Scalable oxygen-ion transport kinetics in metal-oxide films: Impact of thermally induced lattice compaction in acceptor doped ceria films

In this paper, we focus on the effect of processing-dependent lattice strain on oxygen ion conductivity in ceria based solid electrolyte thin films. This is of importance for technological applications, such as micro-SOFCs, microbatteries, and resistive RAM memories. The oxygen ion conductivity can be significantly modified by control of lattice strain, to an extent comparable to the effect of doping bulk ceria with cations of different diameters. The interplay of dopant radii, lattice strain, microstrain, anion-cation near order and oxygen ion transport is analyzed experimentally and interpreted with computational results. Key findings include that films annealed at 600 °C exhibit lattice parameters close to those of their bulk counterparts. With increasing anneal temperature, however, the films exhibited substantial compaction with lattice parameters decreasing by as much as nearly 2% (viz, Δd600-1100°C: -1.7% (Sc+3) > -1.5% (Gd +3) > -1.2% (La+3)) for the annealing temperature range of 600-1100°C. Remarkably 2/3rd of the lattice parameter change obtained in bulk ceria upon changing the acceptor diameter from the smaller Sc to larger La, can be reproduced by post annealing a film with fixed dopant diameter. While the impact of lattice compaction on defect association/ordering cannot be entirely excluded, DFT computation revealed that the main effect appears to result in an increase in migration energy and consequent drop in ionic conductivity. As a consequence, it is clear that annealing procedures should be held to a minimum to maintain the optimum level of oxygen ion conductivity for energy-related applications. Results reveal also the importance to understand the role of electro-chemo-mechanical coupling that is active in thin film materials. Electro-chemo-mechanic coupling is investigated for ionic conducting ceria-based materials. The impact of lattice strain on the near order characteristics and ionic conductivity is experimentally studied for bulk pellets and thin films. Density functional theory computation reveals an increase in migration energy and consequent drop in ionic conductivity, observed for lattice strains of up to 2% in doped ceria thin films. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim