The path towards a high-performance solution-processed kesterite solar cell

Despite the promise of thin-film Cu(In,Ga)(S,Se)₂ (CIGSSe) chalcopyrite and CdTe photovoltaic technologies with respect to reducing cost per watt of solar energy conversion, these approaches rely on elements that are either costly and/or rare in the earth's crust (e.g., In, Ga, Te) or that present toxicity issues (e.g., Cd), thereby potentially limiting these technologies in terms of future cost reduction and production growth. In order to develop a photovoltaic technology that is truly compatible with terawatt deployment, it is desirable to consider material systems that employ less toxic and lower cost elements, while maintaining the advantages of the chalcopyrite and CdTe materials with respect to appropriate direct band gap tunability over the solar spectrum, high device performance (e.g., >10% power conversion efficiency) and compatibility with low-cost manufacturing. In this review, the development of kesterite-based Cu₂ZnSn(S,Se)₄ (CZTSSe) thin-film solar cells, in which the indium and gallium from CIGSSe are replaced by the readily available elements zinc and tin, will be reviewed. While vacuum-deposited devices have enabled optimization within the compositional phase space and yielded selenium-free CZTS device efficiencies of as high as 6.8%, more recently a liquid-based approach has been described that has enabled deposition of CZTSSe devices with power conversion efficiency of 9.7%, bringing the kesterite-based technology into a range of potential commercial interest. Electrical characterization studies on these high-performance CZTSSe cells reveal some of the key loss mechanisms (e.g., dominant interface recombination, high series resistance and low minority carrier lifetime) that limit the cell performance. Further elucidation of these mechanisms, as well as building an understanding of long-term device stability, are required to help propel this relatively new technology forward.     

The influence of hydrogen in the incorporation of Zn during the growth of Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (CZTS) is a p-type semiconductor, candidate to replace Cu(In,Ga)Se₂ as absorber layer in thin film solar cells. The best solar cells based on CZTS present efficiencies up to 6.8%. These results were improved when metallic Zn was replaced by ZnS, which may imply a different chemical path for the formation of CZTS. In this study it is compared with the diffusion of Zn on Cu₂SnS₃ by introducing metallic Zn or ZnS. For this CZTS films were grown by sulphurization of Cu₂SnS₃, some with a Zn layer and others with a ZnS layer. The influence of H₂ during the annealing process is also studied and for this some sulphurizations were done in the presence of a partial atmosphere of H₂.The SEM micrographs of the samples show a columnar growth structure of the films with different degrees of compactness. The compactness is improved in the samples where a ZnS layer was present in the precursor and the sulphurization was done in the presence of H₂. EDS chemical profiling revealed regular zinc distribution for the samples with metallic Zn whilst the ones with ZnS exhibited a Zn-rich surface. X-ray diffraction (XRD) indicated the presence of CZTS and Cu_2−xS phases in all samples. These results were confirmed by Raman scattering.It was concluded that the sulphurization of Cu₂SnS₃ films with the use of ZnS layers under H₂ atmosphere produces better quality CZTS thin films, since it promotes Zn diffusion and avoids Zn losses by evaporation.     

The crystallisation of Cu2ZnSnS4 thin film solar cell absorbers from co-electroplated Cu-Zn-Sn precursors

The best CZTS solar cell so far was produced by co-sputtering continued with vapour phase sulfurization method. Efficiencies of up to 5.74% were reached by Katagiri et al. The one step electrochemical deposition of copper, zinc, tin and subsequent sulfurization is an alternative fabrication technique for the production of Cu₂ZnSnS₄ based thin film solar cells. A kesterite based solar cell (size 0.5 cm²) with a conversion efficiency of 3.4% (AM1.5) was produced by vapour phase sulfurization of co-electroplated Cu-Zn-Sn films. We report on results of in-situ X-ray diffraction (XRD) experiments during crystallisation of kesterite thin films from electrochemically co-deposited metal films. The kesterite crystallisation is completed by the solid state reaction of Cu₂SnS₃ and ZnS. The measurements show two different reaction paths depending on the metal ratios in the as deposited films. In copper-rich metal films Cu₃Sn and CuZn were found after electrodeposition. In copper-poor or near stoichiometric precursors additional Cu₆Sn₅ and Sn phases were detected. The formation mechanism of Cu₂SnS₃ involves the binary sulphides Cu_2 − xS and SnS₂ in the absence of the binary precursor phase Cu₆Sn₅. The presence of Cu₆Sn₅ leads to a preferred formation of Cu₂SnS₃ via the reaction educts Cu_2 − xS and SnS₂ in the presence of a SnS₂(Cu₄SnS₆) melt. The melt phase may be advantageous in crystallising the kesterite, leading to enhanced grain growth in the presence of a liquid phase.     

