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.     

Charge transport in polythiophene:fullerene:nanotube bulk heterojunction photovoltaic devices investigated by impedance spectroscopy

P3HT:PCBM bulk heterojunction devices incorporating SWNTs, which are predominantly metallic in character, have been analyzed using impedance spectroscopy to understand the effect of SWNTs on their charge carrier transport properties. SWNTs reduce the effective lifetime of injected charge carriers. Frequency dependence of capacitance and conductance of P3HT:PCBM devices show monotonic variations without any clear peak positions. Simulations of the complex admittance of the P3HT:PCBM devices under trap free space charge limited current within the framework of Scher–Montrol theory are used to qualitatively show that such characteristics are a signature of charge transport which is highly dispersive in nature. The position of peak τ_peak in the imaginary part of impedance Im(Z), which is essentially same as the first transition frequency of Cole–Cole plot, has a direct relation with the effective dc mobility of charge carriers which varies with dispersion parameters. Using the dc mobility values and the voltage variation of peak frequency of Im(Z), the ratio of τ_dc to τ_peak has been calculated. The magnitude of this ratio is indicative of the degree of dispersiveness in transport. It has been shown that, SWNTs at low concentrations tend to reduce the dispersiveness in charge transport.     

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%.     

Improving the performance of polymer solar cells by adjusting the 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 the polymer crystallinity and nanoscale phase separation using an ultrasonic irradiation mixing approach for the polymer. The grazing incidence X-ray diffraction, UV/Vis spectroscopic, and atomic force microscopic measurement results for the P3HT/PCBM blend films reveal that the P3HT/PCBM film fabricated by ultrasonic irradiation mixing of the P3HT and PCBM solutions for 10 min has a higher degree of crystallinity, a higher absorption efficiency, and better phase separation, which together account for the higher charge transport properties and photovoltaic cell performance.     

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.     

Post-fabrication annealing effects on the performance of P3HT:PCBM solar cells with/without ZnO nanoparticles

In this study, P3HT:PCBM organic photovoltaic (OPV) devices, with or without ZnO nanoparticles buffer layer between the photoactive layer (P3HT:PCBM) and the cathode (Al top electrode), were fabricated. The devices were annealed at 145 °C either before or after depositing the top electrode. The objective of this study was to investigate the effects of the ZnO buffer layer and pre-/post-fabrication annealing on the general performance of these devices. The short-circuit current density (J_SC), open-circuit voltage (V_OC) and the external quantum efficiency (EQE) of the OPV devices were improved by the insertion of the ZnO layer and post-fabrication annealing. The post-fabrication annealed devices, with or without the ZnO layer, exhibited higher values of J_SC, V_OC and EQE than those of similar devices annealed before depositing the Al metal. This can be attributed to, among other things, improved charge transport across the interface between the photoactive layer and the Al top electrode as a result of post-annealing induced modification of the interface morphology.     

The improvement of bulk-heterojunction order in polymer photovoltaic device

The blend morphology and vertical arrangement are critical to the performance of organic bulk-heterojunction photovoltaic devices.In the present paper,the authors proposed a new annealing method that controls the blend morphology and vertical arrangement of two materials by means of simultaneously applying external electrical field and violet irradiation on the active layer of poly(3-hexylthiophene) (P3HT) and -phenyl C61-butyric acid methyl ester(PCBM) during annealing process.By using this annealing metho...     

Annealed Treatment Effect in Poly（3-hexylthiophene）：Methanofullerene Solar Cells

Polymer photovoltaic devices based on poly（3-hexylthiophene） （P3HT） ： [6,6]-phenyl-C61-butyricacid methyl ester （PCBM） 1：1 weight-ratio blend are reported. The effects of various annealing treatments on the device performance are investigated. Thermal annealing shows significant improvement of the device performances. For devices at 130℃ annealing, maximum power conversion efficiency （PCE） of 3.3% and All factor up to 60.3% is achieved under air mass 1.5, 100 m W/cm^2 illumination. We discuss the effect of thermal annealing by the results of ultraviolet-visible absorption spectroscopy （UV-vis）, dark current-voltage curve, atomic force microscopy （AFM）.     

