简单的溶胶–凝胶法制备致密的铜锌锡硫硒薄膜

采用溶胶–凝胶后硒化法制备了铜锌锡硫硒薄膜, 其薄膜表面平整、无裂纹。通过简化铜锌锡硫前驱体溶胶的制备以及后退火时避免使用硫化氢气体（H₂S）等方法使铜锌锡硫硒薄膜的制备工艺得到简化。选用低毒有机物乙二醇为溶剂,Cu(CH₃COO)₂、Zn(CH₃COO)₂、SnCl₂•2H₂O和硫脲为原料, 制备铜锌锡硫前驱体溶胶。XRD、Raman、EDX和SEM 分析表明制备的铜锌锡硫硒薄膜为锌黄锡矿结构, 所有薄膜均贫铜富锌, 用0.2 g硒粉、硒化20 min得到的铜锌锡硫硒薄膜其结晶较好, 表面晶粒可达1.0 μm左右。透射光谱分析结果表明, 随硒含量的增加, 铜锌锡硫硒薄膜的光学带隙从1.51 eV减小到1.14 eV。     

Fabrication and Evaluation of Low-cost Cu2ZnSn(S,Se)4 Counter Electrodes for Dye-sensitized Solar Cells

Nano-Micro Letters - We explore a simple and eco-friendly approach for preparing CZTS powders and a screen-printing process for Cu2ZnSn(S,Se)4 (CZTSSe) counter electrodes (CEs) in dye-sensitized...     

In situ, real-time thickness measurement techniques for bath-deposited CdS thin films on Cu(In,Ga)Se2

A technique has been developed that can measure the thickness of a 30-70 nm thin film of cadmium sulfide on a Cu(In,Ga)Se₂ substrate, in real time, as it grows in a chemical bath. The technique does not damage the film, and can be used to monitor batch depositions and roll-to-roll depositions with equal accuracy. The technique is based on reflectance spectroscopy through the chemical bath.     

GaSe Formation at the Cu(In,Ga)Se2/Mo Interface–A Novel Approach for Flexible Solar Cells by Easy Mechanical Lift‐Off

Implementing photovoltaic devices based on high efficiency thin‐film technologies on cheap, light‐weight and flexible polymeric substrates is highly appealing to cut down costs in industrial production and to accelerate very large scale deployment of photovoltaics in the upcoming years. Lift‐off processes, which allow separating active layers from primary substrates and subsequent transfer onto an alternative substrate without modifying the upstream production process and without performance losses, are an emerging alternative to direct growth on polymeric substrates. This study concerns the feasibily of direct mechanical lift‐off process for high efficiency Cu(In,Ga)Se₂ (CIGS) thin film solar cells grown by coevaporation on glass/molybdenum substrates without performance losses. The study presents an in depth characterization (SEM,AFM,GIXRD,XPS) of samples leading to excellent lift‐off properties. They are explained by a specific gallium rich CIGS graded interface structure according to the interfacial sequence glass/Mo/MoSe₂/Ga_xSe_y/Ga‐rich‐CIGS. The interfacial layer, attributed to GaSe, has a layered structure and out performs the molybdenum diselenide layered layer which forms spontaneously at the interface Mo/CIGS. It allows a very easy lift‐off process at the interface GaSe/CIGS thanks to Van‐der‐Waals adhesion mechanism in GaSe. Key physical‐chemical parameters are identified and analyzed. After lift‐off, an efficiency of 14.3%, higher than the initial reference CIGS solar cell efficiency (13.8%) is measured.     

CuIn(S,Se)2thin film solar cells from nanocrystal inks: Effect of nanocrystal precursors

CuIn(S,Se)₂ thin film solar cells are fabricated by selenizing CuInS₂ nanocrystals synthesized using a variety of copper and indium precursors. Specifically, copper and indium acetates, acetylacetonates, iodides, chlorides and nitrates are investigated to determine the effect of precursors on electronic properties and device performance. Nanocrystal synthesis with each of these precursors can be optimized to yield similar nanocrystal composition, size and structure. In addition, dense chalcopyrite CuIn(S,Se)₂ thin films with micron sized grains at the surface are formed upon selenization regardless of precursor type. Surprisingly, solar cells fabricated from each nanocrystal ink have roughly the same carrier concentrations of 10¹⁶ to 10¹⁷ cm^− 3 in the absorber layer and achieve active area efficiencies of approximately 5%.     

基于对氯苄胺的2D/3D钙钛矿太阳能电池

三维(3D)有机–无机金属卤化物钙钛矿薄膜的表面和晶界处存在大量缺陷,容易导致载流子的非辐射复合并加快3D钙钛矿分解,进而影响钙钛矿太阳能电池(PSCs)能量转换效率(PCE)及稳定性.本研究通过引入对氯苄胺阳离子,与3D钙钛矿薄膜及其表面过剩的碘化铅反应后原位形成了二维(2D)钙钛矿,实现了对3D钙钛矿薄膜表面和晶界...     

