Journal
CHEMISTRY OF MATERIALS
Volume 26, Issue 6, Pages 2005-2014Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm403423e
Keywords
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Funding
- Singapore Ministry of Education [R-284-000-113-112, MOE2013-T2-1-096]
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The appearance of impurity phases in a Cu2ZnSnS4 (CZTS) layer is a big problem and challenge for high-performance CZTS photovoltaic devices. In spite of some experimental observations of secondary impurity phases, their growth mechanisms are not well established, especially in an S and Se coupled Cu2ZnSn(S,Se)(4) (CZTSSe) system. This work carried out a systematic experimental study on the formation of secondary phases in CZTSSe, i.e., CuxSe and SnSe on the top surface and ZnS at the bottom. Interestingly, a clear reaction pathway for the formation of uniform CZTSSe film was revealed through a temperature dependent annealing of a near-stoichiometric sample. A further reaction thermodynamic analysis was applied to explore the fundamentals of the secondary phase formation mechanisms. Besides, a diagrammatic CZTSSe film growth model was proposed to illustrate the detailed phase development procedures during selenization of a sulfur-contained precursor. A deeper insight in the formation of CZTSSe film can not only provide a better understanding of the experimental phenomena but also guide possible improvement routes of the film formation strategy to achieve a more promising absorber of a thin film solar cell.
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