraction of the planar acceptor. Furthermore, the planar K12 co‐assembles with P3HT into a disordered, glassy phase that partly accounts for the poor electron‐transport properties, and may also enhance recombination due to the strong intermolecular interactions between the donor and the acceptor. The implication for the performance of organic photovoltaic devices with the two acceptors is also discussed.     

Cove‐Edge Nanoribbon Materials for Efficient Inverted Halide Perovskite Solar Cells

Two cove‐edge graphene nanoribbons hPDI2‐Pyr‐hPDI2 ( 1 ) and hPDI3‐Pyr‐hPDI3 ( 2 ) are used as efficient electron‐transporting materials (ETMs) in inverted planar perovskite solar cells (PSCs). Devices based on the new graphene nanoribbons exhibit maximum power‐conversion efficiencies (PCEs) of 15.6 % and 16.5 % for 1 and 2 , respectively, while a maximum PCE of 14.9 % is achieved with devices based on [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM). The interfacial effects induced by these new materials are studied using photoluminescence (PL), and we find that 1 and 2 act as efficient electron‐extraction materials. Additionally, compared with PC₆₁BM, these new materials are more hydrophobic and have slightly higher LUMO energy levels, thus providing better device performance and higher device stability.     

Phase diagram of P3HT:PC70BM thin films based on variable-temperature spectroscopic ellipsometry

In this article, we present the research on the influence of the composition of thin films of a blend of poly (3-hexylthiophene −2,5-diyl) - P3HT with fullerene derivatives [6,6]-phenyl-C71-butyric acid methyl ester – PC70BM and [6,6]-phenyl-C61-butyric acid methyl ester – PC60BM on their thermal transitions. The influence of molar mass (Mw) of P3HT (Mw = 65.2; 54.2 and 34.1 kDa) and PCBM (PC60BM – Mw = 911 g/mol and PC70BM – Mw = 1031 g/mol) is examined in details. The article presents significantly expanded research compared to our previous work on thermal transitions in thin films of blend P3HT (Mw = 65.2 kDa) with PC60BM. For this reason, we also compare current results with previous ones. Here, we present for the first time a phase diagram of thin films of the P3HT(Mw = 65.2 kDa):PC70BM blend using variable-temperature ellipsometry. Our research reveals the presence of characteristic temperatures of pure phases in thin films of P3HT: PCBM blends. It turns out that the cold crystallization temperature of the P3HT phase in P3HT(Mw = 65.2 kDa):PC70BM blend films is lower than corresponding temperature in P3HT(Mw = 65.2 kDa):PC60BM blend films. At the same time, the cold crystallization temperature of the PC70BM phase behaves inversely. We demonstrate also that variable-temperature spectroscopic ellipsometry is a very sensitive technique for studying thermal transitions in these thin films. In addition, we show that the entire phase diagram can be determined based on the raw ellipsometric data analysis, e.g. using a delta angle at wavelength λ = 280 nm.     

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/P₃ HT:PC₆₁ BM/C₆₀/Al were prepared by using P₃ HT as the donor material and PC₆₁ 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 C₆₀ as the hole blocking layer, the dark current density of the device can be reduced b...     

High performance low band gap polymer solar cells with a non-conventional acceptor

A novel C70 fullerene derivative was designed and synthesized by [4+2] cyclic addition reaction between indene derivative (methyl 1H-indene-3-carboxylate) and C70. The absorption and photoluminescence of H120 and its mixed films with different polymer donor materials were investigated, as well as its electrochemical property and electron mobility. It was found that H120 has 0.05 eV higher LUMO level than that of PC(70)BM. Its electron mobility reached 6.32 × 10(-4) cm(2) V(-1) s(-1), which is slightly lower than 9.55 × 10(-4) cm(2) V(-1) s(-1) of PC(70)BM. The photovoltaic devices based on P3HT, and two high efficiency low band gap polymers, PBDTTT-C and PBDTTDPP as donors, with H120 as an acceptor gave power conversion efficiencies of 4.2%, 6.0% and 6.2%, respectively.     

Structural tuning of low band gap intermolecular push/pull side-chain polymers for organic photovoltaic applications

A series of novel low band gap donor-acceptor (D-A) type organic co-polymers (BT-F-TPA,BT-CZ-TPA and BT-SI-TPA) consisting of electron-deficient acceptor blocks both in main chains (M1) and at the pendant (M2) were polymerized with different electron rich donor (M3-M5) blocks,i.e.,9,9-dihexyl-9H-fluorene,N-alkyl-2,7-carbazole,and 2,6-dithinosilole,respectively,via Suzuki method.These polymers exhibited relatively low band gaps (1.65-1.88 eV) and broad absorption ranges (680-740 nm).Bulk heterojunction (BHJ) solar cells incorporating these polymers as electron donors,blended with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as electron-acceptors in different weight ratios were fabricated and tested under 100 mW/cm2 of AM 1.5 with white-light illumination.The photovoltaic device containing donor BT-SI-TPA and acceptor PC71BM in 1:2 weight ratio showed the best power conversion efficiency (PCE) value of 1.88％,with open circuit voltage (Voc) =0.75 V,short circuit current density (Jsc) =7.60 mA/cm2,and fill factor (FF) =33.0％.     

