Effect of post-deposition annealing on crystal structure of RF magnetron sputtered germanium dioxide thin films

In this work, we demonstrate the growth and phase stabilization of ultrawide bandgap polycrystalline rutile germanium dioxide (GeO2) thin films. GeO2 thin films were deposited using RF magnetron sputtering on r-plane sapphire (Al2O3) substrates. As-deposited films were x-ray amorphous. Postdeposition annealing was performed at temperatures between 650 and 950 °C in an oxygen or nitrogen ambient. Annealing at temperatures from 750 to 950 °C resulted in mixed-phase polycrystalline films containing tetragonal (rutile) GeO2, hexagonal (α-quartz) GeO2, and/or cubic (diamond) germanium (Ge). When nitrogen was used as the anneal ambient, mixed GeO2 phases were observed. In contrast, annealing in oxygen promoted stabilization of the r-GeO2 phase. Grazing angle x-ray diffraction showed a preferred orientation of (220) r-GeO2 for all crystallized films. The combination of O2 annealing and O2 flux during growth resulted in r-GeO2 films with highly preferential alignment. Using electron microscopy, we observed an interfacial layer of hexagonal-oriented GeO2 with epitaxial alignment to the (11¯02) Al2O3 substrate, which may help stabilize the top polycrystalline r-GeO2 film.