Molten-droplet synthesis of composite CdSe hollow nanoparticles

Abstract

Many colloidal synthesis routes are not scalable to high production rates, especially for nanoparticles of complex shape or composition, due to precursor expense and hazards, low yields, and the large number of processing steps. The present work describes a strategy to synthesize hollow nanoparticles (HNPs) out of metal chalcogenides, based on the slow heating of a low-melting-point metal salt, an elemental chalcogen, and an alkylammonium surfactant in octadecene solvent. The synthesis and characterization of CdSe HNPs with an outer diameter of 15.6 ± 3.5 nm and a shell thickness of 5.4 ± 0.9 nm are specifically detailed here. The HNP synthesis is proposed to proceed with the formation of alkylammonium-stabilized nano-sized droplets of molten cadmium salt, which then come into contact with dissolved selenium species to form a CdSe shell at the droplet surface. In a reaction–diffusion mechanism similar to the nanoscale Kirkendall effect it is speculated that the cadmium migrates outwardly through this shell to react with more selenium, causing the CdSe shell to thicken. The proposed CdSe HNP structure comprises a polycrystalline CdSe shell coated with a thin layer of amorphous selenium. Photovoltaic device characterization indicates that HNPs have improved electron transport characteristics compared to standard CdSe quantum dots, possibly due to this selenium layer. The HNPs are colloidally stable in organic solvents even though carboxylate, phosphine, and amine ligands are absent; stability is attributed to octadecene-selenide species bound to the particle surface. This scalable synthesis method presents opportunities to generate hollow nanoparticles with increased structural and compositional variety.