Absorption and luminescence in amorphous SixGe1―xO2 films fabricated by SPCVD

Optical absorption and photoluminescence of Ge-doped silica films fabricated by the surface-plasma chemical vapor deposition (SPCVD) are studied in the 2-8 eV spectral band. The deposited on silica substrate films of about 10 μm in thickness are composed as x·GeO2(1-x)·SiO2 with x ranging from 0.02 to 1. It is found that all as-deposited films do not luminesce under the excitation by a KrF (5 eV) excimer laser, thus indicating lack of oxygen deficient centers (ODCs) in them. After subsequent fusion of silicon containing (x<1) films by a scanning focused CO2 laser beam absorption band centered at 5 eV as well as two luminescence bands centered at blue (3.1 eV) and UV (4.3 eV) wavelengths arise, highlighting the formation of the ODCs. The excitation of unfused SPCVD films by an ArF (6.4 eV) excimer laser yields a luminescence spectrum with two bands typical for the ODCs, but with a faster decay kinetics. Intensities of these bands grow up with samples cooling down to a temperature of 80-60 K. Unfused films excited by the ArF laser also demonstrate luminescence due to recombination of a trapped charge resulted from the excitation of localized electron states of the glass network. In the unfused GeO2 film luminescence related to a self-trapped exciton (STE) typical for GeO2 crystals with α-quartz structure is observed. The observed STE luminescence can be indicative of the crystalline fraction availability in the film. Whereas GeO2 crystals are known as not containing twofold coordinated germanium, a polycrystalline inclusion in the SPCVD GeO2 film serves as a factor explaining the absence of any spectroscopic manifestation of this type of defects in it even after fusion. On the other hand, lack of STE luminescence in other unfused films with x < 1 testifies truly amorphous state of the matter in them.