Hafnium carbide formation in oxygen deficient hafnium oxide thin films

On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO$_{2-x}$) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC$_x$) at the surface during vacuum annealing at temperatures as low as 600 {deg}C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC$_x$ surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO$_2$ thin films prepared and measured under identical conditions, the formation of HfC$_x$ was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.