Nanoparticles Prepared by Salt Vapor‐Solvent Vapor Cocondensation and Controlled Nucleation: Metal Sulfides (ZnS,CdS, CdSe,PbS), and Metal Halide (LiF). Size,Aggregates, Structures,Digestive Ripening,Superlattices, and Impregnations

A versatile method for the production of gram quantities of nanocrystals of metal sulfides and metal halides has been developed, based on vaporization of the bulk materials followed by controlled nucleation of the molecular vapor species in cold solvent matrices (cocondensate). This approach worked well with ZnS, CdS, CdSe, CdTe, SnS, PbS, and LiF as examples, and is applicable for a large number of semiconductors, ionic salts, as well as metals. Choice of solvent (polar or non‐polar), vaporization rate, and rate of warm‐up of the cocondensate (period of nucleation) allows some control of crystallite size, aggregate size, and surface area. Interestingly, polar solvents lead to smaller nanocrystals, but larger, less porous aggregates. Also, molar mass of the molecular species has an effect on crystallite size, with heavier molecules giving smaller crystals, apparently due to slower migration in the warming cocondensate. Studies of sintering temperature and crystal growth have shown the nanocrystals are quite thermally stable. Addition of ligands, such as thiols, followed by heating in solvent (digestive ripening) has allowed more monodisperse materials to be formed. Finally, this molecular vapor synthesis approach can be used for impregnating semiconductors (CdS, CdSe) of controlled crystal size on solid supports, such as TiO₂ or SiO₂.