Study of a ternary blend system for bulk heterojunction thin film solar cells

In this research, we report a bulk heterojunction(BHJ) solar cell consisting of a ternary blend system. Poly(3-hexylthiophene) P3 HT is used as a donor and [6,6]-phenyl C61-butyric acid methylester(PCBM) plays the role of acceptor whereas vanadyl 2,9,16,23-tetraphenoxy-29 H, 31H-phthalocyanine(VOPc Ph O) is selected as an ambipolar transport material. The materials are selected and assembled in such a fashion that the generated charge carriers could efficiently be transported rightwards within the blend. The organic BHJ solar cells consist of ITO/PEDOT:PSS/ternary BHJ blend/Al structure. The power conversion efficiencies of the ITO/ PEDOT:PSS/P3HT:PCBM/Al and ITO/PEDOT:PSS/P3HT:PCBM:VOPcPhO/Al solar cells are found to be 2.3% and 3.4%, respectively.     

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.     

空间电荷限制电流法测量共混体系中空穴的迁移率

载流子迁移率测量是有机半导体材料与器件研究中的重要内容之一.以聚噻吩为电子给体材料, C₆₀的衍生物为电子受体材料,制备了一种单电荷传输器件.用空间电荷限制电流法测出了不同溶剂形成的 活性层及不同温度热处理后器件中空穴的迁移率.结果表明:器件中电荷的传输J-V曲线符合Mott-Gurney方程, 不同溶剂形成活性层中空穴具有不同的迁移率,高沸点的溶剂1, 2-二氯苯形成的活性层具有较高的空穴迁移率, 热处理有利于器件中空穴迁移率的提高.同时还进一步分析了空穴迁移率变化的原因.     

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.     

阴极缓冲层对于不同惰性气氛气压退火处理的 P3HT∶PCBM光伏性能的影响

制备了基于聚(3-己基噻吩)(P3HT)与可溶性富勒烯衍生物(PCBM)共混体系的太阳能电池。通过改变活性层退火处理时惰性气氛环境的压强,在一定程度上实现对共混物相分离以及聚合物结晶度的控制,研究了LiF作为阴极缓冲层对不同压强下退火处理的器件性能的影响。实验发现,LiF层的关键作用在于稳定开路电压以及提升短路电流,从而带动转化效率整体提升。结果表明,LiF层可以改善器件活性层与金属电极接触的界面形态,而器件的最终性能则由活性层的微观形貌与电极界面形态共同决定。     

热处理对不同溶剂制备的共混体系太阳电池性能影响

本文以poly(3-hexylthiophene) (P3HT)为电子给体材料, -phenyl C₆₁-butyric acid methyl ester (PCBM)为电子受体材料, 制备出不同溶剂形成的共混体系太阳电池.从薄膜的紫外—可见吸收光谱(UV-vis)、光致发光谱(PL)、原子力表面图形(AFM)等方面,分析了热处理对不同溶剂制备的共混体系太阳电池性能的影响.结果表明较高沸点的溶剂有利于P3HT:PCBM共混体系中P3HT的有序化排列,薄膜的紫外—可见吸收和光致发光增 关键词： 热处理 不同溶剂 太阳电池 性能     

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.     

Plasmon enhanced light absorption in bulk heterojunction organic solar cells

Silver nanospheres (Ag NSs) buffer layers were introduced via a solution casting process to enhance the light absorption in poly (3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) bulk heterojunction organic solar cells. These Ag NSs, as surface plasmons, could increase the optical electric field in the photoactive layer whilst simultaneously improving the light scattering. As a result, this buffer layer improves the light absorption of P3HT:PCBM blend and consequently improves the external quantum efficiency (EQE) of organic solar cells. In this work, different sizes of Ag NSs plasmon‐enhanced layer were investigated, with the aim of optimizing the performance of devices. UV‐vis spectrometer measurement demonstrates that the total optical absorption of P3HT:PCBM blend films in the spectral range of 350–650 nm is increased by ～4 and 6% with incorporation of the 20 and 40 nm Ag NSs, respectively. The J_sc was shown to increase by ～21 and 24% for 20 and 40 nm Ag NSs, respectively. This is due to the extra photogenerated excitons by the plasmonic resonance of Ag NSs. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Field-effect transistor structures on the basis of poly(3-hexylthiophene), fullerene derivatives [60]PCBM, [70]PCBM,and nickel nanoparticles

