skip to main content


Title: Nitride perovskite becomes polar
There is a strong drive behind the quest for thin-film materials that are oxygen-free and polar. Oxygen hinders the integration of ferroelectric oxides with semiconductors, which affects efforts to develop nonvolatile memory—that is, a memory that can sustain its information without power. Ideally, one would use single-crystalline perovskite films to construct these devices so that the polarization can be maximized. However, when depositing crystalline polar perovskite oxides onto silicon or germanium, a nonpolar oxide buffer layer ( 1 ) or a native oxide layer ( 2 ) can be present at the interface, compromising device performance. A nitrogen-based perovskite may overcome this limitation ( 3 ). On page 1488 of this issue, Talley et al. ( 4 ) report the synthesis of lanthanum tungsten nitride (LaWN 3 ) thin films, which marks the first demonstration of polar nitride perovskite. This may lead to oxygen-free integration of functional perovskite on a semiconductor platform.  more » « less
Award ID(s):
2044049 1710461
NSF-PAR ID:
10313701
Author(s) / Creator(s):
Date Published:
Journal Name:
Science
Volume:
374
Issue:
6574
ISSN:
0036-8075
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    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 (LaWN3−δOδ) 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. 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. Abstract

    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)O3−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. Abstract

    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
  5. Abstract

    As a class of semiconductor nanocrystals that exhibit high photoluminescence quantum yield (PLQY) at tunable wavelengths, perovskite nanocrystals (PNCs) are attractive candidates for optoelectronic and light‐emitting devices. However, attempts to optimize PNC integration into such applications suffer from PNC instability and loss of PL over time. Here, we describe the impact of organic and polymeric N‐oxides when used in conjunction with PNCs, whereby a significant increase in PNC quantum yield is observed in solution, and stable PL emission is obtained in polymeric nanocomposites. Specifically, when using aliphatic N‐oxides in ligand exchange with CsPbBr3PNCs in solution, a substantial boost in PNC brightness is observed (~40% or more PLQY increase), followed by an alteration of the perovskite chemistry. When N‐oxide substituents are positioned pendent to a poly(n‐butyl methacrylate) backbone, the optically clear flexible nanocomposite films obtained have bright PL emission and maintain optical clarity for months. X‐ray diffraction is useful for characterizing the PNC crystalline structure following exposure to aliphatic N‐oxides, while electron microscopy (EM) and small‐angle X‐ray scattering (SAXS) measurements of the PNC‐polymer nanocomposites show this polymeric N‐oxide platform to cleanly disperse PNCs in flexible polymer films.

     
    more » « less