Accelerating metal nanoparticle exsolution by exploiting tolerance factor of perovskite stannate.

The octahedral symmetry in ionic crystals can play a critical role in atomic nucleation and migration during solid-solid phase transformation. Similarly, octahedron distortion, which is characterized by Goldschmidt tolerance factor, strongly influences the exsolution kinetics in the perovskite lattice framework during high-temperature annealing. However, a fundamental study on manipulating the exsolution process by octahedron distortion is still lacking. In this study, we accelerate Ni metal exsolution on the surface of perovskite stannates by increasing the [BO6] octahedron distortion in the lattices. Decreasing the A-site ionic radius (rBa2+ = 161 pm → rSr2+ = 144 pm → rCa2+ = 134 pm) increased the density of exsolved Ni nanoparticles by up to 640% (i.e., 47 particles µm-2 of Ba(Sn, Ni)O3 → 304 particles µm-2 of Ca(Sn, Ni)O3) after the identical exsolution process. Based on the theoretical calculation and experimental characterization, the decrease in crystal symmetry by octahedral distortion promoted the Ni exsolution owing to the boosted Ni migration by weakening the bond strength and generating domain boundaries. The findings highlight the importance of octahedral distortion to control atomic migration through the perovskite lattice framework and provide a strategy to tailor the density of uniformly populated nanoparticles in nanocomposite oxides for multifunctional material design.

Piezo strain-controlled phase transition in single-crystalline Mott switches for threshold-manipulated leaky integrate-and-fire neurons.

Electrical manipulation of the metal-insulator transition (MIT) in quantum materials has attracted considerable attention toward the development of ultracompact neuromorphic devices because of their stimuli-triggered transformations. VO2 is expected to undergo abrupt electronic phase transition by piezo strain near room temperature; however, the unrestricted integration of defect-free VO2 films on piezoelectric substrates is required to fully exploit this emerging phenomenon in oxide heterostructures. Here, we demonstrate the integration of single-crystalline VO2 films on highly lattice-mismatched PMN-PT piezoelectric substrates using a single-crystal TiO2-nanomembrane (NM) template. Using our strategy on heterogeneous integration, single-crystal-like steep transition was observed in the defect-free VO2 films on TiO2-NM-PMN-PT. Unprecedented TMI modulation (5.2 kelvin) and isothermal resistance of VO2 [ΔR/R (Eg) ≈ 18,000% at 315 kelvin] were achieved by the efficient strain transfer-induced MIT, which cannot be achieved using directly grown VO2/PMN-PT substrates. Our results provide a fundamental strategy to realize a single-crystalline artificial heterojunction for promoting the application of artificial neurons using emergent materials.

Anionic Flow Valve Across Oxide Heterointerfaces by Remote Electron Doping.

As an analogue of charged electron flows, the ionic flow could be controlled by the electronic band alignment due to the ambipolar nature of diffusion in the ionic crystal. Here, we demonstrate the active control of the anionic diffusion across heterointerfaces through remote electron doping in the capping layers. In contrast to the spontaneous ionic flux from the underlying VO2 layers to the undoped TiO2 capping layers, the activated Nb dopants in the TiO2 capping layers substantially restrict the ionic flux, despite identical growth conditions. The increase of Fermi level by Nb donors in TiO2 prevents electron flux from being generated across the interfaces by the heightening of a Schottky barrier; this electron shortage generates a kinetic close valve for the flow of negatively charged oxygen ions. Thus, these results demonstrate the importance of electron supply on charged ionic flow, thereby suggesting an unprecedented strategy for ionic-defect-induced emergent properties at interfaces.

Reversible Manipulation of Photoconductivity Caused by Surface Oxygen Vacancies in Perovskite Stannates with Ultraviolet Light.

