Cu2ZnSnS4 (CZTS) thin films were prepared by post-annealing films of metal sulfides of Cu2S, ZnS and SnS2 precursors deposited on soda-lime glass substrates by photo-chemical deposition (PCD) from aqueous solution containing CuSO4, ZnSO4, SnSO4 and Na2S2O3. In this study, sulfurization was employed to prepare high quality CZTS thin films. Deposited films of metal sulfides were annealed in a furnace in an atmosphere of N2 or N2+H2S(5%) at the temperature of 300°, 400° or 500 °C. The sulfured films showed X-ray diffraction peaks from (112), (220), and (312) planes of CZTS and the peaks became sharp by an increase in the sulfurization temperature. CZTS thin film annealed in atmosphere of N2 was S-poor. After annealing atmosphere was changed from N2 into N2+H2S(5%), the decrease of a composi- tional ratio of sulfur could be suppressed. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
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