Fullerene solubility–current density relationship in polymer solar cells

During the last decade polymer solar cells have undergone a steady increase in overall device efficiency. To date, essential efficiency improvements of polymer–fullerene solar cells require the development of new materials. Whilst most research efforts aim at an improved or spectrally extended absorption of the donor polymer, not so much attention has been paid to the fullerene properties themselves. We have investigated a number of structurally related fullerenes, in order to study the relationship between chemical structure and resulting polymer–fullerene bulk heterojunction photovoltaic properties. Our study reveals a clear connection between the fullerene solubility as material property on one hand and the solar cells short circuit photocurrent on the other hand. The tendency of the less soluble fullerene derivates to aggregate was accounted for smaller current densities in the respective solar cells. Once a minimum solubility of approx. 25 mg/ml in chlorobenzene was overcome by the fullerene derivative, the short circuit current density reached a plateau, of about 8–10 mA/cm². Thus the solubility of the fullerene derivative directly influences the blend morphology and displays an important parameter for efficient polymer–fullerene bulk heterojunction solar cell operation. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Effect of a buffer layer, composition and annealing on the performance of a bulk heterojunction polythiophene/fullerene composite photovoltaic device

Post-annealing of P3HT/C₆₀-based plastic solar cells, composite ratio and, incorporation of a buffer layers at the ITO–polymer/fullerene composite interface and the polymer/fullerene composite–Al interface have shown significant improvement in the performance of the photovoltaic device, both in terms of open-circuit voltage and short-circuit current. The annealing temperature, time duration and P3HT/C₆₀ composite ratios have been optimized for the best performance of typical ITO/PEDOT:PSS/P3HT:C₆₀/LiF/Al solar cell. The C₆₀ content is very crucial because it improves the photocurrent in the beginning but after a certain value it leads to decrease in absorption, thereby decreasing the photocurrent.     

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.     

新型高效聚合物/富勒烯有机光伏电池研究进展

有机聚合物/富勒烯本体异质结光伏电池以其不断提高的能量转换效率受到了研究人员的广泛关注, 近年来成为光伏电池研究领域的热点之一. 本文主要通过对聚合物/富勒烯太阳能电池的内部机理,包括光吸收、激子扩散和解离以及自由载流子输运和提取等关键科学问题, 从器件材料和结构优化、形貌控制和界面修饰等不同侧面介绍了提高聚合物/富勒烯太阳能电池性能的方法, 讨论了各种器件的结构和能量转换效率, 对于进一步开展这方面的研究工作指明了方向, 最后对其未来的发展前景做出了展望.     

Cu（In,Ga）Se2 Thin Films on Flexible Polyimide Sheet： Structural and Electrical Properties versus Composition

The structural and electrical properties of Cu（In,Ga）Se2 （CIGS） films grown on polyimide （PI） sheet using the three-stage co-evaporation process are investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM）, Raman spectra, and Hall effect measurements, respectively. The results show that the properties of CIGS films on PI sheet are strongly dependent on the compositional ratio of Cu/（In＋Oa） （Cu/Ⅲ）. In contrast to the non-stoichiometric CIGS films, stoichiometric CIGS films show better structural and electrical properties, such as a relatively larger grain size, lower resistivity and higher carrier concentration. The flexible CIGS solar cells on PI sheet with the conversion efficiencies of 9.7% and 6.6% are demonstrated for the CIGS absorber layer with Cu/Ⅲ of 0.96 and 0.76, respectively （active area, 0.20cm^2）. The cell efficiency for Cu-poor CIGS films is limited by a relatively lower open circuit voltage and fill factor.     

Inverse relation between photocurrent and absorption layer thickness in polymer solar cells

Organic solar cells based on polymer–fullerene bulk heterojunctions were optimised with respect to the short circuit photocurrent by means of optical modelling. Due to interference effects present in the thin film multilayer device, an inverse relation between active layer thickness and photocurrent was predicted and experimentally verified. Optimised photovoltaic devices yield power conversion efficiencies of 4%. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Zinc oxide nanostructures for applications as ethanol sensors and dye-sensitized solar cells

ZnO nanostructures were prepared by thermal oxidation technique for applying as ethanol sensors and dye-sensitized solar cells. To improve sensitivity of the sensor based on ZnO nanostructures, gold doping was performed in ZnO nanostructures. Gold-doped with 0%, 5%, and 10% by weight were investigated. The improvement of sensor sensitivity toward ethanol due to gold doping was observed at entire operating temperature and ethanol concentration. The sensitivity up to 145 was obtained for 10% Au-doped ZnO sensor. This can be explained by an increase of the quantity of oxygen ion due to catalytic effect of gold. Also, it was found that oxygen ion species at the surface of the Au-doped ZnO sensor remained O²⁻ as pure ZnO sensor. For dye-sensitized solar cell application, the dye-sensitized solar cell structure based on ZnO as a photoelectrode was FTO/ZnO/Eosin-Y/electrolyte/Pt counter electrode. ZnO with different morphologies of nanobelt, nano-tetrapod, and powder were investigated. It was found that DSSCs with ZnO powder showed higher photocurrent, photovoltage and overall energy conversion efficiencies than that of ZnO nanobelt and ZnO nano-tetrapod. The best results of DSSCs were the short circuit current (J_sc) of 1.25 mA/cm², the open circuit voltage (V_oc) of 0.45 V, the fill factor (FF) of 0.65 and the overall energy conversion efficiency (η) of 0.68%.     

