Phase formation in Cu2ZnSnSe4 thin films deposited with multi-stage co-evaporation processes

The deposition of Cu2ZnSnSe4 (CZTSe) thin films with a two-stage co-evaporation process was investigated with in situ laser light scattering (LLS) and ex situ characterization methods. As a result of the process conditions as well as intrinsic reactions, the film growth is divided into distinct growth phases with characteristic phase formation processes in each phase. In a first phase, under supply of Cu, Zn, Sn and Se, only Cu2-xSe and ZnSe are deposited on the substrate. A film with several hundred nanometer thickness is necessary to initiate the CZTSe formation. Then, in a second phase, CZTSe grows by incorporation of Cu and Sn in ZnSe while Cu2-xSe remains as secondary phase. In the second process stage with terminated Cu evaporation, the remaining Cu2-xSe is consumed and the film stoichiometry turns from Cu-rich to Cu-poor. A substantial influence on the growth process is found for the Mo substrate, CZTSe growth is hindered by a detrimental interaction between Mo and CZTSe. During the whole process, the Cu2-xSe phase plays an important role in the grain growth process and supports the formation of large CZTSe grains. (C) 2013 Elsevier B.V. All rights reserved.