Improving performance of polymer solar cell by adjusting crystallinity and nanoscale phase separation

In this paper, we report a high-performance P3HT/PCBM bulk-heterojunction solar cell with a power conversion efficiency of 4.85% fabricated by adjusting polymer crystallinity and nanoscale phase separation using an ultrasonic irradiation mixing approach of the polymer. The results of grazing incidence X-ray diffraction, UV/Vis spectroscopic, and atomic force microscopic measurements of the P3HT/PCBM blend films reveal that the P3HT/PCBM film fabricated by ultrasonic irradiation mixing P3HT and PCBM solutions for 10 min has higher degree of crystallinity, higher absorption efficiency, and better phase separation, which altogether account for the higher charge transport properties and photovoltaic cell performance.     

不同环境压强下溶剂退火对聚合物太阳能电池性能的影响

通过改变溶剂退火时的环境压强控制溶剂的蒸发速率,在不同压强下进行加压溶剂退火制备了基于聚-3己基噻吩:富勒烯衍生物(P3HT:PCBM)的体异质结聚合物太阳能电池。X射线衍射(XRD)、紫外-可见吸收光谱(UV-Vis)以及原子力显微镜(AFM)的测试结果表明,增大溶剂退火的环境气压改善了薄膜的结晶度,增强了有源层的光吸收,提高了P3HT和PCBM的相分离程度,更有利于激子的解离和载流子传输。与在常压下溶剂退火相比,在2.0 MPa压强下对有源层进行溶剂退火的器件的光电转换效率提高了29%,达到了3.69%。     

刮涂法制备聚合物薄膜太阳能电池

系统地研究了采用刮涂法制备聚合物薄膜太阳能电池时刮涂速度和基底温度对活性层厚度以及形貌的影响。当刮涂速度增加或者基底温度降低时,由于溶液粘度和表面张力的变化导致活性层厚度增加。与旋涂方法相比,刮涂方法制备的活性层薄膜具有更小的粗糙度和精细的相分离结构,从而减少了光伏电池的漏电流并提高了填充因子。利用刮涂方法制备的聚合物太阳能电池能量转换效率达到了4.2%。     

退火气压对于P3HT∶PCBM微观形貌及光伏性能的影响

通过精确设定不同的退火环境气压,实现对P3HT(Poly(3-hexylthiophene -2,5-diyl)与PCBM([6,6]-Phenyl C₆₁ butyric acid methyl ester)体系中聚噻吩结晶度以及共混相分离程度的控制,并在此基础上制备了结构为ITO/PEDOT∶PSS/P3HT∶PCBM/Al的正型光伏器件。在允许的压强设定范围内,器件各项性能参数均随退火环境压强的增大表现出先升高后下降的变化规律,并统一于气压设定为1 500 mTorr时获得最大值。从活性层的紫外-可见(UV-Vis)吸收光谱中发现P3HT在510 nm吸收峰以及550和600 nm肩峰附近的吸收强度随退火气压升高而增大,在气压为1 500 mTorr时达到最高,吸收强度的提升源于聚合物分子π—π堆叠的增加。原子力显微镜(AFM)进一步分析结果表明,高气压环境(>1 000 mTorr)能够促进P3HT∶PCBM共混组分在退火过程中形成较大程度的相分离,而当环境压强合适时(1 500 mTorr)适度的相分离利于聚合物形成良好有序结晶,从而能够提升活性层内部载流子传输能力,保证较高的短路电流与填充因子,制备的器件也因此表现出良好的光伏性能,光电转化效率达到3.56%。     

The inverted solar cells with the polymer:fullerene blend film possessing a stratified composition profile

The inverted polymer:fullerene solar cells with structure of ITO/TiO₂/P3HT:PCBM/MoO₃/Al have been fabricated, where P3HT and PCBM stand for poly (3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methyl ester, respectively. It is discovered that the P3HT:PCBM blend film manipulated into the improved stratification structure, characterized as P3HT crystallite-rich zone close to the top surface and PCBM constituent-rich zone adjacent to the bottom surface, can offer nearly the same power conversion efficiency of solar cell, compared to the one grown into the bulk heterojunction structure, characterized as the bicontinuous interpenetrating network of P3HT and PCBM. We provide an alternative insight to the morphology control of inverted polymer:fullerene solar cells.     

NiO_x作为空穴传输层对有机太阳能电池光吸收的影响

基于多层膜系模型的传输矩阵方法、麦克斯韦方程和光子吸收方程,研究了NiOx作为替代3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐(PEDOT:PSS)的空穴传输材料对聚3-己噻吩(P3HT)和富勒烯衍生物([6,6]-phenyl-C61-butyric acid methyl ester,PC61BM)共混体异质结有机太阳能电池器件内部光电场分布和光吸收特性的影响.分别制备了以NiOx和PEDOT:PSS为空穴传输层,P3HT:PCBM为活性层的有机太阳能电池,并通过数值模拟的方法比较了NiOx和PEDOT:PSS两种空穴传输材料对器件光伏特性的影响.结果表明:10 nm的NiOx空穴传输层器件比40 nm的PEDOT:PSS器件获得了更大的短路电流和填充因子,并具有更高的能量转化效率.     