高效CdS量子点敏化B/S共掺杂纳米TiO2太阳能电池的制备及光电性能研究

采用水热法制备硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂), 并配制成浆料, 利用丝网印刷技术在FTO导电玻璃上制备B-S-TiO₂薄膜; 用化学浴沉积(CBD)法制备了CdS量子点敏化B-S-TiO₂薄膜电极, 并用X射线衍射(XRD)、电子显微镜(TEM)、元素分析能谱(EDS)和紫外-可见光谱对其进行表征分析; 结果显示: B/S共掺杂不会改变TiO₂的晶型, 掺杂后的TiO₂吸收边带发生明显红移, 吸收强度显著增强; 同样用化学浴沉积的方法制备NiS工作电极, 用改性的聚硫化物((CH₃)₄N)₂S/((CH₃)₄N)₂S_n)电解液, 组装CdS量子点敏化硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂)太阳能电池, 并测试电池光电性能。测试结果表明, 在AM1.5G的照射下, 电池的能量转化效率(η)由3.21%增大到3.69%, 提高了14.9%, 电池获得高达 (V_oc)1.218 V的开路电压和3.42 mA/cm²的短路光电流(J_sc), 以及高达88.7%的填充因子(ff)。     

电化学沉积太阳电池用CuInSe2和Cu(In,Ga)Se2薄膜的研究进展

综述了电化学沉积太阳电池用CuInSe2(CIS)和Cu(In,Ga)Sez(CIGS)薄膜的研究和发展;对CIS和CIGS预制层的电化学沉积路线,包括一步沉积、分步沉积和特种电沉积的研究进展进行了详细的评述;综述了电沉积预制层的后处理,包括退火、化学处理和PVD调整成分的研究状况.回顾了基于电化学沉积的CIS和CIGS太阳电池研究的发展过程,并介绍了目前实验室和产业化研究的最新成果,指出了存在的问题并展望了其发展趋势.     

Optoelectronic characteristics of Cu(In,Ga)(S,Se)2 thin film solar cells obtained from varied chalcogenization processes

We investigated industrially produced chalcopyrite solar cells based on the absorber modifications Cu(In,Ga)Se₂ and Cu(In,Ga)(S,Se)₂ in order to study the nature of the experimentally verified efficiency improvement, mainly caused by an increased open circuit voltage. We show that the introduction of sulfur during the absorber formation via rapid thermal processing leads to a substantial lowering of the surface doping concentration and widening of the space charge region (SCR). Temperature dependent diode analysis revealed a reduction of the SCR recombination in (Se,S) devices which would lead to a larger splitting of quasi-Fermi levels and hence to an increased open circuit voltage as compared to neat Cu(In,Ga)Se₂ devices.     

Defect Control for 12.5% Efficiency Cu2ZnSnSe4 Kesterite Thin-Film Solar Cells by Engineering of Local Chemical Environment

Kesterite-based Cu₂ZnSn(S,Se)₄ semiconductors are emerging as promising materials for low-cost, environment-benign, and high-efficiency thin-film photovoltaics. However, the current state-of-the-art Cu₂ZnSn(S,Se)₄ devices suffer from cation-disordering defects and defect clusters, which generally result in severe potential fluctuation, low minority carrier lifetime, and ultimately unsatisfactory performance. Herein, critical growth conditions are reported for obtaining high-quality Cu₂ZnSnSe₄ absorber layers with the formation of detrimental intrinsic defects largely suppressed. By controlling the oxidation states of cations and modifying the local chemical composition, the local chemical environment is essentially modified during the synthesis of kesterite phase, thereby effectively suppressing detrimental intrinsic defects and activating desirable shallow acceptor Cu vacancies. Consequently, a confirmed 12.5% efficiency is demonstrated with a high V_OC of 491 mV, which is the new record efficiency of pure-selenide Cu₂ZnSnSe₄ cells with lowest V_OC deficit in the kesterite family by E_g/q-Voc. These encouraging results demonstrate an essential route to overcome the long-standing challenge of defect control in kesterite semiconductors, which may also be generally applicable to other multinary compound semiconductors.     

Direct synthesis of CuIn(Sex, S1 − x)2 films from elemental In, Cu, Se, S particle precursor films and its dependence on energy

CuIn(Se_x, S_1 − x)₂ films were prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se and S particle precursor films by passing an electrical current with precise control through the metal substrate. For a constant reaction period of 1 s, unreacted elemental particles remained in the films for powers below 1 kV A, whereas the reaction to CuIn(Se_x, S_1 − x)₂ (x = 1) appeared to be complete at higher power. Chalcopyrite structure was observed in the range from 1.08 kV A to 1.24 kV A, the sphalerite structure appeared over 1.35 kV A. X-ray diffraction shows single (112) peaks of CuIn(Se_x, S_1 − x)₂ and the peak position agreed with the nominal composition of the precursors.     

Hydrogen effects on deep level defects in proton implanted Cu(In,Ga)Se2 based thin films

Hydrogen effects on deep level defects and a defect generation in proton implanted Cu(In,Ga)Se₂ (CIGS) based thin films for solar cell were investigated. CIGS films with a thickness of 3 μm were grown on a soda-lime glass substrate by a co-evaporation method, and then were implanted with protons. To study deep level defects in the proton implanted CIGS films, deep level transient spectroscopy measurements on the CIGS-based solar cells were carried out, these measurements found 6 traps (including 3 hole traps and 3 electron traps). In the proton implanted CIGS films, the deep level defects, which are attributed to the recombination centers of the CIGS solar cell, were significantly reduced in intensity, while a deep level defect was generated around 0.28 eV above the valence band maximum. Therefore, we suggest that most deep level defects in CIGS films can be controlled by hydrogen effects.