Impact of Alkoxyl Tail of Fullerene Dyad Acceptor on Crystalline Microstructure for Efficient External Treatment-free Polymer Solar Cells with Poly(3-hexylthiophene) as Donor

A series of tri(alkoxyl)benzene-fullerene dyads(PCBB-Cn, n=4, 6, 8, 10, 12) with varied tri(alkoxyl) chain lengths was designed, synthesized and used as acceptor materials in polymer solar cells(PSCs). The five fullerene dyads possess similar absorption spectra in dilute solution, decreased glass-transition temperature(T_g) and gradually elevated lowest unoccupied molecular orbital(LUMO) energy levels from -3.87 eV to -3.73 eV with the increase of the alkoxy chain length. In the fabrication of PSCs with poly(3-hexylthiophene)(P3HT) as donor and the fullerene dyads as acceptor, PCBB-Cn with longer tri(alkoxyl) chains and lower T_g can induce crystalline structure of P3HT during spin-coating the photoactive layer at room temperature and form nanoscale phase separated interpenetrating network of P3HT:PCBB-Cn blend films, which results in the improvement of photovoltaic performance of PSCs. A power conversion efficiency of 3.03% for the PSCs based on P3HT:PCBB-C10 was obtained without thermal annealing or solvent annealing. The thermal and solvent annealing-free fabrication using the fullerene dyads as acceptor is very important for the roll to roll production of PSCs with flexible large area.     

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.     

Inverted polymer solar cells with a solution-processed zinc oxide thin film as an electron collection layer

A solution-processed zinc oxide (ZnO) thin film as an electron collection layer for polymer solar cells (PSCs) with an inverted device structure was investigated. Power conversion efficiencies (PCEs) of PSCs made with a blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) are 3.50% and 1.21% for PSCs with and without the ZnO thin film, respectively. Light intensity dependence of the photocurrent and the capacitance-voltage measurement demonstrate that the increased PCEs are due to the restriction of the strong bimolecular recombination in the interface when a thin ZnO layer is inserted between the polymer active layer and the ITO electrode. These results demonstrate that the ZnO thin film plays an important role in the performance of PSCs with an inverted device structure.     

Bay‐annulated indigo based near‐infrared sensitive polymer for organic solar cells

A new conjugated polymer (PBAIIDTT) based on bay‐annulated indigo and indacenodithieno[3,2‐b]thiophene was designed, synthesized, and characterized. PBAIIDTT shows strong absorption in 400–500 and 600–800 nm, and its HOMO and LUMO energy levels are −5.45 eV and −3.65 eV, respectively. In organic field‐effect transistors, the polymer exhibits a relatively high hole mobility of 0.39 cm² V⁻¹ s⁻¹. PBAIIDTT was added to poly(3‐hexylthiophene) (P3HT) and phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) based organic solar cells. Ternary blend solar cells with 10% PBAIIDTT show an increased short circuit current density due to the broadened photocurrent generated in the near‐infrared region, and a power conversion efficiency of 3.78%, which is higher than that of the P3HT:PC₆₁BM binary control devices (3.33%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 213–220     

An acrylated fullerene derivative for efficient and thermally stable polymer solar cells

The continuous microstructure evolution occurring in active layers of polymer-fullerene solar cells is one of the main causes for their device instability. With aim to tackle it, this work developed a new polymerizable fullerene acceptor, [6,6]-phenyl-C₆₁-butyl acrylate (PC₆₁BA). It was found that PC₆₁BA has similar light-absorption properties and HOMO and LUMO energy levels as [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), and can be converted into insoluble oligomers upon heating at 150 °C. Polymer-fullerene solar cells using poly(3-hexylthiophene) (P3HT) as donor and PC₆₁BA as acceptor exhibited an optimized efficiency of 3.54%, the performance comparable to P3HT/PC₆₁BM cells (optimized efficiency: 3.70%). But, the former possess much better thermal stability than the latter owing to aggregation suppression by the polymerized PC₆₁BA. These results indicate that PC₆₁BA, unlike most previous reported, is a unique polymerizable fullerene derivative that can be used alone as acceptor to achieve both efficient and thermally stable polymer solar cells.