Magnetic Phase Transition-Induced Modulation of Ferroelectric Properties in Hexagonal RFeO3 (R = Tb and Ho).

Hexagonal rare-earth iron oxides (h-RFeO3) exhibit spontaneous magnetization and room-temperature ferroelectricity simultaneously. However, achieving a large magnetoelectric coupling necessitates further exploration. Herein, we report the impact of the magnetic phase transition on the ferroelectric properties of epitaxial h-RFeO3 (R = Tb and Ho) films prepared by pulsed laser deposition. The metastable h-RFeO3 phase is successfully stabilized with high crystallinity and low leakage current due to the ITO buffer layer, making it possible to investigate the ferroelectric properties. The h-TbFeO3 film exhibits a magnetic-field-induced transition from antiferromagnetic (AFM) to weak ferromagnetic (wFM) phases below 30 K, while also exhibiting ferroelectricity at 300 K. The dielectric constants change with the magnetic phase transition, demonstrating hysteresis in the magnetocapacitance. In contrast, the h-HoFeO3 film exhibits antiferroelectric-like behavior and an AFM-wFM phase transition. Notably, the h-HoFeO3 film shows a rapid increase in the remnant polarization during the AFM-wFM phase transition accompanied by an increase in the ferroelectric component. Considering the strong connection between the antiferroelectric behavior in the h-RFeO3 system and the ferroelectric domain wall motion, this considerable modification of ferroelectric properties during the magnetic phase transition is probably due to the faster movement of the ferroelectric domain walls in the wFM phase induced by the clamping effect. Our findings indicate the effectiveness of magnetic phase transitions in enhancing the magnetoelectric coupling, particularly when utilizing domain wall clamping properties.

Solid-State Electrochemical Thermal Transistors with Strontium Cobaltite-Strontium Ferrite Solid Solutions as the Active Layers.

Thermal transistors have potential as thermal management devices because they can electrically control the thermal conductivity (κ) of the active layer. Recently, we realized solid-state electrochemical thermal transistors by utilizing the electrochemical redox reaction of SrCoOy (2 ≤ y ≤ 3). However, the guiding principle to improve the on/off κ ratio has yet to be clarified because the κ modulation mechanism is unclear. This study systematically modulates κ of SrCo1-xFexOy (0 ≤ x ≤ 1, 2 ≤ y ≤ 3) solid solutions used as the active layers in solid-state electrochemical thermal transistors. When y = 3, the lattice κ of SrCo1-xFexOy is ∼2.8 W m-1 K-1 and insensitive to x. When x = 0 and y = 3, κ increases to ∼3.8 W m-1 K-1 due to the contribution of the electron κ. When y = 2, κ slightly depends on the ordered atomic arrangement. Materials that are high electrical conductors with highly ordered lattices when the transistor is on but are electrical insulators with disordered lattices when the transistor is off should be well-suited for the active layers of solid-state electrochemical thermal transistors.

Synthesis and transparent conductivity of crack-free La:BaSnO3 epitaxial flexible sheets.

La-doped BaSnO3 (LBSO), which exhibits both high electron mobility and visible-light transparency, is a promising transparent electrode/transistor material that does not require expensive elements such as indium. However, because a high crystal orientation is necessary for high mobility, the development of a synthetic technique is crucial for next-generation optoelectronic applications. One promising method for achieving this is the lift-off and transfer method. Epitaxial films are first deposited on single-crystal substrates, peeled off from the substrates, and subsequently transferred onto other substrates. However, such transferred sheets typically contain a high density of cracks. Therefore, LBSO sheets with flexibility, high mobility, and transparency have not yet been reported. In this study, we successfully synthesized crack-free LBSO epitaxial sheets via a lift-off and transfer method using a water-soluble Sr3Al2O6 sacrificial layer and amorphous (a-)Al2O3 protection layer. The LBSO sheet simultaneously exhibited a high electron mobility of 80 cm2 V-1 s-1 and a wide optical bandgap of 3.5 eV owing to the epitaxial crystallinity of the sheet. Moreover, two types of LBSO sheets were prepared, flat and rolled sheets, by tuning the lift-off process. The flat sheet had a lateral size of 5 mm × 5 mm, whereas the rolled sheet had a tube shape with a height of 5 mm and a diameter of 1 mm. Such large crack-free area and flexibility were achieved in LBSO sheets owing to the use of the a-Al2O3 protection layer.

