Synthesis Strategy Toward Minimizing Adventitious Oxygen Contents in the Mechanochemically Made Semiconductor Kesterite Cu2ZnSnS4 Nanopowders

A multipronged approach to the refined mechanochemical synthesis of the semiconductor kesterite Cu₂ZnSnS₄ with minimal quantities of adventitious oxygen as well as to optimizing handling procedures from that angle is described. Three precursor systems are used to provide a pool of freshly made cubic prekesterite nanopowders with no semiconductor properties and the thermally annealed at 500 °C tetragonal kesterite nanopowders of the semiconductor. Based on the previously reported high propensity of such nanopowders to long-term deteriorating oxidation in ambient air, suitable modifications of all crucial synthesis steps are implemented, which are directed toward excluding or limiting the materials' exposure to air. The nanopowders are comprehensively characterized by powder XRD, FT-IR/Raman/UV-Vis spectroscopies, solid-state ⁶⁵Cu/¹¹⁹Sn MAS NMR, TGA/DTA-QMS analysis, SEM, BET/BJH specific surface area, and helium density determinations, and, significantly, are directly analyzed for oxygen and hydrogen contents. The important finding is that following the anaerobic procedures and realistically minimizing the materials' exposure to air in certain manipulation steps results in the preparation of better oxidation-resistant nanopowders with a dramatic relative decrease in their oxygen content than previously reported. The adherence to the strict synthesis conditions that limit contact of the no-oxygen-containing kesterite nanopowders with ambient air is emphasized.