Colloidal spherical stibnite particles via high-temperature metallo-organic synthesis

Antimony trisulfide (Sb₂S₃) is an emerging semiconductor with a high absorption coefficient and a bandgap in the visible range. This makes it a promising material for various electronic and optoelectronic applications. However, one of the main challenges is still the synthesis of the material, as it is usually obtained either as a nanomaterial in its amorphous form with inferior optical properties or in crystalline rod-like structures in the micrometer or sub-micrometer range, which leads to application-related difficulties such as clogging in inkjet printing or spraying processes or highly porous layers in film applications. In this study, a one-pot synthesis of highly crystalline, spherical Sb₂S₃ sub-micron particles is presented. The particles are growing encapsulated in a removable, wax-like matrix that is formed together with an intermediate from the precursors SbCl₃ and l-cysteine. Both substances are insoluble in the reaction mixture but well-dispersable in the solvent 1-octadecene (ODE). The intermediate forms a complex crosslinked architecture whose basic building block consists of an Sb atom attached to three cysteine molecules via Sb-S bonds. Embedded in the matrix consisting of excess cysteine, ODE, and chlorine, the intermediate decomposes into amorphous Sb₂S₃ particles that crystallize as the reaction proceeds at 240 °C. The final particles are highly crystalline, spherical, and in the sub-micron range (420 ± 100 nm), making them ideal for further processing. The encapsulation method could not only provide a way to extend the size range of colloidal particles, but in the case of Sb₂S₃, this method circumvents the risk of carbonization of ligands or insufficient crystallization during the annealing of amorphous material.