Long-Term Oxidation Susceptibility in Ambient Air of the Semiconductor Kesterite Cu 2 ZnSnS 4 Nanopowders Made by Mechanochemical Synthesis Method.

The often overlooked and annoying aspects of the propensity of no-oxygen semiconductor kesterite, Cu 2 ZnSnS 4 , to oxidation during manipulation and storage in ambient air prompted the study on the prolonged exposure of kesterite nanopowders to air. Three precursor systems were used to make a large pool of the cubic and tetragonal polytypes of kesterite via a convenient mechanochemical synthesis route. The systems included the starting mixtures of (i) constituent elements (2Cu + Zn + Sn + 4S), (ii) selected metal sulfides and sulfur (Cu 2 S + ZnS + SnS + S), and (iii) in situ made copper alloys (from the high-energy ball milling of the metals 2Cu + Zn + Sn) and sulfur. All raw products were shown to be cubic kesterite nanopowders with defunct semiconductor properties. These nanopowders were converted to the tetragonal kesterite semiconductor by annealing at 500 °C under argon. All materials were exposed to the ambient air for 1, 3, and 6 months and were suitably analyzed after each of the stages. The characterization methods included powder XRD, FT-IR/UV-Vis/Raman/NMR spectroscopies, SEM, the determination of BET/BJH specific surface area and helium density (d He ), and direct oxygen and hydrogen-content analyses. The results confirmed the progressive, relatively fast, and pronounced oxidation of all kesterite nanopowders towards, mainly, hydrated copper(II) and zinc(II) sulfates, and tin(IV) oxide. The time-related oxidation changes were reflected in the lowering of the energy band gap E g of the remaining tetragonal kesterite component.