Programmable optoelectronic devices call for the reversible control of the photocarrier recombination process by in-gap states in oxide semiconductors. However, previous approaches to produce oxygen vacancies as a source of in-gap states in oxide semiconductors have hampered the reversible formation of oxygen vacancies and their related phenomena. Here, a new strategy to manipulate the 2D photoconductivity from perovskite stannates is demonstrated by exploiting spatially selective photochemical reaction under ultraviolet illumination at room temperature. Remarkably, the ideal trap-free photocurrent of air-illuminated BaSnO3 (≈200 pA) is reversibly switched into three orders of magnitude higher photocurrent of vacuum-illuminated BaSnO3 (≈335 nA) with persistent photoconductivity depending on ambient oxygen pressure under illumination. Multiple characterizations elucidate that ultraviolet illumination of BaSnO3  under low oxygen pressure induces surface oxygen vacancies as a result of surface photolysis combined with the low oxygen-diffusion coefficient of BaSnO3 ; the concentrated oxygen vacancies are likely to induce a two-step transition of photocurrent response by changing the characteristics of in-gap states from the shallow level to the deep level. These results suggest a novel strategy that uses light-matter interaction in a reversible and spatially confined way to manipulate functionalities related to surface defect states, for the emerging applications using newly discovered oxide semiconductors.

Heterogeneous integration of single-crystalline rutile nanomembranes with steep phase transition on silicon substrates.

Unrestricted integration of single-crystal oxide films on arbitrary substrates has been of great interest to exploit emerging phenomena from transition metal oxides for practical applications. Here, we demonstrate the release and transfer of a freestanding single-crystalline rutile oxide nanomembranes to serve as an epitaxial template for heterogeneous integration of correlated oxides on dissimilar substrates. By selective oxidation and dissolution of sacrificial VO2 buffer layers from TiO2/VO2/TiO2 by H2O2, millimeter-size TiO2 single-crystalline layers are integrated on silicon without any deterioration. After subsequent VO2 epitaxial growth on the transferred TiO2 nanomembranes, we create artificial single-crystalline oxide/Si heterostructures with excellent sharpness of metal-insulator transition ([Formula: see text] > 103) even in ultrathin (<10 nm) VO2 films that are not achievable via direct growth on Si. This discovery offers a synthetic strategy to release the new single-crystalline oxide nanomembranes and an integration scheme to exploit emergent functionality from epitaxial oxide heterostructures in mature silicon devices.

Directional ionic transport across the oxide interface enables low-temperature epitaxy of rutile TiO2.

Heterogeneous interfaces exhibit the unique phenomena by the redistribution of charged species to equilibrate the chemical potentials. Despite recent studies on the electronic charge accumulation across chemically inert interfaces, the systematic research to investigate massive reconfiguration of charged ions has been limited in heterostructures with chemically reacting interfaces so far. Here, we demonstrate that a chemical potential mismatch controls oxygen ionic transport across TiO2/VO2 interfaces, and that this directional transport unprecedentedly stabilizes high-quality rutile TiO2 epitaxial films at the lowest temperature (≤ 150 °C) ever reported, at which rutile phase is difficult to be crystallized. Comprehensive characterizations reveal that this unconventional low-temperature epitaxy of rutile TiO2 phase is achieved by lowering the activation barrier by increasing the "effective" oxygen pressure through a facile ionic pathway from VO2-δ sacrificial templates. This discovery shows a robust control of defect-induced properties at oxide interfaces by the mismatch of thermodynamic driving force, and also suggests a strategy to overcome a kinetic barrier to phase stabilization at exceptionally low temperature.

Accelerated Hydrogen Diffusion and Surface Exchange by Domain Boundaries in Epitaxial VO2 Thin Films.

Electronic phase modulation based on hydrogen insertion/extraction is kinetically limited by the bulk hydrogen diffusion or surface exchange reaction, so slow hydrogen kinetics has been a fundamental challenge to be solved for realizing faster solid-state electrochemical switching devices. Here we accelerate electronic phase modulation that occurs by hydrogen insertion in VO2 through vertically aligned 2D defects induced by symmetry mismatch between epitaxial films and substrates. By using domain-matching epitaxial growth of monoclinic VO2 films with lattice rotation and twinning on hexagonal Al2O3 substrates, the domain boundaries naturally align vertically; they provide a "highway" for hydrogen diffusion and surface exchange in VO2 films and overcome the limited rates of bulk diffusion and surface reaction. From the quantitative analysis of the deuterium (2H) isotope tracer exchange, it is confirmed that the tracer diffusion coefficient (D*) and surface exchange coefficient (k*) were increased by several orders of magnitude in VO2 films that had domain boundaries. These results yield fundamental insights into the mechanism by which mobile ions are inserted along extended defects and provide a strategy to overcome a limitation to switching speed in electrochemical devices that exploit ion insertion.