Liberation of Ion Implanted Ge Nanocrystals from a Silicon Dioxide Matrix via Hydrofluoric Acid Vapor Etching

A method to liberate germanium (Ge) nanocrystals from silicon dioxide (SiO₂) thin films by hydrofluoric acid (HF) vapor etching is presented. Multi-energy implantation of mass separated Ge ions into 500-nm-thick wet oxide layers on silicon (Si) substrates followed by thermal annealing produces nanocrystals that are 2 to 8 nm in diameter. Raman spectra exhibit the expected asymmetric line shapes due to the phonon confinement effect, but with a higher peak frequency than predicted. To free the nanocrystals, samples are etched in HF vapor to selectively remove the SiO ₂ matrix and expose the nanocrystal surfaces. Raman spectra of etched samples display peak frequencies consistent with relief of compressive stress. The liberated nanocrystals show long-term stability under ambient atmospheric conditions. Ge nanocrystals can be removed from etched surfaces using an ultrasonic methanol cleaning procedure. The nanocrystal-containing solution is applied to a TEM grid and the solvent is evaporated. Subsequently obtained electron diffraction patterns confirm that the nanocrystals survive this transfer step. Thus, liberated Ge nanocrystals are expected to be accessible for a wide range of manipulation processes and direct characterization techniques.