XRD and EXAFS studies on the structure of Er3+-doped SiO2-HfO2 glass-ceramic waveguides: Er3+-activated HfO2 nanocrystals

This paper describes the structure of Er3+-doped SiO2-HfO2 waveguides containing nanocrystals of HfO2. Pure and 1 mol% Er3+-doped 70SiO2-30HfO2 films were deposited by the sol-gel method on amorphous SiO2 substrates using the dip-coating technique. Each waveguide has experienced a single thermal treatment at temperatures ranging from 900 to 1200 deg. C, for either short (30 min) or long (24 h) durations. Crystallization and microstructure were studied by x-ray diffraction (XRD). The local environments of hafnium and erbium ions were determined, respectively, from Hf and Er L3-edges extended x-ray absorption fine structure (EXAFS) experiments. Both XRD and EXAFS results demonstrate the substitution of Hf4+ by Er3+ ions in the crystalline structure. XRD shows the nucleation of tetragonal HfO2 nanocrystals after heat treatment at 1000 deg. C for 30 min in the pure waveguide, and at 900 deg. C for 24 h in the waveguide doped with Er3+. In both series, partial transformation from tetragonal to monoclinic HfO2 nanocrystals starts after heat treatment at 1100 deg. C for 24 h. The average crystallite size and size distribution can be controlled by thermal annealing temperature and duration, respectively, with brief treatment yielding a more homogeneous nanocrystal size.