More Like this

1. Synthesis of Lanthanum Tungsten Oxynitride Perovskite Thin Films

   https://doi.org/10.1002/aelm.201900214  

   Talley, Kevin R. ; Mangum, John ; Perkins, Craig L. ; Woods‐Robinson, Rachel ; Mehta, Apurva ; Gorman, Brian P. ; Brennecka, Geoff L. ; Zakutayev, Andriy ( June 2019 , Advanced Electronic Materials)

   Ternary metal‐oxide material systems commonly crystallize in the perovskite crystal structure, which is utilized in numerous electronic applications. In contrast to oxides, there are no known nitride perovskites, likely due to the competition with oxidation, which makes the formation of pure nitride materials difficult and synthesis of oxynitride materials more common. While deposition of oxynitride perovskite thin films is important for many electronic applications, it is difficult to control oxygen and nitrogen stoichiometry. Lanthanum tungsten oxynitride (LaWN_3−δO_δ) thin films with varying La:W ratio are synthesized by combinatorial sputtering and characterized for their chemical composition, crystal structure, and microstructure. A three‐step synthesis method, which involves co‐sputtering, capping layer deposition, and rapid thermal annealing, is established for producing crystalline thin films while minimizing the oxygen content. Elemental depth profiling results show that the cation‐stoichiometric films contain approximately one oxygen for every five nitrogen (δ = 0.5). Synchrotron‐based diffraction indicates a tetragonal perovskite crystal structure. These results are discussed in terms of the perovskite tolerance factors, octahedral tilting, and bond valence. Overall, this synthesis and characterization is expected to pave the way toward future thin film property measurements of lanthanum tungsten oxynitrides and eventual synthesis of oxygen‐free nitride perovskites.

    

   more » « less
2. Anisotropic spin-orbit torque generation in epitaxial SrIrO 3 by symmetry design

   https://doi.org/10.1073/pnas.1812822116  

   Nan, T. ; Anderson, T. J. ; Gibbons, J. ; Hwang, K. ; Campbell, N. ; Zhou, H. ; Dong, Y. Q. ; Kim, G. Y. ; Shao, D. F. ; Paudel, T. R. ; et al ( August 2019 , Proceedings of the National Academy of Sciences)

   Spin-orbit coupling (SOC), the interaction between the electron spin and the orbital angular momentum, can unlock rich phenomena at interfaces, in particular interconverting spin and charge currents. Conventional heavy metals have been extensively explored due to their strong SOC of conduction electrons. However, spin-orbit effects in classes of materials such as epitaxial 5 d -electron transition-metal complex oxides, which also host strong SOC, remain largely unreported. In addition to strong SOC, these complex oxides can also provide the additional tuning knob of epitaxy to control the electronic structure and the engineering of spin-to-charge conversion by crystalline symmetry. Here, we demonstrate room-temperature generation of spin-orbit torque on a ferromagnet with extremely high efficiency via the spin-Hall effect in epitaxial metastable perovskite SrIrO 3 . We first predict a large intrinsic spin-Hall conductivity in orthorhombic bulk SrIrO 3 arising from the Berry curvature in the electronic band structure. By manipulating the intricate interplay between SOC and crystalline symmetry, we control the spin-Hall torque ratio by engineering the tilt of the corner-sharing oxygen octahedra in perovskite SrIrO 3 through epitaxial strain. This allows the presence of an anisotropic spin-Hall effect due to a characteristic structural anisotropy in SrIrO 3 with orthorhombic symmetry. Our experimental findings demonstrate the heteroepitaxial symmetry design approach to engineer spin-orbit effects. We therefore anticipate that these epitaxial 5 d transition-metal oxide thin films can be an ideal building block for low-power spintronics. 

   more » « less
3. In Situ Method Correlating Raman Vibrational Characteristics to Chemical Expansion via Oxygen Nonstoichiometry of Perovskite Thin Films

   https://doi.org/10.1002/adma.201902493  

   Sediva, Eva ; Defferriere, Thomas ; Perry, Nicola H. ; Tuller, Harry L. ; Rupp, Jennifer L. M. ( June 2019 , Advanced Materials)

