|Title||Scalable Oxygen- Ion Transport Kinetics in Metal- Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films|
|Publication Type||Journal Article|
|Year of Publication||2014|
|Authors||Rupp, JLM, Fabbri, E, Marrocchelli, D, Han, J-W, Chen, D, Traversa, E, Tuller, HL, Yildiz, B|
|Journal||Advanced Functional Materials|
|Pagination||1562 - 1574|
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 degrees 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, d(600-1100 degrees C): -1.7% (Sc+3) > -1.5% (Gd+3) > -1.2% (La+3)) for the annealing temperature range of 600-1100 degrees C. Remarkably 2/3(rd) 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.