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.

Revealing the three-dimensional arrangement of polar topology in nanoparticles.

In the early 2000s, low dimensional ferroelectric systems were predicted to have topologically nontrivial polar structures, such as vortices or skyrmions, depending on mechanical or electrical boundary conditions. A few variants of these structures have been experimentally observed in thin film model systems, where they are engineered by balancing electrostatic charge and elastic distortion energies. However, the measurement and classification of topological textures for general ferroelectric nanostructures have remained elusive, as it requires mapping the local polarization at the atomic scale in three dimensions. Here we unveil topological polar structures in ferroelectric BaTiO3 nanoparticles via atomic electron tomography, which enables us to reconstruct the full three-dimensional arrangement of cation atoms at an individual atom level. Our three-dimensional polarization maps reveal clear topological orderings, along with evidence of size-dependent topological transitions from a single vortex structure to multiple vortices, consistent with theoretical predictions. The discovery of the predicted topological polar ordering in nanoscale ferroelectrics, independent of epitaxial strain, widens the research perspective and offers potential for practical applications utilizing contact-free switchable toroidal moments.

Promotion of Probabilistic Bit Generation in Mott Devices by Embedded Metal Nanoparticles.

Considerable attention has been drawn to the use of volatile two-terminal devices relying on the Mott transition for the stochastic generation of probabilistic bits (p-bits) in emerging probabilistic computing. To improve randomness and endurance of bit streams provided by these devices, delicate control of the transient evolution of switchable domains is required to enhance stochastic p-bit generation. Herein, it is demonstrated that the randomness of p-bit streams generated via the consecutive pulse inputs of pump-probe protocols can be increased by the deliberate incorporation of metal nanoparticles (NPs), which influence the transient dynamics of the nanoscale metallic phase in VO2 Mott switches. Among the vertically stacked Pt-NP-containing VO2 threshold switches, those with higher Pt NP density show a considerably wider range of p-bit operation (e.g., up to ≈300% increase in ΔVprobe upon going from (Pt NP/VO2)0 to (Pt NP/VO2)11) and can therefore be operated under the conditions of high speed (400 kbit s-1), low power consumption (14 nJ per bit), and high stability (>105 200 bits) for p-bit generation. Thus, the study presents a novel strategy that exploits nanoscale phase control to maximize the generation of nondeterministic information sources for energy-efficient probabilistic computing hardware.

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.

Enhancing durability of automotive fuel cells via selective electrical conductivity induced by tungsten oxide layer coated directly on membrane electrode assembly.

The poor durability, attributed to catalyst corrosion during start-up/shutdown (SU/SD), is a major obstacle to the commercialization of fuel cell electric vehicles (FCEVs). We recently achieved durability enhancement under SU/SD conditions by implementing a metal-insulator transition (MIT) using proton intercalation/deintercalation in WO3. However, such oxide-supported catalysts were unsuitable for direct application to the mass production stage of membrane electrode assembly (MEA) process due to their physical and chemical properties. Here, we report a unique approach that achieves the same durability enhancement in SU/SD situations while being directly applicable to the conventional MEA fabrication process. We coated WO3 on the bipolar plate, gas diffusion layer, and MEA to investigate whether the MIT phenomenon was realized. The WO3-coated MEA demonstrated 94% performance retention during SU/SD, the highest level to our knowledge. It can directly contribute to enhancing the durability of commercial FCEVs and be immediately applied to the MEA mass production process.

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.

Embedded metallic nanoparticles facilitate metastability of switchable metallic domains in Mott threshold switches.

Mott threshold switching, which is observed in quantum materials featuring an electrically fired insulator-to-metal transition, calls for delicate control of the percolative dynamics of electrically switchable domains on a nanoscale. Here, we demonstrate that embedded metallic nanoparticles (NP) dramatically promote metastability of switchable metallic domains in single-crystal-like VO2 Mott switches. Using a model system of Pt-NP-VO2 single-crystal-like films, interestingly, the embedded Pt NPs provide 33.3 times longer 'memory' of previous threshold metallic conduction by serving as pre-formed 'stepping-stones' in the switchable VO2 matrix by consecutive electical pulse measurement; persistent memory of previous firing during the application of sub-threshold pulses was achieved on a six orders of magnitude longer timescale than the single-pulse recovery time of the insulating resistance in Pt-NP-VO2 Mott switches. This discovery offers a fundamental strategy to exploit the geometric evolution of switchable domains in electrically fired transition and potential applications for non-Boolean computing using quantum materials.

