Crystallinity and Size Control of Colloidal Germanium Nanoparticles from Organogermanium Halide Reagents

Germanium (Ge) nanoparticles are gaining increasing interest due to their properties that arise in the quantum confinement regime, such as the development of the band structure with changing size. While promising materials, significant challenges still exist related to the development of synthetic schemes allowing for good control over size and morphology in a single step. Herein, we investigate a synthetic method that combines sulfur and primary amines to promote the reduction of organometallic Ge(IV) precursors to form Ge nanoparticles at relatively low temperatures (300 °C). We propose a reaction mechanism and examine the effects of solvents, sulfur concentration, and organogermanium halide precursors. Hydrosulfuric acid (H₂S) produced in situ acts as the primary reducing species, and we were able to increase the particle size more than 2-fold by tuning both the reaction time and quantity of sulfur added during the synthesis. We found that we are able to control the crystalline or amorphous nature of the resulting nanoparticles by choosing different solvents and propose a mechanism for this interaction. The reaction mechanism presented provides insight into how one can control the resulting particle size, crystallinity, and reaction kinetics. While we demonstrated the synthesis of Ge nanoparticles, this method can potentially be extended to other members of the group IV family.