   Effective integration of perovskite films into devices requires knowledge of their electro‐chemomechanical properties. Raman spectroscopy is an excellent tool for probing such properties as the films' vibrational characteristics couple to the lattice volumetric changes during chemical expansion. While lattice volumetric changes are typically accessed by analyzing Raman shifts as a function of pressure, stress, or temperature, such methods can be impractical for thin films and do not capture information on chemical expansion. An in situ Raman spectroscopy technique using an electrochemical titration cell to change the oxygen nonstoichiometry of a model perovskite film, Sr(Ti,Fe)O_3−y , is reported and the lattice vibrational properties are correlated to the material's chemical expansion. How to select an appropriate Raman vibrational mode to track the evolution in oxygen nonstoichiometry is discussed. Subsequently, the frequency of the oxygen stretching mode around Fe⁴⁺is tracked, as it decreases during reduction as the material expands and increases during reoxidation as the material shrinks. This methodology of oxygen pumping and in situ Raman spectroscopy of oxide films enables future in operando measurements even for small material volumes, as is typical for applications of films as electrodes or electrolytes utilized in electrochemical energy conversion or memory devices.

    

   more » « less
4. Self-regulated growth of [111]-oriented perovskite oxide films using hybrid molecular beam epitaxy

   https://doi.org/10.1063/5.0040047  

   Roth, Joseph ; Kuznetsova, Tatiana ; Miao, Leixin ; Pogrebnyakov, Alexej ; Alem, Nasim ; Engel-Herbert, Roman ( February 2021 , APL Materials)

   Exotic material properties and topological nontrivial surface states have been theoretically predicted to emerge in [111]-oriented perovskite layers. The realization of such [111]-oriented perovskite superlattices has been found challenging, and even the growth of perovskite oxide films along this crystallographic direction has been proven as a formidable task, attributed to the highly polar character of the perovskite (111) surface. Successful epitaxial growth along this direction has so far been limited to thin film deposition techniques involving a relatively high kinetic energy, specifically pulsed laser deposition and sputtering. Here, we report on the self-regulated growth of [111]-oriented high-quality SrVO3 by hybrid molecular beam epitaxy. The favorable growth kinetics available for the growth of perovskite oxides by hybrid molecular beam epitaxy on non-polar surfaces was also present for the growth of [111]-oriented films, resulting in high-quality SrVO3(111) thin films with residual resistivity ratios exceeding 20. The ability to grow high-quality perovskite oxides along energetically unfavorable crystallographic directions using hybrid molecular beam epitaxy opens up opportunities to study the transport properties of topological nontrivial and correlated electron systems.

    

   more » « less
5. Manipulation of the Ferromagnetism in LaCoO 3 Thin Films Through Cation‐Stoichiometric Engineering

   https://doi.org/10.1002/aelm.202201245  

   Huang, Tongtong ; Lyu, Yingjie ; Huyan, Huaixun ; Ni, Jinyang ; Saremi, Sahar ; Wang, Yujia ; Yan, Xingxu ; Yi, Di ; He, Qing ; Martin, Lane W. ; et al ( March 2023 , Advanced Electronic Materials)

   Spin‐state transitions are an important research topic in complex oxides with the diverse magnetic states involved. In particular, the low‐spin to high‐spin transition in LaCoO₃thin films has drawn a wide range of attention due to the emergent ferromagnetic state. Although various mechanisms (e.g., structural distortion, oxygen‐vacancy formation, spin‐state ordering) have been proposed, an understanding of what really underlies the emergent ferromagnetism remains elusive. Here, the ferromagnetism in LaCoO₃thin films is systematically modulated by varying the oxygen pressure during thin‐film growth. Although the samples show dramatic different magnetization, their cobalt valence state and perovskite crystalline structure remain almost unchanged, ruling out the scenarios of both oxygen‐vacancy and spin‐ordering. This work provides compelling evidence that the tetragonal distortion due to the tensile strain significantly modifies the orbital occupancy, leading to a low‐spin to high‐spin transition with emergent ferromagnetism, while samples grown at reduced pressure demonstrate a pronounced lattice expansion due to cation‐off‐stoichiometry, which suppresses the tetragonal distortion and the consequent magnetization. This result not only provides important insight for the understanding of exotic ferromagnetism in LaCoO₃thin films, but also identifies a promising strategy to design electronic states in complex oxides through cation‐stoichiometry engineering.

    

   more » « less