Ge-Si-O phase separation and Ge nanocrystal growth in Ge:SiO(x)/SiO(2) multilayers--a new dc magnetron approach.

Ge:SiO(x)/SiO(2) multilayers are fabricated using a new reactive dc magnetron sputtering approach. The influence of the multilayer stoichiometry on the ternary Ge-Si-O phase separation and the subsequent size-controlled Ge nanocrystal formation is explored by means of x-ray absorption spectroscopy, x-ray diffraction, electron microscopy and Raman spectroscopy. The ternary system Ge-Si-O reveals complete Ge-O phase separation at 400 °C which does not differ significantly to the binary Ge-O system. Ge nanocrystals of < 5 nm size are generated after subsequent annealing below 700 °C. It is shown that Ge oxides contained in the as-deposited multilayers are reduced by a surrounding unsaturated silica matrix. A stoichiometric regime was found where almost no GeO(2) is present after annealing. Thus, the Ge nanocrystals become completely embedded in a stoichiometric silica matrix favouring the use for photovoltaic applications.