Quantitative evaluation of biaxial compressive strain and its impact on proton conduction and diffusion in yttrium-doped barium zirconate epitaxial thin films

Abstract Proton-conducting oxides, including 20 mol% yttrium-doped BaZrO₃ (BZY20), have attracted considerable attention as electrolytes for environmentally friendly electrochemical cells, such as proton ceramic fuel cells (PCFCs) and proton-conducting solid oxide cells. These oxides exhibit fast proton conduction due to the complex physicochemical phenomena of hydration, chemical lattice expansion, proton migration, proton trapping, and local distortion. Using a proton-conducting oxide as an electrolyte film in electrochemical devices introduces an interface, which thermally and chemically generates mechanical strain. Here, we briefly review the current state of research into proton-conducting oxides in bulk samples and films used in electrochemical devices. We fabricated 18 and 500 nm thick 20 mol% BZY20 epitaxial films on (001) Nb-doped SrTiO₃ single-crystal substrates to form a model interface between proton-conductive and non-proton-conductive materials, using pulsed laser deposition, and quantified the mechanical strain, proton concentration, proton conductivity, and diffusivity using thin-film x-ray diffractometry, thermogravimetry, secondary ion mass spectrometry, and AC impedance spectroscopy. Compressive strains of −2.1% and −0.85% were measured for the 18 and 500 nm thick films, respectively, and these strains reduced both the proton conduction and diffusion by five and one orders of magnitude, respectively, at 375 °C. Analysis based on a simple trapping model revealed that the decrease in proton conduction results from the slower diffusion of mobile protons with a negligible change in the proton trapping contribution. The model shows that the high ohmic resistance reported for a high-performance PCFC with a power density of 740 mW cm⁻² at 600 °C can be solely explained by the estimated compressive strain in the cells. This study shows that minimizing biaxial compressive strain by appropriate choices of the electrolyte–electrode combination and fabrication process is important for maximizing the performance of electrochemical cells.