Direct Imaging of Ion Migration in Amorphous Oxide Electronic Synapses with Intrinsic Analog Switching Characteristics.

Amorphous metal oxides with analog resistive switching functions (i.e., continuous controllability of the electrical resistance) are gaining emerging interest due to their neuromorphic functionalities promising for energy efficient electronics. The mechanisms are currently attributed to field-driven migration of the constituent ions, but the applications are being hindered by the limited understanding of the physical mechanisms due to the difficulty in analyzing the causal ion migration, which occurs on a nanometer or even atomic scale. Here, the direct electrical transport measurement of analog resistive switching and ångström scale imaging of the causal ion migration is demonstrated in amorphous TaOx (a-TaOx) by conductive atomic force microscopy. Atomically flat thin films of a-TaOx, which is a practical material for commercial resistive random access memory, are fabricated in this study, and the mechanisms of the three known types of analog resistive switching phenomena (current-dependent set, voltage-dependent reset, and time-dependent switching) are directly visualized on the surfaces. The observations indicate that highly analog type of resistive switching can be induced in a-TaOx by inducing the continuous redox reactions for 2.0 < x < 2.5, which are characteristic of a-TaOx. The measurements also demonstrate drastic control of the switching stochasticity, which is attributable to controlled segregation of a metastable a-TaO2 phase. The findings provide direct clues for tuning the analog resistive switching characteristics of amorphous metal oxides and developing new functions for future neuromorphic computing.

Significant Suppression of Cracks in Freestanding Perovskite Oxide Flexible Sheets Using a Capping Oxide Layer.

Flexible and functional perovskite oxide sheets with high orientation and crystallization are the next step in the development of next-generation devices. One promising synthesis method is the lift-off and transfer method using a water-soluble sacrificial layer. However, the suppression of cracks during lift-off is a crucial problem that remains unsolved. In this study, we demonstrated that this problem can be solved by depositing amorphous Al2O3 capping layers on oxide sheets. Using this simple method, over 20 mm2 of crack-free, deep-ultraviolet transparent electrode La:SrSnO3 and ferroelectric Ba0.75Sr0.25TiO3 flexible sheets were obtained. By contrast, the sheets without any capping layers broke. The obtained sheets showed considerable flexibility and high functionality. The La:SrSnO3 sheet simultaneously exhibited a wide bandgap (4.4 eV) and high electrical conductivity (>103 S/cm). The Ba0.75Sr0.25TiO3 sheet exhibited clear room-temperature ferroelectricity with a remnant polarization of 17 µC/cm2. Our findings provide a simple transfer method for obtaining large, crack-free, high-quality, single-crystalline sheets.

Ba1/3CoO2: A Thermoelectric Oxide Showing a Reliable ZT of ∼0.55 at 600 °C in Air.

Thermoelectric energy conversion technology has attracted attention as an energy harvesting technology that converts waste heat into electricity by means of the Seebeck effect. Oxide-based thermoelectric materials that show a high figure of merit are promising because of their good chemical and thermal stability as well as their harmless nature compared to chalcogenide-based state-of-the-art thermoelectric materials. Although several high-ZT thermoelectric oxides (ZT > 1) have been reported thus far, the reliability is low due to a lack of careful observation of their stability at elevated temperatures. Here, we show a reliable high-ZT thermoelectric oxide, Ba1/3CoO2. We fabricated Ba1/3CoO2 epitaxial films by the reactive solid-phase epitaxy method (Na3/4CoO2) followed by ion exchange (Na+ → Ba2+) treatment and performed thermal annealing of the film at high temperatures and structural and electrical measurements. The crystal structure and electrical resistivity of the Ba1/3CoO2 epitaxial films were found to be maintained up to 600 °C. The power factor gradually increased to ∼1.2 mW m-1 K-2 and the thermal conductivity gradually decreased to ∼1.9 W m-1 K-1 with increasing temperature up to 600 °C. Consequently, the ZT reached ∼0.55 at 600 °C in air.

Modulation of electrical and thermal transports through lattice distortion in BaTi1-xNbxO3solid solutions.

