Chemically Stable Group IV–V Transition Metal Carbide Thin Films in Hydrogen Radical Environments

Hydrogen is a crucial element in the green energy transition. However, its tendency to react with and diffuse into surrounding materials poses a significant challenge. Therefore, developing coatings to protect system components in hydrogen environments (molecular, radicals (H*), and plasma) is essential. In this work, we report group IV-V transition metal carbide (TMC) thin films as potential candidates for protective coatings in H* environments at elevated temperatures. We expose TiC, ZrC, HfC, VC, NbC, TaC, and Co₂C thin films, with native surface oxycarbides/oxides (TMO _<i>x</i> C _<i>y</i> /TMO _<i>x</i> ), to H* at elevated temperatures. Based on X-ray photoelectron spectroscopy performed on the samples before and after H*-exposure, we identify three classes of TMCs. HfC, ZrC, TiC, TaC, NbC, and VC (class A) are found to have a stable carbidic-C (TM-C) content, with a further subdivision into partial (class A1: HfC, ZrC, and TiC) and strong (class A2: TaC, NbC, and VC) surface deoxidation. In contrast to class A, a strong carbide reduction is observed in Co₂C (class B), along with a strong surface deoxidation. The H* interaction with TMC/TMO _<i>x</i> C _<i>y</i> /TMO _<i>x</i> is hypothesized to entail three processes: (i) hydrogenation of surface C/O atoms, (ii) formation of CH _<i>x</i> /OH _<i>x</i> species, and (iii) subsurface C/O atom diffusion to the surface vacancies. The number of adsorbed H atoms required to form CH _<i>x</i> /OH _<i>x</i> species (i) and the corresponding thermodynamic energy barriers (ii) are estimated based on the change in the Gibbs free energy (Δ<i>G</i>) for the reduction reactions of TMCs and TMO _<i>x</i> . Hydrogenation of surface carbidic-C atoms is proposed to limit the reduction of TMCs, whereas the deoxidation of TMC surfaces is governed by the thermodynamic energy barrier for forming H₂O.