On the Formation of IR-Light-Emitting Ge Nanocrystals in Ge:SiO₂ Films

The study is concerned with light-emitting Ge nanocrystals formed during the annealing of Ge_x[SiO₂]_{1 –x} films produced by the high-vacuum cosputtering of germanium and quartz targets onto substrates at a temperature of 100°C. In accordance with the conditions of growth, the Ge molar fraction was varied from 10 to 40%. By means of electron microscopy and Raman spectroscopy, amorphous Ge nanoclusters ~4–5 nm in dimensions are detected in as-deposited films with a Ge content higher than 20 mol %. To crystallize amorphous nanoclusters, annealing at temperatures of up to 650°C is used. The kinetics of the crystallization of Ge nanoclusters is studied, and it is established that up to ~1/3 of the amorphous phase is retained in the system, supposedly at the interfaces between nanocrystals and the surrounding amorphous SiO₂ matrix. It is found that, upon annealing in normal atmosphere, germanium nanoclusters are partially or completely oxidized (at a Ge molar fraction of 30% and smaller). An intense infrared photoluminescence signal from quantum-confined Ge nanocrystals and a visible photoluminescence signal defined by defect complexes (oxygen vacancy + excess Ge atoms) are observed.