Magnetism of Kesterite Cu₂ZnSnS₄ Semiconductor Nanopowders Prepared by Mechanochemically Assisted Synthesis Method

High energy ball milling is used to make first the quaternary sulfide Cu₂ZnSnS₄ raw nanopowders from two different precursor systems. The mechanochemical reactions in this step afford cubic pre-kesterite with defunct semiconducting properties and showing no solid-state ⁶⁵Cu and ¹¹⁹Sn MAS NMR spectra. In the second step, each of the milled raw materials is annealed at 500 and 550 °C under argon to result in tetragonal kesterite nanopowders with the anticipated UV-Vis-determined energy band gap and qualitatively correct NMR characteristics. The magnetic properties of all materials are measured with SQUID magnetometer and confirm the pre-kesterite samples to show typical paramagnetism with a weak ferromagnetic component whereas all the kesterite samples to exhibit only paramagnetism of relatively decreased magnitude. Upon conditioning in ambient air for 3 months, a pronounced increase of paramagnetism is observed in all materials. Correlations between the magnetic and spectroscopic properties of the nanopowders including impact of oxidation are discussed. The magnetic measurements coupled with NMR spectroscopy appear to be indispensable for comprehensive kesterite evaluation.