Kinetic Processes and surfactant design of Group I elements on CZTS (1\bar1\bar2\bar) surface

Cu₂ZnSnS₄ (CZTS) is a promising thin-film solar-cell material consisted of earth abundant and nontoxic elements. Yet, there exists a fundamental bottle neck that hinders the performance of the device due to complexed intrinsic defects properties and detrimental secondary phases. Recently, it was proven experimentally that Na and K in co-evaporation growth of CZTS can enlarge the grain size and suppress ZnS secondary phase near surface, but the reasons are not well understood. We used first principle calculations to investigate the kinetic processes on CZTS (1\bar1\bar2\bar) surface involving Group I elements, including Na, K, and Cs, to demonstrate their surfactant effects. Both the structure of the reconstructed surfaces involving Group I elements and various diffusion paths of a Zn ad-atom in these reconstructed surfaces were explored. The advantages and concerns of the surfactant effects of Na, K, Cs, were systematically compared and discussed. Also, a disordered metastable configuration with a diffusion barrier of about 400meV was found. In addition, our studies provide a systematical design principle for surfactant effects during the growth.