Cooperative coupling of anisotropic phonon modes intensifies visible thermochromism in layered α-MoO3.

Applications that provide versatile, high temperature warnings require the development of thermochromic materials based on solid-state oxides. To boost the visible thermochromic properties, a fundamental approach to reveal the unclear roles of local structure on band structure modulation should be considered by scrutinizing the thermal motion of phonon modes. Herein, we demonstrate that selective coupling of intra-layer phonon modes intensifies the visible thermochromism of layered oxides α-MoO3. As a result of thermally induced band gap reduction in α-MoO3, the observed color reversibly changes from white at 25 °C to yellow at 300 °C owing to a red shift of the absorption edge with an increase of temperature. This high-temperature thermochromism is attributed to the anisotropic change of layered α-MoO3 crystal structures characterized by synchrotron X-ray diffraction. Notably, quantitative characterizations combined with theoretical calculations reveal that the cooperative coupling of active Raman modes in intra-layer [MoO6] octahedra are responsible for the band gap reduction at high temperature; this defies the general belief regarding the origin of visible thermochromism in layered oxides as the modulation of a van der Waals inter-layer distance. These original results can aid the development of a new strategy to further intensify high-temperature thermochromism by anion doping for highly sensitive temperature-indicating applications.

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.

Effect of Lattice Strain on the Formation of Ruddlesden-Popper Faults in Heteroepitaxial LaNiO3 for Oxygen Evolution Electrocatalysis.

A great deal of research has recently been focused on Ruddlesden-Popper (RP) two-dimensional planar faults consisting of intervened [AO] monolayers in an ABO3 perovskite framework due to the structurally peculiar shear configuration. In this work, we scrutinize the effect of elastic strain on the generation behavior of RP faults, which are electrocatalytically very active sites for the oxygen evolution reaction (OER), in (001) epitaxial LaNiO3 thin films through by using two distinct single-crystal substrates with different cubic lattice parameters. Atomic-scale direct observations reveal that RP faults can be more favorably created when tensile misfit strain is exerted. Furthermore, we demonstrate that the controlled growth of thin films show notably enhanced OER activity by the RP faults. The findings in this study highlight the impact of symmetry-breaking defect formation for better oxygen electrocatalysis in perovskite oxides.

Reconfigurable all-dielectric Fano metasurfaces for strong full-space intensity modulation of visible light.

Dynamically reconfigurable nanoscale tuning of visible light properties is one of the ultimate goals both in the academic field of nanophotonics and the optics industry demanding compact and high-resolution display devices. Among various efforts incorporating actively reconfigurable optical materials into metamaterial structures, phase-change materials have been in the spotlight owing to their optical tunability in wide spectral regions including the visible spectrum. However, reconfigurable modulation of visible light intensity has been limited with small modulation depth, reflective schemes, and a lack of profound theoretical background for universal design rules. Here, all-dielectric phase-change Fano metasurface gratings are demonstrated for strong dynamic full-space (reflection and transmission) modulation of visible intensities based on Fano resonances. By judicious periodic couplings between densely arranged meta-atoms containing VO2, phase-change induced thermo-optic modulation of full-space intensities is highly enhanced in the visible spectrum. By providing intuitive design rules, we envision that the proposed study would contribute to nanophotonics-enabled optoelectronics technologies for imaging and sensing.

Metal Nanoparticle Exsolution on a Perovskite Stannate Support with High Electrical Conductivity.

In situ exsolution of metal nanoparticles (NPs) is emerging as an alternative technique to deliver thermally stable and evenly dispersed metal NPs, which exhibit excellent adhesion with conducting perovskite oxide supports. Here we provide the first demonstration that Ni metal NPs with high areal density (∼175 µm-2) and fine size (∼38.65 nm) are exsolved from an A-site-deficient perovskite stannate support (La0.2Ba0.7Sn0.9Ni0.1O3-δ (LBSNO)). The NPs are strongly anchored and impart coking resistance, and the Ni-exsolved stannates show exceptionally high electrical conductivity (∼700 S·cm-1). The excellent conductivity is attributed to conduction between delocalized Sn 5s orbitals along with structural improvement toward ABO3 stoichiometry in the stannate support. We also reveal that experimental conditions with strong interaction must be optimized to obtain Ni exsolution without degrading the perovskite stannate framework. Our finding suggests a unique process to induce the formation of metal NPs embedded in stannate with excellent electrical properties.

