染料敏化太阳电池中TiO2颗粒界面接触对电子输运影响的研究

采用溶胶-凝胶法制备TiO₂浆料,通过丝网印刷技术印刷和不同温度曲线烧结TiO₂薄膜,并应用于染料敏化太阳电池(DSC).高分辨透射电子显微镜发现,低温下多孔薄膜中TiO₂颗粒之间呈现点接触,510 ℃烧结后TiO₂颗粒间由点接触变为面接触,近邻颗粒数增多,接触面积增大.同时采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,研究了不同颗粒接触方式和接触面积对电子传输与复合的影响.结果表明:在420- 510 ℃之间,随着烧结温度提高,颗粒接触面积增大,电子传输时间(τ _d)缩短,电子有效扩散长度(L _n)增大,暗电流减小;当烧结温度达到550 ℃时,薄膜比表面积减小,多孔结构坍塌,表面态密度增大,电子传输时间(τ _d)增大.电池光伏特性研究表明:在480-510 ℃范围内烧结得到的TiO₂薄膜,电池短路电流密度(J_sc)最佳,电池效率(η)最好. 关键词： 界面接触 电子输运 暗电流 染料敏化太阳电池     

电极表面改性对染料敏化太阳电池性能影响的机理研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,从染料敏化太阳电池(DSC)电子传输和复合角度对比了不同光强下导电玻璃表面阻挡层及TiO₂薄膜优化使电池性能改善的内在原因.阻挡层的引入和TiO₂薄膜的优化均通过电沉积法实现.结果表明,对多孔薄膜电极的不同改性均提高了电池的短路电流J_sc和效率η,但对电子传输和复合过程的作用机理有所不同:前者延长了电子寿命τ _n,但电子传输时间τ _d变化不明显;而后者则主要是延长τ _n的同时也缩短了τ _d. 关键词： 染料敏化 太阳电池 调制光电流谱/调制光电压谱 电子输运     

Recent advances of interface engineering in inverted perovskite solar cells

Perovskite solar cells (PSCs) have witnessed great achievement in the past decade. Most of previous researches focus on the n—i—p structure of PSCs with ultra-high efficiency. While the n—i—p devices usually used the unstable charge transport layers, such as the hygroscopic doped spiro-OMeTAD, which affect the long-term stability. The inverted device with the p—i—n structure owns better stability when using stable undoped organic molecular or metal oxide materials. There are significant progresses in inverted PSCs, most of them related to charge transport or interface engineering. In this review, we will mainly summarize the inverted PSCs progresses related to the interface engineering. After that, we prospect the future direction on inverted PSCs.     

调制光/电作用下染料敏化太阳电池中电荷传输和界面转移研究

详细讨论了染料敏化太阳电池(DSC)在稳态光照射或外加偏压下电荷的传输和转移过程,以及在调制光/电作用下电池的频率响应特点.通过电化学阻抗谱、光电化学阻抗谱、强度调制光电流谱和强度调制光电压谱等四种频谱光电测试手段,对DSC中TiO₂薄膜电子传输和界面转移的相关时间常数进行测量.详细分析和比较了电荷的传输及转移过程对时间常数的影响.结果表明,在低光强或低偏压下电荷传输和转移过程对时间常数影响较小,但在高光强或高偏压下对电子寿命影响明显.     

载流子复合及能量无序对聚合物太阳电池开路电压的影响

聚合物太阳电池中载流子的复合与能量无序对器件的开路电压有着深刻的影响.本文同时研究了基于传统富勒烯(PC71BM)和非富勒烯(O-IDTBR)电子受体的聚合物太阳电池.通过交流阻抗谱、低温电流密度-电压谱、瞬态光电压以及电致发光光谱等手段重点研究了载流子复合及能量无序对电池器件开路电压的影响.具体地,交流阻抗谱和瞬态光电压测试结果表明,富勒烯体系载流子复合损失较为严重.电致发光光谱研究显示,PC71BM器件的发光峰随着注入电流的增加不断向短波长处移动,而O-IDTBR体系发光峰位置基本不变,该结果证明PC71BM体系中能量无序度更高.载流子复合严重及能量无序度更高共同作用导致了富勒烯器件开路电压的降低.     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