Effects of rubrene mixing on the electronic structures of donor/acceptor interface in organic photovoltaic device

Rubrene mixing has been shown to be an effect mean for enhancing both the open circuit voltage (Voc) and the short-circuit current (Jsc) of copper-phthalocyanine (CuPc)/fullerene (C₆₀) based solar cell. While the increase in Jsc can be readily explained by the additional rubrene absorption and the introduction of a bulk heterojunction; causes for Voc increase are still not clear. The energy offset between the highest occupied molecular orbital (HOMO) level of donor and the lowest unoccupied molecular orbital (LUMO) level of acceptor (HOMO_D-LUMO_A) at the CuPc/C₆₀ interface was found to increase substantially upon rubrene mixing in either side of the interface. As the HOMO_D-LUMO_A is generally considered to limit the Voc, its increase agrees well with the device results. Energy level bending and associated built-in electric fields were also observed and their possible implications to device performance are discussed.     

Fabrication and characterization of fullerene/porphyrin bulk heterojunction solar cells

Fullerene/porphyrin bulk heterojunction solar cells were fabricated and, the electronic and optical properties were investigated. Effects of exciton-diffusion blocking layer of perylene derivative on the solar cells between active layer and metal layer were also investigated. Optimized structures with the exciton-diffusion blocking layer improved conversion efficiencies. Energy levels of the molecules were calculated and discussed. Nanostructures of the solar cells were investigated by X-ray and electron diffraction, which indicated formation of fullerene/porphyrin mixed crystals. Electronic structures of the molecules were investigated by molecular orbital calculation, and energy levels of the solar cells were discussed.     

Metal oxide buffer layer for improving performance of polymer solar cells

We report the application of aluminum doped ZnO (ZnO:Al) layer as a buffer on ITO glass for fabrication of non-inverted polymer solar cells. The ZnO:Al thin film was deposited using DC magnetron sputtering, with the thickness being varied from 23 to 100 nm. The devices showed most discernible improvements in their efficiencies when a thin layer of ZnO:Al film of thickness ∼40 nm was introduced. The observed enhancement in short circuit current density and open circuit voltage is likely attributed to the role of the ZnO:Al film as an optical tuner and an interfacial diffusion barrier. The result suggests that a metal oxide layer inserted between ITO and polymer layers can be a route for improving both efficiency and stability of polymer solar cells.     

不同受体对PTB7聚合物太阳能电池的性能影响的研究

使用两种或者更多种类的富勒烯衍生物作为受体可以使poly(3-己基噻吩)(P3TH)系的混合异质结太阳能电池效率明显提升。这样的提升源于当受体使用富勒烯多重加合物的最低未占轨道(LUMO)提升而使其开路电压升高。虽然其他聚合物也同样能获得高的开路电压,但是大多数的聚合物却不像P3TH一样获得性能提升,在与像苯基-C61-丁酸甲酯 (bis-PCBM)或者the indene-C60 bis-adduct (ICBA)混合后表现出下降的光电流。在此,我们研究这些性能改变的原因。使用[6,6]-苯基C₇₀-丁酸甲酯(PC₇₀BM), ICBA和bis-PC₇₀BM作为受体并且PTB7作为给体,其结构为：ITO/PEDOT：PSS/活性层/LiF/Al,聚合物太阳能电池的表现的性能分别为7.29%, 4.92% 和3.33%。性能的改变可能主要归因于不同受体影响器件激子产生和电荷收集。     

Decoupling crystalline volume fraction and VOC in microcrystalline silicon pin solar cells by using a µc‐Si:F:H intrinsic layer

Microcrystalline silicon thin film pin solar cells with a highly crystallized intrinsic μc‐Si:F:H absorber were prepared by RF‐plasma enhanced chemical vapour deposition using SiF₄ as the gas precursor. The cells were produced with a vacuum break between the doped layer and intrinsic layer depositions, and the effect of different subsequent interface treatment processes was studied. The use of an intrinsic μc‐Si:H p/i buffer layer before the first air break increased the short circuit current density from 22.3 mA/cm² to 24.7 mA/cm². However, the use of a hydrogen‐plasma treatment after both air breaks without an interface buffer layer improved both the open circuit voltage and the fill factor. Although the material used for the absorber layer showed a very high crystalline fraction and thus an increased spectral response at long wavelengths, an open‐circuit voltage (V_OC) of 0.523 V was nevertheless observed. Such a value of V_OC is higher than is typically obtained in devices that employ a highly crystallized absorber as reported in the literature (see abstract figure). Using a hydrogen‐plasma treatment, a single junction μc‐Si:F:H pin solar cell with an efficiency of 8.3% was achieved.

