Structural evolution of reduced GeO_x nanoparticles

GeO_x nanoparticles (NPs) are of growing interest in lithium storage and optoelectronics. GeO_x NPs prepared by chemical reduction, exposed to air or retained under N₂, then annealed under H₂ at various temperatures are studied herein using soft X-ray spectroscopy. We find that fresh and air-exposed GeO_x NPs evolve rather differently under annealing. The fresh GeO_x NPs start as a very amorphous heterogeneous mixture of GeO_x and Ge, and during annealing both the valence band and conduction band edges evolve. In contrast, the air-exposed GeO_x NPs initially contain quartz-phase GeO₂, and during annealing only the conduction band edge evolves due to increased oxygen vacancies forming unoccupied defect states (the valence band does not change until annealing at high temperture, at which point almost all of the GeO₂ is removed). These findings suggest a preparation and annealing strategy that could be used to tailor GeO_x NPs for their intended use in lithium storage or optoelectronic applications.