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.

Direct Probing of Oxygen Loss from the Surface Lattice of Correlated Oxides during Hydrogen Spillover.

Hydrogen spillover is a catalytic process that occurs by surface reaction and subsequent diffusion to reversibly provide a massive amount of hydrogen dopants in correlated oxides, but the mechanism at the surface of correlated oxides with metal catalyst are not well understood. Here we show that a significant amount of oxygen is released from the surface of correlated VO2 films during hydrogen spillover, contrary to the well-established observation of the formation of hydrogen interstitials in the bulk part of VO2 films. By using ambient-pressure X-ray photoelectron spectroscopy, we prove that the formation of surface oxygen vacancies is a consequence of a favorable reaction for the generation of weakly adsorbed H2O from surface O atoms that have low coordination and weak binding strength. Our results reveal the importance of in situ characterization to prove the dynamic change during redox reaction and present an opportunity to control intrinsic defects at the surface.

Steep-Slope Threshold Switch Enabled by Pulsed-Laser-Induced Phase Transformation.

Super-steep two-terminal electronic devices using NbO2, which abruptly switch from insulator to metal at a threshold voltage (Vth), offer diverse strategies for energy-efficient and high-density device architecture to overcome fundamental limitation in current electronics. However, the tight control of stoichiometry and high-temperature processing limit practical implementation of NbO2 as a component of device integration. Here, we demonstrate a facile room-temperature process that uses solid-solid phase transformation induced by pulsed laser to fabricate NbO2-based threshold switches. Interestingly, pulsed laser annealing under a reducing environment facilitates a two-step nucleation pathway (a-Nb2O5 → o-Nb2O5-δ → t-NbO2) of the threshold-enabled NbO2 phase mediated by oxygen vacancies in o-Nb2O5-δ. The laser-annealed devices with embedded NbO2 crystallites exhibit excellent threshold device performance with low off-current and high on/off current ratio. Our strategy that exploits the interactions of pulsed lasers with multivalent metal oxides can guide the development of a rational route to achieve NbO2-based threshold switches that are compatible with current semiconductor fabrication technology.

All-Solid-State Synaptic Transistors with High-Temperature Stability Using Proton Pump Gating of Strongly Correlated Materials.

Designing energy-efficient artificial synapses with adaptive and programmable electronic signals is essential to effectively mimic synaptic functions for brain-inspired computing systems. Here, we report all-solid-state three-terminal artificial synapses that exploit proton-doped metal-insulator transition in a correlated oxide NdNiO3 (NNO) channel by proton (H+) injection/extraction in response to gate voltage. Gate voltage reversibly controls the H+ concentration in the NNO channel with facile H+ transport from a H+-containing porous silica electrolyte. Gate-induced H+ intercalation in the NNO gives rise to nonvolatile multilevel analogue states due to H+-induced conductance modulation, accompanied by significant modulation of the out-of-plane lattice parameters. This correlated transistor operated by a proton pump shows synaptic characteristics such as long-term potentiation and depression, with nonvolatile and distinct multilevel conductance switching by a low voltage pulse (≥ 50 mV), with high energy efficiency (∼1 pJ) and tolerance to heat (≤150 °C). These results will guide the development of scalable, thermally-stable solid-state electronic synapses that operate at low voltage.

Facet-Dependent in Situ Growth of Nanoparticles in Epitaxial Thin Films: The Role of Interfacial Energy.

Nucleation of nanoparticles using the exsolution phenomenon is a promising pathway to design durable and active materials for catalysis and renewable energy. Here, we focus on the impact of surface orientation of the host lattice on the nucleation dynamics to resolve questions with regards to "preferential nucleation sites". For this, we carried out a systematic model study on three differently oriented perovskite thin films. Remarkably, in contrast to the previous bulk powder-based study suggesting that the (110)-surface is a preferred plane for exsolution, we identify that other planes such as (001)- and (111)-facets also reveal vigorous exsolution. Moreover, particle size and surface coverage vary significantly depending on the surface orientation. Exsolution of (111)-oriented film produces the largest number of particles, the smallest particle size, the deepest embedment, and the smallest and most uniform interparticle distance among the oriented films. Based on classic nucleation theory, we elucidate that the differences in interfacial energies as a function of substrate orientation play a crucial role in controlling the distinct morphology and nucleation behavior of exsolved nanoparticles. Our finding suggests new design principles for tunable solid-state catalyst or nanoscale metal decoration.