     

Molecular gated transistors: Role of self-assembled monolayers

In order to understand the biosensing mechanism of field-effect based biosensors and optimize their performance, the effect of each of its molecular building block must be understood. In this work the gating effect of self-assembled linker molecules on field-effect transistor was studied in detail. We have combined Kelvin probe force microscopy, current-voltage measurements, capacitance-voltage measurements, equivalent circuit modeling and device simulations in order to trace the mechanism of silicon-on-insulator biological field-effect transistors. The measurements were conducted on the widely used linker molecules (3-aminopropyl)-trimethoxysilane (APTMS) and 11-aminoundecyl-triethoxysilane (AUTES), which were self-assembled on ozone activated silicon oxide surface covering the transistor channel. In a dry environment, the work function of the modified silicon oxide decreased by more than 1.5 eV, and the transistor threshold voltage increased by about 30 V following the self-assembly. A detailed analysis indicates that these changes are due to negative induced charges on the top dielectric layer, and an effective dipole due to the polar monolayer. However, the self-assembly did not change the silicon flat-band voltage when in contact with an electrolyte. This is attributed to electrostatic screening by the electrolyte.     

Morphology controlled open circuit voltage in polymer solar cells

We report a strong dependence of open circuit voltage on the altered morphology of block copolymer (P3HT‐b ‐PPerAcr) based solar cells. The open circuit voltage increases dramatically by about 300 mV by increasing the amount of acceptor homopolymer within the block copolymer/homopolymer blends. The change in open circuit voltage is found to be in correlation with the enrichment of acceptor moiety at the film surface as identified by Atomic force microscopy (AFM) and X‐ray photoelectron spectroscopy (XPS). Based on this fact, an additional increase in open circuit voltage to its maximum values is achieved by introducing an acceptor buffer layer at the cathode interface. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interaction of polymers with fullerene C60

The fundamentals of the method for estimating the fullerene-binding power of polymer macromolecules and supramolecular formations are developed for fullerene C₆₀. Polymers with covalently attached anthracene groups (one group per macromolecule) whose luminescence decreases in the presence of fullerene in solution in direct proportion to the stability of the fullerene-polymer complex are used. The effect of the anthracene mark on the fullerene-binding power of a luminescent-marked polymer is taken into account or discarded on the basis of an analysis of the interaction between fullerene and low-molecular models of luminescent marks.     

Experimental analysis and modeling of the IV characteristics of photovoltaic solar cells under solar spectrum spot illumination

In this paper, some models that have been put forward to explain the characteristics of a photovoltaic solar cell device under solar spot-illumination are investigated. In the experimental procedure, small areas of the cell were selected and illuminated at different solar intensities. The solar cell open circuit voltage (V_oc) and short circuit current (I_sc) obtained at different illumination intensities was used to determine the solar cell ideality factor. By varying the illuminated area on the solar cell, changes in the ideality factor were studied. The ideality factor obtained increases with decreasing illumination surface ratio. The photo-generated current at the illuminated part of the cell is assumed to act as a dc source that injects charge carriers into the p-n junction of the whole solar cell while the dark region of the solar cell operates in a low space charge recombination regime with small diffusion currents. From this analysis, a different model of a spot illuminated cell that uses the variation of ideality factor with the illuminated area is proposed.     

基于聚多巴胺/氧化锌复合阴极缓冲层的倒置聚合物太阳能电池的研究

利用多巴胺氧化自聚合形成聚多巴胺(PDA)与ZnO结合形成PDA/ZnO复合阴极缓冲层,制备了以P3HT:PC_(61)BM为活性层的倒置结构聚合物太阳能电池,通过改变PDA的自聚合时间来分析复合阴极缓冲层对器件性能的影响.实验发现,随着PDA的自聚合时间的增加,聚合物太阳能电池的光电转换效率先增大后减小,当自聚合时间为10 min时,相应器件光伏性能达到最优值,其开路电压V_(OC)为0.66 V,短路电流密度J_(SC)为9.70 mA/cm~2,填充因子FF为68.06%,光电转换效率PCE为4.35%.器件性能改善的原因是由于PDA/ZnO复合阴极缓冲层减小了ZnO与ITO之间的接触电阻,同时PDA中存在大量的氨基有利于倒置太阳能电池阴极对电子的收集.     

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。     

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。