@article{rasic_sachan_prater_narayan_2019, title={Structure-property correlations in thermally processed epitaxial LSMO films}, volume={163}, ISSN={["1873-2453"]}, DOI={10.1016/j.actamat.2018.10.023}, abstractNote={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.}, journal={ACTA MATERIALIA}, author={Rasic, Daniel and Sachan, Ritesh and Prater, John and Narayan, Jagdish}, year={2019}, month={Jan}, pages={189–198} }
 @article{rasic_sachan_temizer_prater_narayan_2018, title={Oxygen Effect on the Properties of Epitaxial (110) La0.7Sr0.3MnO3 by Defect Engineering}, volume={10}, ISSN={["1944-8252"]}, DOI={10.1021/acsami.8b05929}, abstractNote={The multiferroic properties of mixed valence perovskites such as lanthanum strontium manganese oxide (La0.7Sr0.3MnO3) (LSMO) demonstrate a unique dependence on oxygen concentration, thickness, strain, and orientation. To better understand the role of each variable, a systematic study has been performed. In this study, epitaxial growth of LSMO (110) thin films with thicknesses ∼15 nm are reported on epitaxial magnesium oxide (111) buffered Al2O3 (0001) substrates. Four LSMO films with changing oxygen concentration have been investigated. The oxygen content in the films was controlled by varying the oxygen partial pressure from 1 × 10-4 to 1 × 10-1 Torr during deposition and subsequent cooldown. X-ray diffraction established the out-of-plane and in-plane plane matching to be (111)MgO ∥ (0001)Al2O3 and ⟨11̅0⟩MgO ∥ ⟨101̅0⟩Al2O3 for the buffer layer with the substrate, and an out-of-plane lattice matching of (110)LSMO ∥ (111)MgO for the LSMO layer. For the case of the LSMO growth on MgO, a novel growth mode has been demonstrated, showing that three in-plane matching variants are present: (i) ⟨11̅0⟩LSMO ∥ ⟨11̅0⟩MgO, (ii) ⟨11̅0⟩LSMO ∥ ⟨101̅⟩MgO, and (iii) ⟨11̅0⟩LSMO ∥ ⟨01̅1⟩MgO. The atomic resolution scanning transmission electron microscopy (STEM) images were taken of the interfaces that showed a thin, ∼2 monolayer intermixed phase while high-angle annular dark field (HAADF) cross-section images revealed 4/5 plane matching between the film and the buffer and similar domain sizes between different samples. Magnetic properties were measured for all films and the gradual decrease in saturation magnetization is reported with decreasing oxygen partial pressure during growth. A systematic increase in the interplanar spacing was observed by X-ray diffraction of the films with lower oxygen concentration, indicating the decrease in the lattice constant in the plane due to the point defects. Samples demonstrated an insulating behavior for samples grown under low oxygen partial pressure and semiconducting behavior for the highest oxygen partial pressures. Magnetotransport measurements showed ∼36.2% decrease in electrical resistivity with an applied magnetic field of 10 T at 50 K and ∼1.3% at room temperature for the highly oxygenated sample.}, number={24}, journal={ACS APPLIED MATERIALS & INTERFACES}, author={Rasic, Daniel and Sachan, Ritesh and Temizer, Namik K. and Prater, John and Narayan, Jagdish}, year={2018}, month={Jun}, pages={21001–21008} }
 @article{rasic_sachan_chisholm_prater_narayan_2017, title={Room Temperature Growth of Epitaxial Titanium Nitride Films by Pulsed Laser Deposition}, volume={17}, ISSN={1528-7483 1528-7505}, url={http://dx.doi.org/10.1021/ACS.CGD.7B01278}, DOI={10.1021/acs.cgd.7b01278}, abstractNote={Reducing the thermal budget of epitaxial thin film growth has been one of the biggest challenges for the electronics industry. In this report, the room-temperature epitaxial growth of titanium nitride (TiN) thin films (∼75 nm) on (0001) Al2O3 substrates is demonstrated using a pulsed laser deposition technique. In TiN thin films, the epitaxial relationship is established by X-ray diffraction for (111)TiN//(0001) Al2O3 and TiN // Al2O3 which corresponds to a 30° rotation of titanium and nitrogen atoms with respect to the hexagon arrangement of aluminum atoms. An increase in the defect concentration is shown in the room-temperature thin film growth as compared to the ones grown at elevated temperature. A shift and broadening of the diffraction peaks is observed in the thin films as compared to the bulk value, indicating a higher residual tensile strain with decreasing growth temperature and an increase in defect concentration at room temperature. The increased defect concentration observed at...}, number={12}, journal={Crystal Growth & Design}, publisher={American Chemical Society (ACS)}, author={Rasic, Daniel and Sachan, Ritesh and Chisholm, Matthew F. and Prater, John and Narayan, Jagdish}, year={2017}, month={Oct}, pages={6634–6640} }