New synthesis route to kesterite Cu 2 ZnSnS 4 semiconductor nanocrystalline powders utilizing copper alloys and a high energy ball milling-assisted process

Presented is a new mechanochemically assisted synthesis route to kesterite Cu 2 ZnSnS 4 semiconductor for perspective photovoltaic applications. Initially, the combined copper Cu, zinc Zn, and tin Sn powders in atomic ratio 2:1:1 were subjected to high energy ball milling in a planetary ball mill under the highest reported to date rotation speeds of 900 and 1000 rpm to yield a definite nanopowder mixture of the copper intermetallic phases, i.e., γ Cu 5 Zn 8 -type and η’ Cu 6 Sn 5 -type of non-stoichiometric compositions. Upon addition of a suitable amount of sulfur S, the reactive milling was continued affording a pure sphalerite-type cubic phase tentatively called a pre-kesterite. As expected from our earlier research, this by-product did not exhibit any 65 Cu and 119 Sn MAS NMR spectra or clearly-defined absorption in the UV–vis range. The disordered and very much random Cu-Zn-Sn metal site occupation of all metal layers in the structure is proposed to account for the observed properties of pre-kesterite. The subsequent annealing under argon at temperatures around 500−550 °C resulted in the cubic phase conversion to the tetragonal phase of kesterite, prevailingly, by metal center reconfiguration into distinct Cu-Sn and Cu-Zn layers accompanied by crystal growth/particle recrystallization. The micro-Raman spectra were consistent with similar bonding and lattice phonon characteristics in both related materials. The XPS data confirmed the same oxidation states and comparable energy level characteristics of the constituent elements. The annealed nanocrystalline powders showed the anticipated 65 Cu and 119 Sn MAS NMR features, while supporting remnant paramagnetism, and UV–vis semiconducting characteristics of the target kesterite.