Impact of nongeminate recombination on the performance of pristine and annealed P3HT:PCBM solar cells

Transient photovoltage (TPV) and voltage dependent charge extraction (CE) measurements were applied to poly(3‐hexyl‐thiophene) (P3HT):[6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) bulk heterojunction solar cells to analyze the limitations of solar cell performance in pristine and annealed devices. From the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n (V), the nongeminate loss current j_loss of the device is accessible. We found that j_loss alone is sufficient to describe the j –V characteristics across the whole operational range, for annealed and, not yet shown before, also for the lower performing pristine solar cells. Even in a temperature range from 300 K to 200 K nongeminate recombination is found to be the dominant and, therefore, performance limiting loss process. Consequently, charge photogeneration is voltage independent in the voltage range studied. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical study of electronic structure and excited states properties of two dyes for dye-sensitized solar cells

Two conjugated organic dyes comprising the benzo[b]furan moieties as the electron donor and cyanoacetic acid moieties as the electron acceptor/anchoring groups have been investigated using a quantum chemical method. The molecular equilibrium geometries and ground state character were studied using density functional theory. Absorption spectra were obtained using time-dependent density functional theory and semiempirical ZINDO. The nature of absorption spectra was further studied using 2D and 3D real-space analysis; here, 2D real-space analysis showed electron–hole coherence, and 3D real-space analysis showed intramolecular charge transfer during photo-excitation. As important parameters, excited state oxidation potential and driving force energy were obtained to reveal the relationship between molecular structure and performance of two compounds.     

负偏压作用下染料敏化太阳电池界面及光电性能研究

太阳电池组件由于局部电压不匹配,其中部分电池可能较长时间工作在负偏压状态下,从而影响电池光电性能.借助拉曼光谱、电化学阻抗谱和入射单色光量子效率(IPCE)等测试手段,研究长期负偏压作用下染料敏化太阳电池光电性能的变化及其影响机理.拉曼光谱研究结果表明:电池在1000 h负偏压作用下,电解质中阳离子(Li⁺)会向光阳极(TiO₂电极)移动并嵌入TiO₂薄膜中;长期负偏压作用还会致使TiO₂/电解质界面阻抗增大和IPCE下降,导致电池开路电压升高和短路电流减小.通过加入苯并咪唑(BI)添加剂,经1000 h负偏压后电池的拉曼光谱实验表明,BI能在一定程度阻碍Li⁺的嵌入,电池具有较好的长期稳定性.不同负偏压下的老化实验进一步表明,通过加入添加剂能够使电池在长期负偏压下保持较好的稳定性. 关键词： 染料敏化 太阳电池 组件 负偏压     

双电子传输层结构硫硒化锑太阳电池的界面特性优化

硫硒化锑薄膜太阳电池因其制备方法简单、原材料丰富无毒、光电性质稳定等优点,成为了光伏领域的研究热点.经过近几年的发展,硫硒化锑太阳电池的光电转换效率已经突破10%,极具发展潜力.本文针对硫硒化锑太阳电池中n/i界面引起的载流子复合进行了深入研究.发现硫硒化锑太阳电池的界面特性会受到界面电子迁移能力和能带结构两方面的影响.界面电子迁移率的提高能使电子更有效地传输至电子传输层,实现器件短路电流密度和填充因子的有效提升.在此基础上,引入ZnO/Zn_1-xMg_xO双电子传输层结构能够进一步优化硫硒化锑太阳电池性能.其中,Zn_1-xMg_xO能级位置的改变可以同时调节界面和吸光层的能级分布,在Zn_1-xMg_xO导带能级为-4.2 eV,对应Mg含量为20%时,抑制载流子复合的效果最为明显,硫硒化锑太阳电池也获得了最佳的器件性能.在去除缺陷态的理想情况下,双电子传输层结构硫硒化锑太阳电池在600 nm厚时获得了20.77%的理论光电转换效率,该研究结果为硫硒化锑太阳电池...     

