Static and dynamic components of Debye–Waller coefficients in the novel cubic polymorph of low-temperature disordered Cu2ZnSnS4

Abstract

Cu2ZnSnS4(CZTS) is an attractive material for sustainable photovoltaics and thermoelectrics, and several properties originate from its marked polymorphism. High-energy mechanical alloying is found to lead to a disordered phase that possesses a sphalerite-like cubic structure. This is investigated in detail with the aid of laboratory and synchrotron radiation X-ray diffraction, Raman spectroscopy, electron microscopy andab initiomolecular dynamics. The disordered cubic polymorph is preserved below 663 K. With thermal treatments above 663 K, the tetragonal kesterite phase forms, used here as a reference for structural and microstructural features. Particular attention is paid to the stacking arrangement: a significant fraction of twin faults was found in the disordered cubic samples, which then progressively annealed with domain growth and with the transition to the ordered tetragonal phase. This study also focuses on Debye–Waller coefficients, which were found to be considerably larger for the disordered cubic than the tetragonal sample. Indeed, disorder leads to an ∼1 Å2upward shift through the temperature range 100–700 K, a feature confirmed byab initiocalculations, which points to a particularly high contribution from disordered Sn cations. This supports the general understanding that structural disorder introduces a temperature-independent static contribution to the atomic mean-square displacement. Debye–Waller coefficients are found to be a good measure of this disorder, known to have a critical effect on transport properties.