Hydrogen diffusion in cerium oxide thin films fabricated by pulsed laser deposition.

Cerium oxide (CeO 2) is well known to be reducible by hydrogen (H 2), yet the diffusion and solution properties of hydrogen in ceria at elevated temperatures have remained challenging to evaluate. We therefore fabricated nanometer-thin (∼100 nm) cerium oxide films on Si(111) substrates by pulsed laser deposition (PLD) and quantitatively investigated the H depth distributions therein by means of resonant 1H(15N,αγ)12C nuclear reaction analysis (NRA) before and after annealing in H 2 gas at 773–973 K. X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) reveal that the as-deposited films exhibit single phase CeO 2 structure and partially reduced stoichiometry (CeO 1.69). H 2 annealing does not largely change the H content of the as-deposited films; in all conditions several atomic percent of hydroxyl (OH) are found to exist in a thin (∼4 nm) surface layer, whereas stably bound hydrogen in the bulk of the films is almost uniformly distributed and of much smaller quantity (∼0.2 at.%) than the oxygen vacancy concentration in the partially reduced ceria. Its low concentration and high thermal stability identify this bulk H species as likely being strongly bound to defects in the polycrystalline films rather than as a hydride species that interacts weakly with O-vacancies. The H diffusion coefficient and activation energy in the ceria films are determined as > 10−18 m2 s−1 at 773–973 K and <1.69 eV, respectively. The observed diffusion activation energy is somewhat larger than theoretical predictions for thermal diffusion of H in stoichiometric bulk CeO 2 , suggesting that defects and oxygen vacancies in the PLD-fabricated ceria thin films possibly have an impact on the H mobility. [Display omitted] • As-deposited films (∼100 nm) are partially reduced stoichiometry (CeO 1.69). • H 2 annealing of CeO 2-x films at 773–973 K results in a partial depletion of OH groups. • H is quite stable as OH in the surface layer up to about 4 nm, but not as hydride in the bulk. • The H species observed in the bulk of the films are rather small abundance (∼0.2 at.%). • Imperfections and vacancies are likely routes for hydrogen diffusion in CeO 2-x thin films. [ABSTRACT FROM AUTHOR]