Gas-Phase Synthesis of Tunable-Size Germanium Nanocrystals by Inert Gas Condensation

Size-dependent optical properties of germanium (Ge) nanocrystals (NCs) make them a desirable material for optoelectronic applications. So far, the synthesis of ligand-free and tunable-size Ge NCs by inert gas condensation has been scarcely reported. In this work, we introduce a gas-phase approach to synthesize quantum-confined Ge NCs by inert gas condensation, where the size of the Ge NCs can be readily tuned by controlling the thickness of a Cu plate supporting the Ge target. As explained by simulations using the finite element method, the magnetic field configuration above the target can be manipulated by varying the thickness of the Cu backing plate. In-depth analysis based on transmission electron microscopy (TEM) results reveals the morphology and crystalline structure of Ge NCs. X-ray photoelectron spectroscopy has proven the formation of a substoichiometric Ge oxide shell for the as-deposited Ge NCs. In addition, Raman spectroscopy indicated peak shifts according to the phonon confinement model that yielded nanoparticle sizes in a good agreement with the TEM results. Furthermore, the quantum confinement effect for Ge NCs was demonstrated by analysis of the absorption (UV-vis-NIR) spectrum, which indicated that the band gap of the Ge NCs was increased from ∼0.8 to 1.1 eV with decreasing size of Ge NCs. Comparison with theory shows that the quantum confinement effect on the band gap energy for different-sized Ge NCs follows the tight-binding model rather well.