Preheated solvent exposure on P3HT:PCBM thin film: A facile strategy to enhance performance in bulk heterojunction photovoltaic cells

In this study, we explored the ability of a preheated solvent (methanol) to induce characteristic changes at the organic active layer/metal interface, thereby improving the performance of fabricated organic photovoltaic (OPV) cells composed of poly(3-hexylthiopene) (P3HT) and a [6,6]-phenyl-C₇₁-butyric acid methyl ester (PCBM) photoactive blend. Our results demonstrate that exposure to methanol (at room temperature, or preheated at 45 °C or 65 °C) improves the performance of the fabricated OPV cells. After preheated methanol exposure, the P3HT:PCBM thin films were tested for crystallinity, morphology, mobility, and photovoltaic characteristics. Our results revealed that use of the preheated solvent on the organic active layer significantly influences the micro/nano scale morphology and phase segregation of the P3HT:PCBM thin films, as well as the charge carrier mobility. It is hypothesized that the side chain ordering of P3HT and redistribution of PCBM could be results of the modified active layer. Consequently, OPV cells modified with the methanol preheated at 65 °C exhibited a power conversion efficiency (PCE) of 3.36%, with open-circuit voltage of 0.59 V, short-circuit current density of 13.83 mA/cm², and fill-factor of 0.41. In contrast, the unmodified P3HT:PCBM thin film (without methanol exposure) showed a PCE of only 2.13%.     

Effect of solvents on the performance and morphology of polymer photovoltaic devices

In the polymer photovoltaic devices (PVDs), the performance of devices was strongly influenced by region-regularity, number average molecular weight and casting solvents of polymers. In this work, we fabricated p–n bulk-hetero-junction PVDs based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₀-butyric acid methyl ester (PCBM) using various solvents such as chloroform (CF), chlorobenzene (CB), dichlorobenzene (DCB), and mixed solvent (CF/CB, CF/DCB). Thin film of active layer with P3HT/PCBM was prepared by spin coating and thermal annealing at 150 °C with fixed thickness about 110 nm by adjusting solution concentration. The crystalline morphology and layered phase for the active layer were studied by atomic force microscopy and X-ray diffraction, respectively. We investigated the performance of solar cells according to different morphology and crystallinity of active layer by various solvent and mixed solvent.     

掺杂石墨烯量子点对P3HT:PCBM太阳能电池性能的影响

为研究掺杂石墨烯量子点(GQDs)对聚合物电池的影响,采用溶剂热法制备了GQDs,掺杂到聚3-己基噻吩和富勒烯衍生物(P3HT∶PCBM)中作光敏层制备了聚合物太阳能电池。掺杂不同浓度的GQDs后,聚合物电池的开路电压和填充因子都比未掺杂器件高。GQDs掺杂质量分数为0.15%时,形成的掺杂薄膜平整、均匀,填充因子提高了17.42%。GQDs经还原后,随还原时间的延长,填充因子FF增大。到45 min时,电池的FF基本稳定,从31.57%提高至40.80%,提高了29.24%。退火后,获得了最佳的掺杂GQDs的聚合物太阳能电池,开路电压Voc为0.54 V,填充因子FF为55.56%,光电转换效率为0.75%。     

二甲基亚砜添加剂对聚合物太阳能电池性能的影响

研究了二甲基亚砜(DMSO)掺杂浓度对基于聚(3-己基噻吩)(P3HT)和(6,6)-苯基碳60丁酸甲酯(PCBM)为有源层的聚合物太阳能电池性能影响。结果表明,掺杂DMSO可以提高聚合物太阳能电池短路电流密度和填充因子。DMSO掺杂质量比为3%时,电池短路电流密度提高到7.88 mA·cm-2,填充因子为55.5%。能量转换效率达到2.54％,相比没有掺杂DMSO的电池,能量转换效率提高了17%。傅里叶变换红外光谱被用于鉴定和分析掺杂DMSO对材料P3HT∶PCBM化学性质的影响。傅里叶变换红外光谱表明,掺杂后P3HT和PCBM的化学性质都没有改变。为分析掺杂DMSO改善器件能量转换效率的原因,通过紫外-可见光谱和电流密度-电压特性曲线分别表征器件的光吸收能力以及电致发光器件的载流子迁移率。与P3HT∶PCBM薄膜相比,P3HT∶PCBM∶DMSO薄膜在可见光范围内的吸收峰有明显红移且吸收强度增强。可见光吸收的改善是实现短路电流密度提高的有力保障。太阳能电池性能的增强是因为DMSO的掺杂提高了P3HT∶PCBM的载流子迁移率和吸收光谱宽度。     

