铜锡硫和铜锌锡硫半导体光伏材料的制备及表征

发布时间：2018-03-22 16:16

  本文选题：薄膜太阳能电池　切入点：铜锡硫　出处：《电子科技大学》2014年硕士论文　论文类型：学位论文

【摘要】：铜锡硫(Cu2SnS3, CTS)和铜锌锡硫(Cu2ZnSnS4, CZTS)是一类典型的多元化合物半导体光伏材料,它们凭借自身的p型导电特性、与太阳辐射匹配的禁带宽度、在可见光区域的高吸收系数、丰富无毒的元素特性等优点,成为薄膜太阳能电池吸收层材料领域的重点研究对象。但现阶段的实验室制备技术仍不能得到结晶性能特别良好的薄膜,工艺参数仍有待改进。本论文针对上述Cu2SnS3和Cu2ZnSnS4薄膜制备研究中出现的问题和挑战,以制备出具有柱状晶粒的Cu2SnS3薄膜为主要目的,探索研究了采用不同前驱体结构的Cu2SnS3制备技术,优化了硫化退火工艺条件；以适应大规模生产技术为目的,探索了电沉积法制备Cu2ZnSnS4的实验条件。本论文的具体研究内容如下：(1)采用Cu/Sn叠层结构金属前驱体硫化退火的方法,制备出具有柱状晶粒的Cu2SnS3薄膜；研究了前驱体硫化退火时出现的Sn元素流失问题,发现了Cu2SnS3薄膜生长过程中的Cu/Sn比例自适应现象；提出了通过选择具有恰当Cu/Sn比例(略小于2.00)的前驱体,来避免硫化退火时出现Sn流失现象的解决方案。(2)尝试采用Cu/Sn比例为1.88的Cu-Sn合金单靶,溅射制备出Cu/Sn比例一定(约为2.00)的Cu-Sn合金前驱体,其硫化退火后成功制备出了Cu2SnS3薄膜；该制备路径的高温(≥450℃)热处理过程中,没有出现Sn流失现象；通过增加预退火步骤和长时间(18 h)低温(250℃)条件下S气氛扩散步骤,得到了具有柱状大晶粒的Cu2SnS3薄膜；通过控制退火时硫源和硒源的比例,可控地调节了Cu2Sn(S,Se)3薄膜中的S/Se比例,实现了Cu2Sn(S,Se)3薄膜禁带宽度可调的目标；成功在Mo电极层上完成该路径的Cu2SnS3薄膜制备,为进一步制备Cu2SnS3薄膜太阳能电池器件做好了准备。(3)提出“采用Cu金属单质层作为前驱体,气相引入Sn、S元素制备Cu2SnS3薄膜”的实验思路,并验证了该制备路径的可行性,在一定程度上简化了前驱体制备时间,开辟Cu2SnS3薄膜制备的新途径。(4)得到了一套采用电沉积法硫化退火制备Cu2ZnSnS4薄膜的工艺技术,为今后在大规模生产中采用电沉积法制备目标薄膜积累了宝贵的经验。
[Abstract]:Cu2SnS3 (CTS) and CuZnSnS4 (CZTS) are a kind of typical multicomponent compound semiconductor photovoltaic materials. They have high absorption coefficient in visible region by their own p-type conductivity, band gap matching with solar radiation. Rich in nontoxic elemental properties and other advantages, it has become an important research object in the field of absorbing layer materials for thin film solar cells. The process parameters still need to be improved. Aiming at the problems and challenges in the preparation of Cu2SnS3 and Cu2ZnSnS4 thin films mentioned above, the preparation of Cu2SnS3 films with columnar grains is the main purpose of this paper, and the preparation technology of Cu2SnS3 with different precursor structures is explored. The technological conditions of vulcanization annealing were optimized, and the experimental conditions for preparing Cu2ZnSnS4 by electrodeposition were explored in order to adapt to the large-scale production technology. The specific research contents of this paper are as follows: 1) the method of vulcanization annealing of metal precursor with Cu/Sn laminated structure is adopted. Cu2SnS3 thin films with columnar grains were prepared, and Sn loss during vulcanization annealing of precursors was studied, and the Cu/Sn proportional adaptive phenomenon in the growth of Cu2SnS3 films was found. A solution to avoid Sn loss in vulcanization annealing by selecting precursors with proper Cu/Sn ratio (slightly less than 2.00) is proposed. The single target of Cu-Sn alloy with Cu/Sn ratio of 1.88 is tried. The precursor of Cu-Sn alloy with a certain proportion of Cu/Sn (about 2.00) was prepared by sputtering, and the Cu2SnS3 film was successfully prepared after vulcanization annealing, and no Sn loss occurred during the high temperature (鈮，

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