Optimized hot injection and HCl purification for high quality Cu₂ZnSnS₄ nanoparticles

Cu₂ZnSnS₄ (CZTS) is a narrow band gap, non-toxic, and environmentally friendly semiconductor with important properties for photovoltaic and electro-/photo-catalytic applications. In this study, we report on the synthesis of CZTS nanoparticles (NPs) by a simple and promising hot-injection technique using environmentally friendly, earth-abundant, and low-cost copper and zinc acetates in combination with tin chloride and elemental sulphur. Oleylamine was used as solvent and capping agent. The influence of injection temperatures on the crystalline size, morphology and crystal structure were studied. The formation of detrimental phases has been investigated, as well as their removal by using an HCl treatment during the purification step of the CZTS NPs synthesis process. Raman spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) analyses were used to investigate the formation mechanism of the CZTS NPs. The experimental results showed that the injection temperature influences the NPs growth. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR-ATR) analyses were used to confirm the removal of both organic traces and detrimental phases. It was found that HCl treatment plays a key role in the successful removal of impurities without altering the final crystalline composition profile or NPs surface.