Composition-dependent phase separation effects of organic solar cells using P3HT:PCBM as active layer and chromium oxide as hole transporting layer

Phase separation of the poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) active layer (ATL) was investigated by varying their relative ratio in the organic solar cells (OSCs). With the help of the UV/visible spectrophotometer, optical microscopy and scanning electron microscope, we found that the cluster of PCBM at the interface or surface was affected by Al cathode, the composition of the blends and thermal annealing. The disc-like shape crystals of PCBM substituted for the needle-like ones at higher PCBM compositions at the ATL/Al interface, which led to stronger contacts and bigger contact area. It could make short circuit current density increase, but may affect the blend morphology and result in parallel resistance and open circuit voltage decreased with the PCBM ratio increasing from 40 to 60%. The microstructure of the P3HT:PCBM ATL, determined by the composition dependent phase separation, supported the optimized performance of the OSCs with the composition of 40-50% PCBM.     

Improved performance of polymer solar cells by using inorganic,organic, and doped cathode buffer layers

The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester(P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer(CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode(OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs_2CO_3, bathophenanthroline(Bphen), and 8-hydroxyquinolatolithium(Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies(PCEs) of 3.0%–3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs_2CO_3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL.     

三元P3HT:PTB7-Th:PCBM聚合物太阳能电池性能的研究

将窄带隙聚合物PTB7-Th作为第三种物质掺入到P3HT:PCBM中制备了双给体结构的三元聚合物太阳能电池, 并且通过改变PTB7-Th的浓度来研究PTB7-Th对器件性能的影响. 研究发现, 掺入PTB7-Th后, 聚合物太阳能电池的短路电流和填充因子同时获得了提高, 使器件的光电转换效率得到了改善. 进一步分析表明, PTB7-Th的加入能够拓宽活性层的吸收光谱, 增加活性层吸收的光子数目, 有利于短路电流的提升. PTB7-Th与P3HT之间以电荷转移的形式相互作用, 这种作用方式有利于激子的解离, 从而使器件的填充因子得到了提高.     

微波退火对聚合物太阳能电池性能的提高

利用微波对基于poly(3-hexylthiophene) (P3HT)和 -phenyl-C61-buytyric acid methyl ester (PCBM) 的体异质结太阳能电池进行退火处理,提高了器件的效率。使用的微波频率为2.45 GHz,当处理时间为10 min时,获得的短路电流为9.13 mA/cm²,开路电压为0.63 V,能量转化效率为3.21%,其性能参数完全可以与普通真空干燥箱退火相比拟。研究了微波对活性层的作用,从微波退火处理后的UV-Vis吸收谱和SEM图发现,微波退火主要改善了活性层的粗糙度,提高了相分离程度,有利于激子在界面处的解离和载流子的传输。     

P3HT:PCBM薄膜成膜过程对聚合物太阳能电池性能的影响

P3HT:PCBM薄膜的快速和缓慢成膜过程能显著的改变异质结聚合物太阳能电池性能.通过调节旋转时间以及薄膜退火前的间隔时间,研究了P3HT:PCBM混合薄膜缓慢生长所需最佳时间.结果表明,在转速800 r·min-1下旋涂薄膜,经过50～80 s的旋涂,接着放置样品薄膜30 min以上,然后再对薄膜进行退火处理,电池效...     

纳米银增强聚合物太阳能电池光吸收的研究

基于共轭聚合物给体材料P3HT和富勒烯衍生物受体材料PCBM共混的体异质结结构 的聚合物太阳能电池因其空穴载流子迁移率低而限制了P3HT:PCBM功能层厚度, 从而影响了器件对入射光的吸收. 在聚合物功能层内引入金属纳米颗粒可以利用金属表面等离子体效应增强器件内电场并改善器件的光吸收. 本文基于时域有限差分法(finite difference time domain, FDTD)方法模拟得到了聚合物功能层内包含了直径为50 nm纳米银球并且球间距为50 nm的聚合物太阳能 电池器件在波长分别为400 nm和500 nm照射时的二维光电场分布以及入射角分别为15°, 45°, 60°时包覆纳米银聚合物功能层横截面内的光电场强度分布; 计算得到了银纳米颗粒尺寸分别为10 nm, 20 nm和50 nm时以及分布在空穴传输层PEDOT:PSS的纳米银器件的光吸收; 并计算了斜入射时包覆纳米银的聚合物功能层光吸收. 理论分析表明: 聚合物功能层加入纳米银球后, 因为纳米银球的表面等离子体效应使入射光在功能层内散射增强而使器件内的光电场重新分布; 直径较大的纳米银颗粒能产生大角度的光散射, 更有利于聚合物功能层对光的吸收. 这里, 基于有机银盐还原法制备了纳米银颗粒并制备了银等离子体增强的聚合物太阳能电池, 其结构为: glass/ITO (～100 nm)/PEDOT:PSS (40 nm)/P3HT:PCBM (～100 nm)(nano-Ag)/LiF (1 nm)/Al (120 nm). 该器件与平板器件的性能对比实验证实: 通过在聚合物功能层内上引入纳米银颗粒可以有 效增加器件光吸收并改善器件电学性能, 器件外量子效率在520 nm处最大增加了17.9%. 关键词： 纳米银 表面等离子体共振 时域有限差分 聚合物太阳能电池     

