Microstructure of High Temperature Oxidation Resistant Hf6B10Si31C2N50 and Hf7B10Si32C2N44 Films

High-temperature oxidation resistant amorphous Hf6B10Si31C2N50 and Hf7B10Si32C2N44 films were deposited by reactive pulsed dc magnetron sputtering. To investigate the oxidation mechanism, the films were annealed up to 1500 °C in air. The evolved microstructures were studied by X-ray diffraction and transmission electron microscopy. A three-layered microstructure was developed upon exposure to high temperature. An oxidized layer formed at the top surface for both films consisting of monoclinic and/or orthorhombic m-/o-HfO2 nanoparticles embedded in an amorphous SiOx-based matrix. The as-deposited bottom layer of the films remained amorphous (Hf6B10Si31C2N50) or partially recrystallized (Hf7B10Si32C2N44) exhibiting a h-Si3N4 and HfCxN1−x distribution along with formation of t-HfO2 at its top section. The two layers were separated by a partially oxidized transition layer composed of nanocrystalline h-Si3N4 and tetragonal t-HfO2. The oxidation process initiates at the bottom/transition layer interface with oxidation of Hf-rich domains either in the amorphous structure or in HfCxN1−x nanoparticles resulting in t-HfO2 separated by Si3N4 domains. The second stage occurs at the oxidized/transition layer interface characterized by densely packed HfO2, Si3N4 and quartz SiO2 nanostructures that can act as a barrier for oxygen diffusion. The small t-HfO2 nanoparticles merge and transform into large m-/o-HfO2 while h-Si3N4 forms amorphous SiOx matrix. A similar oxidation mechanism was observed in both films despite the different microstructures developed.