Investigation of surface phase formation during Sn-rich growth of Cu2ZnSnS4 polycrystalline thin films for solar cells

Cu2ZnSnS4 (CZTS) is a semiconductor material made of nontoxic, earth abundant elements, making it a promising topic of research for absorber layers in thin film solar cells. We observed that rapid thermal annealing of tin (Sn)-rich co-sputtered CZTS films resulted in crystalline, hexagonal platelets of tin-disulfide (SnS2) 5-30 μm long at the surface of the film. In this work, the formation mechanisms of these surface crystallites and their implications for CZTS absorber layer processing were investigated. The formation and decomposition of these platelets were studied by observing the changes in their structural, morphological, compositional, and vibrational properties accompanying the imposition of lateral temperature gradients as well as different annealing atmospheres. The homogeneous co-sputtered films were annealed in a graphite boat in a quartz reactor using a base heater and halogen lamp. Interrupting annealings to examine stages of crystal formation showed at around 400 oC SnS2 began to form on the surface of films. Near the edges of the film, where temperatures were found to be higher, crystals melted into an amorphous unknown tin-sulfide phase. Diffusion of species from the film into the base of the crystals formed long CZTS grains of which the amorphous phase left behind as it coalesced. Annealing without sulfur (S) increased Sn and S losses from the film and increased the number of crystals nucleated on the surface of the film. For solar cell device applications of CZTS thin films, removal of these SnS2 iv surface crystallites is necessary; thus wet chemical and thermal decomposition etching techniques were studied. Wet etching attempts with KCN and NH4OH solutions did little to etch crystals. HCl solution damaged the CZTS film as much as the crystals and therefore was also unsuitable. Thermal etching by evacuating the chamber near the end of annealing transformed the SnS2 crystals into a grainy, S-poor Sn phase via the decomposition of SnS2 by removing the vapor species with which it is in equilibrium. Understanding the role of Sn species during annealing is important for the complex CZTS system because small deviations from Sn stoichiometry results in drastic changes in the secondary phases and microstructure of the film. The experiments and insight provided in this thesis represent unexplored unconventional methods toward CZTS growth and different approaches for CZTS processing for development of thin film solar cell technology.