The electron and heat transports in solids are through the movement of carrier electrons and quantized lattice vibrations (phonons), which are sensitive to the lattice distortion and ionized impurities, and are essential aspects for the development of novel thermoelectric materials. In this study, we systematically investigated the modulations of electrical and thermal conductivities of BaTi1-xNbxO3solid solution (BTNO, 0 ≤ x ≤ 1) epitaxial films. At room temperature, BaTiO3belongs to tetragonal perovskite and exhibits electron conduction through doubly degenerated Ti 3d-t2gorbitals upon doping, while BaNbO3belongs to cubic perovskite and exhibits metallic electron conduction through partially filled triply degenerate Nb 4d-t2gorbitals. By controlling the Ti/Nb ratio, we found a dual modulation effect on both the lattice structures and conduction band, which affects the electrical and thermal conductivities. Similar to the SrTi1-xNbxO3solid solution (STNO, 0 ≤ x ≤ 1) system, a phase transition was detected atx âˆ¼ 0.5, at which both the electron and heat transports exhibit abrupt changes. Unlike the transition in STNO, which was attributed to a polaronic phase transition, the transition in BTNO was due to contributions from both the lattice distortion and polaron effect. By controlling the lattice distortion, conduction band, and polaronic phase transitions, the electrical and thermal conductivity of BTNO epitaxial films are modulated within a much greater range than those of the STNO epitaxial films. Due to the double contribution of electron carriers and phonon to thermal conductivity (κ), the maximumκmodulation ratio of BTNO epitaxial films was ∼6.9. Our research provides an effective route to design electrical/thermal management materials.

Observation of topological Hall torque exerted on a domain wall in the ferromagnetic oxide SrRuO3.

In a ferromagnetic Weyl metal SrRuO3, a large effective magnetic field Heff exerted on a magnetic domain wall (DW) by current has been reported. We show that the ratio of Heff to current density exhibits nonmonotonic temperature dependence and surpasses those of conventional spin-transfer torques and spin-orbit torques. This enhancement is described well by topological Hall torque (THT), which is exerted on a DW by Weyl electrons emerging around Weyl points when an electric field is applied across the DW. The ratio of the Heff arising from the THT to current density is over one order of magnitude higher than that originating from spin-transfer torques and spin-orbit torques reported in metallic systems, showing that the THT may provide a better way for energy-efficient manipulation of magnetization in spintronics devices.

Solid-State Electrochemical Switch of Superconductor-Metal-Insulators.

Controlling the oxygen content can manipulate the electrical conductivity of transition metal oxides (TMOs). Although the superconductor-metal-insulator transition is useful for functional devices, an electrical path must be developed to manipulate the oxygen deficiency (δ) while maintaining the solid state. YBa2Cu3O7-δ (YBCO, 0 ≤ δ ≤ 1) is a high transition temperature (Tc) TMO that can be modulated from a superconductor (Tc ≈ 92 K when δ = 0) to an insulator (δ ≈ 1). Here, we show a simple and efficient way to manipulate δ in YBCO films using a solid-state electrochemical redox treatment. Applying a negative voltage injects oxide ions to the YBCO films, increasing Tc. Employing a positive voltage suppresses the superconducting transition and modulates the electrical conductivity. The present results demonstrate that the superconductor-metal-insulator transition of YBCO is modulated electrochemically in the solid state, opening possibilities of superconducting oxide-based device applications.

Unveiling the Electronic Structure of Grain Boundaries in Anatase with Electron Microscopy and First-Principles Modeling.

Polycrystalline anatase titanium dioxide has drawn great interest, because of its potential applications in high-efficiency photovoltaics and photocatalysts. There has been speculation on the electronic properties of grain boundaries but little direct evidence, because grain boundaries in anatase are challenging to probe experimentally and to model. We present a combined experimental and theoretical study of anatase grain boundaries that have been fabricated by epitaxial growth on a bicrystalline substrate, allowing accurate atomic-scale models to be determined. The electronic structure in the vicinity of stoichiometric grain boundaries is relatively benign to device performance but segregation of oxygen vacancies introduces barriers to electron transport, because of the development of a space charge region. An intrinsically oxygen-deficient boundary exhibits charge trapping consistent with electron energy loss spectroscopy measurements. We discuss strategies for the synthesis of polycrystalline anatase in order to minimize the formation of such deleterious grain boundaries.

Breaking of Thermopower-Conductivity Trade-Off in LaTiO3 Film around Mott Insulator to Metal Transition.

