Hydrogen (deuterium) dynamics and thermal stability in ion-irradiated platinum-hydride thin films synthesized at low temperature

Abstract

Hydrogen (H) and deuterium (D) interactions with transition metals play a central role in heterogeneous catalysis and hydrogen-related technologies. While H-Pt surface interactions have been extensively studied, direct investigations of hydrogen incorporation and transport in Pt remain limited due to its low solubility. Here, we study H(D) incorporation and desorption dynamics in metastable $PtH(D)_x$ thin films prepared by low-energy ion irradiation, enabling hydrogen loading far above equilibrium concentrations. Nuclear reaction analysis (NRA) reveals a nonuniform hydrogen depth profile with two accumulation regions: the subsurface and the film-substrate interface. Thermal desorption spectroscopy (TDS) exhibits two desorption peaks near 190 and 230 K, consistent with hydrogen release from these sites. Resistance relaxation measurements, analyzed within a two-parallel-channel conduction model, indicate different relaxation kinetics for subsurface and near-interface hydrogen. Arrhenius analysis reveals two thermally activated processes for $PtH_x$ with an average hydrogen concentration of $x = 0.15$, with activation energies of $130 \pm 18$ meV (subsurface) and $164 \pm 26$ meV (near interface). Above 140 K, D exhibits slower relaxation rates with activation energies of $117 \pm 8$ and $121 \pm 7$ meV for $PtD_x$ prepared under the same implantation dose. Within experimental uncertainty, the activation barriers remain comparable, while the prefactors are reduced significantly for D, indicating isotope-dependent attempt frequencies and zero-point energy effects. TDS simulations based on the Polanyi-Wigner formalism reproduce the experimental desorption spectra by resolving subsurface and near-interface contributions, in agreement with the NRA profile. These findings provide insight into hydrogen kinetics in $PtH_x$ for Pt-based catalysis, sensing, and hydrogen-metal interactions.