Surface composition deviation of Cu2ZnSnS4 derivative powdered samples

Powdered samples of Cu2ZnSnS4 derivatives prepared through a solid-state route were investigated by both bulk (electron dispersive X-ray spectroscopy) and surface-sensitive (X-ray photoelectron spectroscopy) methods. We observe a deviation in composition between the surface and the bulk for all non-stoichiometric samples (both Cu-poor and Cu-rich). This behavior has already been observed for slightly Cu-poor CZTS thin films and is reminiscent of that of CIGSe compounds.