基于薄膜电极溶胶修饰的染料敏化太阳电池光电特性研究

染料敏化太阳电池(DSC)中的纳米薄膜电极 是决定太阳电池光电转换性能的重要组成部分. 为改善薄膜电极特性, 采用了不同浓度的TiO₂溶胶对DSC光阳极导电玻 璃和纳米TiO₂多孔薄膜进行不同方式的界面处理. 利用X射线衍射方法对制备得到的多孔薄膜以及溶胶经高温处理 后致密层中纳米TiO₂颗粒的尺寸及晶型进行了测试. 采用高分辨透射电子显微镜和场发射扫描电子 显微镜观察了纳米颗粒及薄膜微结构形貌. 采用强度调制光电流谱/光电压谱分析了TiO₂溶 胶的不同处理方式对电子传输和复合的影响. 在100 mW· cm^-2光强以及暗环境下分别测试了DSC的伏安输出性能以及暗电流. 结果表明, 不同浓度和处理方式均能较好地抑制暗电流. 溶胶处理后光生电子寿命τ_n延长, 电子传输平均时间τ_d相应缩短. 采用浓度为0.10 mol·L^-1的 溶胶对导电玻璃和多孔膜同时处理, DSC的宏观输出特性最佳, 短路电流密度J_sc提高了10.9%, 光电转换效率η提高了11.9%.     

Wet-chemical treatment and electronic interface properties of silicon solar cell substrates

On textured n-type silicon substrates for solar cell manufacturing, the relation between light trapping behavior, structural imperfections, energetic distribution of interface state densities and interface recombination losses were investigated by applying surface sensitive techniques. The field-modulated surface photovoltage (SPV), in-situ photoluminescence (PL) measurements, total hemispherical UV-NIR-reflectance measurements and electron microscopy (SEM) were employed to yield detailed information on the influence of wet-chemical treatments on preparation induced micro-roughness and electronic properties of polished and textured silicon substrates. It was shown that isotropic as well as anisotropic etching of light trapping structures result in high surface micro-roughness and density of interface states. Removing damaged surface layers in the nm range by wet-chemical treatments, the density of these states and the related interface recombination loss can be reduced. In-situ PL measurements were applied to optimise HF-treatment times aimed at undamaged, oxide-free and hydrogen-terminated substrate surfaces as starting material for subsequent solar cell preparations.      

Hole‐extraction layer dependence of defect formation and operation of planar CH3NH3PbI3 perovskite solar cells

Three planar CH₃NH₃PbI₃ (MAPbI₃) solar cells having the same structure except a hole‐extraction layer (HEL) showed distinctive difference in operation characteristics. Analysis of frequency‐dependent capacitance and dielectric‐loss spectra of the three MAPbI₃ devices showed two types of recombination‐loss channels with different time constants that we attributed respectively to interface and bulk defects. Discrepancy in defect formation among the three devices with a HEL of PEDOT:PSS, NiO_x, or Cu‐doped NiO_x was not surprising because grain‐size distribution and crystalline quality of MAPbI₃ can be affected by surface energy and morphology of underlying HELs. We were able to quantify interface and bulk defects in these MAPbI₃solar cells based on systematic and simultaneous simulations of capacitance and dielectric‐loss spectra, and current–voltage characteristics by using the device simulator SCAPS.

     

Nongeminate recombination in organic bulk heterojunction solar cells: Contribution of exciton–polaron interaction

A new model to explain nongeminate recombination in organic bulk heterojunction solar cells is presented. We suggest that the annihilation of excitons on charge carriers at the interface between donor and acceptor phases competes with the bimolecular recombination of Coulombically bound electron–hole pairs. The exciton–polaron interaction gives visible contribution to the reduction of Langevin recombination. An analytical formula, which describes the reduction prefactor, has been derived. We demonstrate that exciton–charge carrier interactions cause an increase of the recombination order. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

有机共混结构叠层太阳电池的研究进展

有机太阳电池由于质轻、价廉、柔性,受到人们的广泛关注.单个有机材料只能吸收部分太阳光,叠层结构的太阳电池将不同吸收带隙的有机材料通过中间层连接起来,既能充分吸收太阳光,又能提高太阳电池的开路电压或短路电流.本文综述了近年来有机共混结构叠层太阳电池的研究进展,介绍了各种叠层有机太阳电池的结构、原理及性能,阐述了国内外有机叠层太阳电池研究的现状及存在问题,为高性能有机太阳电池的研究提供有价值的参考.     