Cu2ZnSnS4 films grown in one-step process by spray pyrolysis with improved properties

This work reports results of a study carried out to improve the optical, electrical and microstructural properties of Cu₂ZnSnS₄ (CZTS) films grown by spray pyrolysis in a one-step process using a precursor solution prepared dissolving thiourea and salts of Cu, Sn and Zn in a solvent constituted by a mixture of dimethyl sulfoxide (DMSO) and acetone. The improvement of the properties of the CZTS films was achieved through a parameters study performed by using an experimental design 2³ face centered central composite design (FCCCD). The study revealed that substrate temperature (T_s), carrier gas pressure (P_g), spray pulse time (t_sp) as well as their interaction are the parameters that most critically affect the above mentioned properties. Special emphasis was done on studying the influence of these parameters on the micro structural properties of the CZTS films using the XRD peak broadening method and Williamson-Hall equations, assuming the models UDM (uniform deformation model), USDM (uniform stress deformation model) and UDEDM (uniform deformation energy density model). Further, information regarding the influence of preparation conditions on the formation of structural defects was achieved through Urbach energy measurements.     

Phase transformation of solution‐based p‐type Cu2ZnSnS4 thin film: applicable for solar cell

In this present work, quaternary Cu₂ZnSnS₄ thin films were deposited on commercial glass substrates at room temperature by a novel solution growth dip coating technique. The influence of annealing temperature of the films at 300 °C in a hot air furnace without the presence of any inert gas, on structural, optical, and electrical properties was investigated and discussed. The structural analyses were analyzed by X‐ray diffraction and Raman spectroscopy, whereas optical and electrical properties were analyzed by means of ultra violet infrared (UV‐ViS/IR). The results analyzed showed that there exists a phase formation from orthorhombic to kesterite crystal structure with an increase in optical bandgap and an optical conductivity, with an increase in annealing temperature. The electrical conductivity was observed of the order of 10^?6 ohm cm^?1. Copyright © 2015 John Wiley & Sons, Ltd.     

电沉积法制备铜锌锡硫太阳电池均匀性研究

电沉积法制备铜锌锡硫薄膜太阳电池,沉积层均匀性对电池质量起到关键作用。在传统二维比较法的基础上加入了三维统计,建立模型讨论了极板间距、隔板孔边长、隔板位置和导体边框位置对沉积层均匀性的影响。结果表明,极板间距15 mm为最佳,平整度为61.7%;隔板孔边长50 mm为最佳,平整度为79.6%;隔板距离阴极板6 mm处为最佳,平整度为79.9%;导体边框距离阴极板左侧2 mm处为最佳,平整度为79.5%。考察了制备中整个电极板的均匀性,给出了统计的平整度和三维视图,有助于改进电沉积法制备CZTS电池的工艺,提高CZTS前驱体的质量。     

溶胶-凝胶法制备铜锌锡硫薄膜及其太阳能电池的研究进展

原料丰富价廉的铜锌锡硫(Cu2ZnSnS4,CZTS)材料与非真空、低成本绿色溶胶-凝胶法相结合在产业化制造高性价比CZTS薄膜太阳能电池方面的应用引人关注。为了了解未来发展方向,综述了溶胶-凝胶法制备CZTS薄膜与器件的研究进展,讨论了不同溶胶-凝胶工艺途径、不同溶剂、硫化等对CZTS薄膜制备与器件特性的影响,分析了Na掺杂及硫化退火对CZTS薄膜的作用,并结合绿色制造的要求探讨了其发展趋势。     

Cu2ZnSnS4/Cu2ZnSnSe4电子结构与光学特性的第一性原理计算

采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,计算Cu2ZnSnS4(CZTS)和Cu2ZnSnSe4(CZTSe)的电子结构和光学特性。计算并系统对比分析CZTS和CZTSe的态密度、吸收系数、复介电函数、复折射率、反射率、复电导率和能量损失函数随光子能量的变化关系。结果表明,锌黄锡矿型CZTS和CZTSe都是直接带隙半导体材料。CZTS和CZTSe的态密度和光学特性的曲线非常相似,但CZTS的禁带宽度比CZTSe的偏大,导致CZTS的各个光学特性曲线相对于CZTSe的略微向高能方向移动。     

溶胶-凝胶非硫化法制备铜锌锡硫薄膜

采用溶胶-凝胶非硫化方法制备了表面平整、致密的铜锌锡硫薄膜.XRD及Raman分析表明制备的铜锌锡硫薄膜为锌黄锡矿结构.能谱分析表明所有薄膜均贫铜富锌贫硫.场发射扫描电子显微镜测得薄膜的厚度在0.7 μm左右.透射光谱表明随后退火温度的提高薄膜的光学带隙从2.13 eV减小到1.52 eV.     

Cu2ZnSn(S,Se)4薄膜太阳电池研究进展

Cu2ZnSn(S,Se)4(CZTS)材料具有与Cu(In,Ga)Se2(CIGS)材料相似的光学性质和半导体性质,且原料丰富,是CIGS薄膜太阳电池重要的后备材料。有关CZTS薄膜制备工艺的研究和电池器件转换效率提升的研究正成为本领域新的研究开发热点。目前,有实力的薄膜太阳电池研究队伍已经针对CZTS薄膜太阳电池开展了持续的研究,试图通过不同的CZTS吸收层制备方式和优化电池组装工艺过程,进一步提高CZTS薄膜太阳电池的光电转换效率。文章阐述了CZTS材料特性,着重介绍了目前国内外所采用的CZTS薄膜制备方法,详细讨论了各种薄膜沉积技术的优缺点。最后展望了CZTS电池的发展趋势。