Fe3O4纳米粒子对P3HT:PCBM电池的影响

为了提高太阳能电池的性能,研究磁性纳米粒子在外加磁场的作用下对聚合物太阳能电池有源层P3HT:PCBM成膜及太阳能电池性能的影响。本文采用热分解法制备了磁性Fe₃O₄纳米粒子,将不同质量分数的Fe₃O₄纳米粒子掺入到P3HT:PCBM溶液中,旋涂后在外加磁场的作用下自组成膜。通过TEM、XRD对制备的Fe₃O₄纳米粒子进行表征,并利用偏光显微镜、原子力显微镜对成膜质量进行探究。结果表明,采用热分解法制备的Fe₃O₄纳米粒子直径在10 nm左右,在外加磁场作用下,Fe₃O₄纳米粒子对成膜有一定的调控作用。当Fe₃O₄纳米粒子掺杂质量分数为1%时,太阳能电池器件的开路电压增加3.77%,短路电流增加24.93%,光电转换效率提高7.82%。     

Raman spectroscopic identification of fullerene inclusions in polymer/fullerene blends

Thin films of the conjugated polymer poly(3‐hexylthiophene) (P3HT) and blends of the soluble fullerene derivative[6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) with P3HT—a well studied but not completely understood donor–acceptor system for organic solar cells—have been studied by means of UV–visible absorption and resonant Raman spectroscopy. Additionally, we have employed atomic force microscopy phase imaging to characterize the nanomorphology of the P3HT : PCBM thin film, revealing a close intermixing of two phases with domain sizes ranging from a few to several tens of nanometers. A systematic analysis of pristine polymer and blend Raman spectra provides evidence that features attributable to PCBM, possibly even depending on the charge state of the fullerene molecule, can be observed. Hence our results suggest that fullerene inclusions in polymer/fullerene blends can be identified via Raman spectroscopy. Copyright © 2011 John Wiley & Sons, Ltd.     

Metal-electrode-free inverted organic photovoltaics using electrospray-deposited PEDOT:PSS and spin-coated HAT-CN exciton blocking layer

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) films were fabricated using an electrospray deposition (ESD) method. The ESD PEDOT:PSS films exhibited higher PSS content on the surface than spin-coated PEDOT:PSS films, which results in a higher work function. Based on this result, metal-electrode-free inverted organic photovoltaics (OPVs) were fabricated. The ESD PEDOT:PSS was used as the top electrode on the poly(3-hexythiophene-2,5-diyl) (P3HT):[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) light-absorbing layer. The power conversion efficiency (PCE) of OPVs was significantly increased with the 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile layer. The improved PCE would be attributed to the suppression of exciton quenching at the P3HT:PCBM and PEDOT:PSS interface.     

Correlation between spectroscopic and morphological properties of composite P3HT/PCBM nanoparticles studied by single particle spectroscopy

We report the fabrication and characterization of composite nanoparticles consisting of a conducting polymer, poly-3-hexylthiophene (P3HT), doped with varying amounts of [6,6]-phenyl C61-butyric acid methyl ester (PCBM), a material blend that is commonly applied in bulk heterojunction organic photovoltaic devices (OPVs). Single particle spectroscopy (SPS) studies, where nanoparticles are studied one particle at a time, reveal that these nanoparticles have spectroscopic characteristics consistent with the existence of two types of crystalline nanodomains, one with a higher energy emission at 660 nm and one with a lower energy emission at 720 nm. In addition, the occurrence of emission at lower peak energy increases with increasing PCBM doping levels, and the intensity of the lower energy peak emission increases with respect to the higher energy peak emission as well. These data reveal a PCBM concentration dependent formation of two types of P3HT crystalline nanodomains in P3HT/PCBM composite nanoparticles, where the lower energy crystal structure becomes more favored with higher PCBM concentration. This work provides a molecular scale insight in the correlation between changes in morphology of conjugated polymer materials with different weight percentages of fullerene dopants.