Structure-property correlations in thermally processed epitaxial LSMO films

Abstract Mixed-valence perovskites have drawn significant research interest in the past due to their exotic properties. Lanthanum Strontium Manganese Oxide (LSMO) shows a ferromagnetic ordering that can be tuned with the control of defects and strain. Here, experiments were performed to decouple the effects of strain and oxygen content, which together control the magnetic properties of the LSMO (La0.7Sr0.3MnO3). In this work, thermal treatments show promise in effectively controlling the ferromagnetic response of LSMO films. A set of three samples were grown on the same substrate-buffer (Al2O3/MgO) platform with different oxygen partial pressures and annealed above their deposition temperature (∼900 °C) in air. The physical and structural properties were measured and showed overall decrease in magnetization saturation as well as decrease in out-of-plane lattice spacing with decreasing oxygen partial pressure. A second anneal at lower (∼700 °C) temperature with flow of pure oxygen was performed for six hours to allow for defect annihilation and grain growth. All three films remained epitaxial allowing for direct correlation of magnetic measurements with defect concentration. Partial recovery of the magnetic properties and a slight increase in interplanar spacing was observed. The inability of the films to fully recover their original magnetic properties suggests irreversible strain relaxation during the initial, high-temperature air anneal. This hypothesis was further supported by the in-situ XRD that showed a linear increase in the interplanar spacing with temperature until ∼520 °C for LSMO and ∼690 °C for MgO. With further increase in temperature, the films experienced both loss of oxygen and irreversible defect nucleation and recombination. High resolution high-angle annular dark field (HAADF) images showed uniform thickness and no interfacial mixing with subsequent annealing treatments while electron energy loss spectroscopy (EELS) showed a loss of characteristic pre-peak A in oxygen indicating formation of oxygen vacancies. Parallel annealing experiments in high vacuum instead of atmosphere were performed, which showed complete loss of crystal structure in the LSMO films due to significant loss of oxygen in the lattice that irreversibly collapsed the perovskite structure. Furthermore, a low-temperature (∼500 °C) oxidation anneal was performed on a pristine sample with no change in the interplanar spacing observed indicating no change in the strain state of the film due to annealing below the deposition temperature. The reversibility of magnetic properties, which is observed as long as the crystal structure of the films is preserved, indicates the importance of bridging oxygen in controlling the magnetic behavior of mixed valence perovskites. Finally, it was determined that the highest magnetization saturation in the films is achieved with a high oxygen partial pressure during growth and subsequent thermal annealing below the deposition temperature.