Light scattering of nanocrystalline TiO2 film used in dye-sensitized solar cells

This paper studies the light scattering and adsorption of nanocrystalline TiO2 porous films used in dye-sensitized solar cells composed of anatase and/or rutile particles by using an optical four-flux radiative transfer model. These light properties are difficult to measure directly on the functioning solar cells and they can not be calculated easily from the first-principle computational or quantitative theoretical evaluations. These simulation results indicate that the light scattering of 1 25 nm TiO2 particles is negligible, but it is effective in the range of 80 and 180 nm. A suitable mixture of small particles （10 nm radius）, which are resulted in a large effective surface, and of larger particles （150 nm radius）, which are effective light scatterers, have the potential to enhance solar absorption significantly. The futile crystals have a larger refractive index and thus the light harvest of the mixtures of such larger rutile and relatively small anatase particles is improved in comparison with that of pure anatase films. The light absorption of the 10μm double-layered films is also examined. A maximal light absorption of double-layered film is gotten when the thickness of the first layer of 10 urn-sized anatase particles is comparable to that of the second larger rutile layer.     

TiO2颗粒尺寸对染料敏化太阳电池内电子输运特性影响研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究了染料敏化太阳电池(DSC)内部电子传输和背反应动力学特性.在纳米TiO₂薄膜厚度相同的情况下,借助于IMPS/IMVS测量了由3种不同TiO₂颗粒尺寸大小薄膜制备出DSC的电荷传输特征参数值.IMPS/IMVS理论模型拟合实验测量数据的结果表明：在不同入射光强下,随着颗粒尺寸的增大,电子扩散系数(D_n)增大,而电子寿命(τ_n 关键词： 染料敏化 太阳电池 IMPS/IMVS 电子传输     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输     

Improvement in IBC-silicon solar cell performance by insertion of highly doped crystalline layer at heterojunction interfaces

By inserting a thin highly doped crystalline silicon layer between the base region and amorphous silicon layer in an interdigitated back-contact(IBC) silicon solar cell, a new passivation layer is investigated. The passivation layer performance is characterized by numerical simulations. Moreover, the dependence of the output parameters of the solar cell on the additional layer parameters(doping concentration and thickness) is studied. By optimizing the additional passivation layer in terms of doping concentration and thickness, the power conversion efficiency could be improved by a factor of2.5%, open circuit voltage is increased by 30 mV and the fill factor of the solar cell by 7.4%. The performance enhancement is achieved due to the decrease of recombination rate, a decrease in solar cell resistivity and improvement of field effect passivation at heterojunction interface. The above-mentioned results are compared with reported results of the same conventional interdigitated back-contact silicon solar cell structure. Furthermore, the effect of a-Si:H/c-Si interface defect density on IBC silicon solar cell parameters with a new passivation layer is studied. The additional passivation layer also reduces the sensitivity of output parameter of solar cell to interface defect density.     

Bulk and interface recombination in planar lead halide perovskite solar cells: A Drift-Diffusion study

A theoretical approach based on Drift-Diffusion equations is presented to study planar mixed lead halide perovskite solar cells. Updated physical parameters such as permittivity, mobility, effective density of states and doping density is employed in simulations. Current-voltage curve data for two experimental sample is imported and through fitting with the model, density of bulk and interface defects is calculated. We obtain the bulk defect density around 10¹⁶ cm⁻³ and surface recombination velocities in the range of 10 cm/s. These values which are in good agreement with experimental measurements and considerably deviated from previous theoretical studies, verify the model and adopted constants. Shockley-Queisser limit is also presented as the ideal device and the effect of bulk and interface defects are presented as loss factors that cause departure from this limit. Our simulations conclude that the overall efficiency of perovskite solar cells is mainly governed by the open-circuit voltage and also identify the interface defects as the major loss factor in these devices.