Sacrificial Silver Nanoparticles: Reducing GeI₂ To Form Hollow Germanium Nanoparticles by Electroless Deposition

Herein we report the electroless deposition of Ge onto sacrificial Ag nanoparticle (NP) templates to form hollow Ge NPs. The formation of AgI is a necessary component for this reaction. Through a systematic study of surface passivating ligands, we determined that tri-n-octylphosphine is necessary to facilitate the formation of hollow Ge NPs by acting as a transport agent for GeI2 and the oxidized Ag(+) cation (i.e., AgI product). Annular dark-field (ADF) scanning transmission electron microscopy (STEM) imaging of incomplete reactions revealed Ag/Ge core/shell NPs; in contrast, completed reactions displayed hollow Ge NPs with pinholes which is consistent with the known method for dissolution of the nanotemplate. Characterization of the hollow Ge NPs was performed by transmission electron microscopy, ADF-STEM, energy-dispersive X-ray spectroscopy, UV-vis spectrophotometry, and Raman spectroscopy. The galvanic replacement reaction of Ag with GeI2 offers a versatile method for controlling the structure of Ge nanomaterials.