In situ electrochemical observation of anisotropic lattice contraction of La(0.6)Sr(0.4)FeO(3−δ) electrodes during pulsed laser deposition

La(0.6)Sr(0.4)FeO(3−δ) (LSF) electrodes were grown on different electrolyte substrates by pulsed laser deposition (PLD) and their oxygen exchange reaction (OER) resistance was tracked in real-time by in situ PLD impedance spectroscopy (i-PLD) inside the PLD chamber. This enables measurements on pristine surfaces free from any contaminations and the direct observation of thickness dependent properties. As substrates, yttria-stabilized zirconia single crystals (YSZ) were used for polycrystalline LSF growth and La(0.95)Sr(0.05)Ga(0.95)Mg(0.05)O(3−δ) (LSGM) single crystals or YSZ single crystals with a 5 nm buffer-layer of Gd(0.2)Ce(0.8)O(2−δ) for epitaxial LSF film growth. While polycrystalline LSF electrodes show a constant OER resistance in a broad thickness range, epitaxially grown LSF electrodes exhibit a continuous and strong increase of the OER resistance with film thickness until ≈60 nm. In addition, the activation energy of the OER resistance increases by 0.23 eV compared to polycrystalline LSF. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) measurements reveal an increasing contraction of the out-of-plane lattice parameter in the epitaxial LSF electrodes over electrode thickness. Defect thermodynamic simulations suggest that the decrease of the LSF unit cell volume is accompanied by a lowering of the oxygen vacancy concentration, explaining both the resistive increase and the increased activation energy.