Phase separation and nanocrystal formation in GeO

The temperature-induced phase separation (disproportionation) and Ge nanocrystal formation in bulk amorphous germanium monoxide (a-GeOx,x≈1) are studied both in situ and ex situ by measurements of the x-ray absorption near edge structure at the Ge K-edge and x-ray diffraction. The considerable amount of suboxides contained in the native a-GeO samples decreases with increasing annealing temperature. The phase separation sets in at a temperature of 260±20 °C and is almost completed at a temperature of 450±18 °C before nanocrystal formation occurs. Ge nanocrystals of a few nanometers in diameter are observed for an annealing temperature of 509±15 °C. The time dependence of the phase separation and the effect of different annealing procedures are discussed. The presented results provide important information for the production of Ge nanocrystals embedded in amorphous oxide matrices which are relevant for optoelectronic applications.