采用循环伏安法研究了制备CZTS薄膜四元预制层的电化学沉积机理.结合XRD,SEM,EDS和Raman技术分析预制层退火的相转变机制.结果表明:溶液中Cu2+和Sn2+浓度不仅影响其本身的沉积速率,还影响溶液中其他金属元素的沉积速率,而Zn2+浓度仅影响其本身沉积速率.四元预制层的沉积以原子层外延为机理,在负电位作用下,Cu2+先转变为Cu原子沉积在衬底表面,且与衬底附近析出的S原子发生化学反应,在衬底上生成CuS,同样,SnS和ZnS也以这种方式交替沉积在衬底上.预制层二元硫化物随着退火温度的升高逐渐转变为Cu2(3) SnS3(4)和Cu2ZnSnS4.利用四元共电沉积预制层550℃退火1h合成的Cu2ZnSnS4薄膜原子比为Cu∶Zn∶Sn∶S=23.72∶12.22∶13.07∶50.99.无偏压下合成的CZTS薄膜光电流达到约6nA.
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