Organic field-effect transistor (OFET) structures with the active layers on the basis of composite films of semiconductor polymer poly(3-hexylthiophene) (P3HT), fullerene derivatives [60]PCBM, [70]PCBM, and nickel (Ni) nanoparticles are obtained, and their optical, electrical, and photoelectrical properties are studied. It is shown that introducing Ni nanoparticles into P3HT: [60]PCBM and P3HT: [70]PCBM films leads to an increase in the absorption and to quenching of photoluminescence of the composite in the 400–600 nm spectral band due to the plasmon effect. In P3HT: [60]PCBM: Ni and P3HT: [70]PCBM: Ni OFET structures at the P3HT: [60]PCBM and P3HT: [70]PCBM concentrations of ~1: 1 and Ni concentrations of ~3–5 wt %, current–voltage (I–V) characteristics typical of ambipolar OFETs with the dominant hole conduction are observed. The charge-carrier (hole) mobilities calculated from the I–V characteristic at V_G =–10 V were found to be ~0.46 cm²/(V s) for P3HT: [60]PCBM: Ni and ~4.7 cm²/(V s) for P3HT: [70]PCBM: Ni, which means that the mobility increases if [60]PCBM in the composition is replaced with [70]PCBM. The effect of light on the I–V characteristics of P3HT: [60]PCBM: Ni and P3HT: [70]PCBM: Ni OFETs is studied.     

非晶/结晶共混对聚合物光伏电池性能的影响

以局域规整聚（3-己基噻吩） （P3HT）制备了TiO₂/聚合物型双层结构光伏电池.利用稳态电流-电压测试和动态强度调制光电压谱,结合差热分析、吸收光谱和荧光光谱, 研究了非晶支化聚亚乙基亚胺（BPEI）作为P3HT膜层的添加成分对TiO₂/P3HT双层电池性能的影响.由于P3HT链的高结晶性,使得TiO₂/P3HT界面接触不好,导致电池性能差.当在P3HT中共混重量比W_BPEI/P3HT=1％—5％的BPEI时,电池性能得到显著改善;尤其是当W_BPEI/P3HT= 1％时,电池表现出近0.8V的开路电压和20μA/cm²的短路电流.结果表明BPEI对电池性能的影响不是源于P3HT-BPEI共混体系光学性能的变化,而主要是由于其改变了TiO₂/P3HT界面接触性能.BPEI对TiO₂/P3HT界面接触有两个相互竞争的影响,这取决于P3HT-BPEI共混体系的组成.一方面,通过降低P3HT的结晶度和增强与TiO₂表面的相互作用,改善P3HT链在TiO₂ 表面的附着;另一方面,当BPEI含量过高时,BPEI在TiO₂表面的附着量将增加,反而会阻碍P3HT与TiO₂表面的接触.良好的TiO₂/P3HT界面接触有利于提高激子的界面分离效率、光生电子的寿命和电池效率.本文结果有望为聚合物光伏电池性能的改善提供新的认识和方法. 关键词： 聚（3-己基噻吩） 二氧化钛 共轭聚合物 光伏电池     

Influence of fullerene derivative replacement with TiO2 nanoparticles in organic bulk heterojunction solar cells

In an effort to develop hybrid organic solar cells with improved power conversion efficiency (PCE), devices based on poly (3-hexylthiophene) (P3HT):phenyl C₆₁-butyric acid methyl ester (PCBM) active layer and poly (3,4-ethylenedioxythiophene) (PEDOT):poly (styrenesulfonate) (PSS) buffer layers were prepared. A systematic replacement of PCBM was achieved by introducing nanostructured TiO₂ (∼15 nm particle size), dissolved separately in chlorobenzene (CB) and 1,2 –dichlorobenzene (DCB), to the (P3HT:PCBM) active layer while keeping a fixed amount for P3HT. To understand the effect of fullerene replacement with the inorganic metal oxide nanoparticles on different properties of resulting devices, a variety of techniques such as Current–Voltage (J–V) characteristics, Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM), Ultravoilet-Visible (UV–Vis) Spectrophotometry and External Quantum Efficiency (EQE) were employed. The addition of TiO₂ nanoparticles in the active layer improved the power conversion efficiency (PCE) of P3HT:PCBM devices. The addition of TiO₂ nanoparticles using CB as solvent enhanced the absorption in visible region and also introduced a red shift in the absorption spectra. A significant increase in EQE was observed for devices with TiO₂ nanoparticles in the active layer. Mixing TiO₂ also increased the surface roughness of the active layer where TiO₂ nanoparticles were found to agglomerate as their concentration increased relative to fullerene derivative. A complete agglomeration of TiO₂ was observed in the absence of PCBM.     

Effect of slow-solvent-vapour treatment on performance of polymer photovoltaic devices

In this work, enhanced poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulkheterojunction photovoltaic devices are achieved via slow-solvent-vapour treatment. The correlations between the morphology of the active layer and the photovoltaic performance of polymer-based solar cell are investigated. The active layers are characterized by atomic force microscopy and optical absorption. The results show that slow-solventvapour treatment can induce P3HT self-organization into an ordered structure, leading to the enhanced absorption and efficient charge transport.