A reliable, colloidal synthesis method of the orthorhombic chalcogenide perovskite, BaZrS3, and related ABS3 nanomaterials (A = Sr, Ba; B = Ti, Zr, Hf): a step forward for earth-abundant, functional materials

Abstract

Recently, chalcogenide perovskites, of the form ABX₃, where typically A = alkaline earth metals Ca, Sr, or Ba; B = group IV transition metals Zr or Hf; and X = chalcogens S or Se, have become of interest for their potential optoelectronic properties. In this work, we build upon recent studies and show a general synthesis protocol, involving the use of carbon disulfide insertion chemistry, to generate highly reactive precursors that can be used towards the colloidal synthesis of numerous ABS₃ nanomaterials, including BaTiS₃, BaZrS₃, BaHfS₃, α-SrZrS₃ and α-SrHfS₃. We overcome the shortcomings in the current literature where BaZrS₃ nanoparticles are synthesized in separate phases via colloidal methods and lack a reproducible protocol for orthorhombic perovskite nanoparticles. We present a high-temperature, hot-injection method that reliably controls the formation of the colloidal BaZrS₃ nanoparticles with the Pnma orthorhombic distorted perovskite structure. We show that the alternate phase, most notably denoted by its extra peaks in the pXRD pattern, is distinct from the distorted perovskite phase as it has a different bandgap value obtained via UV-vis measurements. We also show that the reaction byproducts, resulting from the use of oleylamine and CS₂, have their own photoluminescence (PL) and their residual presence on the surface of the nanoparticles complicates the interpretation of PL from the nanoparticles. The utility of these nanomaterials is also assessed via the measurement of their absorption properties and in the form of highly stable colloidal inks for the fabrication of homogeneous, crack-free thin films of BaZrS₃ nanoparticles.