Introducing artificial strain in epitaxial thin films is an effective strategy to alter electronic structures of transition metal oxides (TMOs) and to induce novel phenomena and functionalities not realized in bulk crystals. This study reports a breaking of the conventional trade-off relation in thermopower (S)-conductivity (σ) and demonstrates a 2 orders of magnitude enhancement of power factor (PF) in compressively strained LaTiO3 (LTO) films. By varying substrates and reducing film thickness down to 4 nm, the out-of-plane to the in-plane lattice parameter ratio is controlled from 0.992 (tensile strain) to 1.034 (compressive strain). This tuning induces the electronic structure change from a Mott insulator to a metal and leads to a 103 -fold increase in σ up to 2920 S cm-1 . Concomitantly, the sign of S inverts from positive to negative, and both σ and S increase and break the trade-off relation between them in the n-type region. As a result, the PF (=S2 σ) is significantly enhanced to 300 µW m- 1 K-2 , which is 102 times larger than that of bulk LTO. Present results propose epitaxial strain as a means to finely tune strongly correlated TMOs close to their Mott transition, and thus to harness the hidden large thermoelectric PF.

Atomistic Origin of Li-Ion Conductivity Reduction at (Li3xLa2/3-x)TiO3 Grain Boundary.

Lithium lanthanum titanate (LLTO) is one of the excellent candidates for an electrolyte in the all-solid-state Li-ion battery, owing to the high Li-ion conductivity in the bulk. However, the Li-ion conductivity at the grain boundary (GB) is largely reduced, and it is therefore important to reveal the origin of Li-ion conductivity reduction at the GB. Here, by using atomic-resolution scanning transmission electron microscopy combined with atomic force microscopy, we investigate the charge states, Li-ion conductivities, atomic and electronic structures at the LLTO Σ5 and Σ13 GBs. Although the Σ5 GB has no significant influence on Li-ion conductivity, the Σ13 GB shows the evident reduction of Li-ion conductivity. We further elucidate that the Σ13 GB is positively charged by the formation of oxygen vacancies at the GB. Such a positive charge would form the Li-ion depletion layers adjacent to the GB, which causes the significant reduction of Li-ion conductivity.

Single-Dislocation Schottky Diodes.

Dislocations often exhibit unique physical properties distinct from those of the bulk material. However, functional applications of dislocations are challenging due to difficulties in the construction of high-performance devices of dislocations. Here we demonstrate unidirectional single-dislocation Schottky diode arrays in a Fe2O3 thin film on Nb-doped SrTiO3 substrates. Conductivity measurements using conductive atomic force microscopy indicate that a net current will flow through individual dislocation Schottky diodes under forward bias and disappear under reverse bias. Under cyclic bias voltages, the single-dislocation Schottky diodes exhibit a distinct resistive switching behavior containing low-resistance and high-resistance states with a high resistance ratio of ∼103. A combined study of transmission electron microscopy and first-principles calculations reveals that the Fe2O3 dislocations comprise mixed Fe2+ and Fe3+ ions due to O deficiency and exhibit a one-dimensional electrical conductivity. The single-dislocation Schottky diodes may find applications for developing ultrahigh-density electronic and memory devices.

Anisotropic Electrical Conductivity of Oxygen-Deficient Tungsten Oxide Films with Epitaxially Stabilized 1D Atomic Defect Tunnels.

Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was ∼5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.

Overlayer deposition-induced control of oxide ion concentration in SrFe0.5Co0.5O2.5 oxygen sponges.

Controlling the oxide ion (O2-) concentration in oxides is essential to develop advanced ionic devices, i.e. solid oxide fuel cells, smart windows, memory devices, energy storage devices, and so on. Among many oxides several transition metal (TM)-based perovskite oxides show high oxide ion conductivity, and their physical properties show high sensitivity to the change of the oxide ion concentration. Here, the change in the oxide ion concentration is shown through the overlayer deposition on the SrFe0.5Co0.5O2.5 (SFCO) oxygen sponge film. We grew SFCO films followed by the deposition of two kinds of complex oxide films under exactly the same growth conditions, and observed the changes in the crystal structure, valence states, and magnetic ground states. As the NSMO overlayer grows, strong evidence of oxidation at the O K edge is shown. In addition, the Fe4+ feature is revealed, and the electron valence state of Co increased from 3 to 3.25. The oxide ion concentration of SFCO changes during layer growth due to oxidation or reduction due to differences in chemical potential. The present results might be useful to develop advanced ionic devices using TM-based perovskite oxides.

Development of Novel Thermal Diffusivity Analysis by Spot Periodic Heating and Infrared Radiation Thermometer Method.

A spot periodic heating method is a highly accurate, non-contact method for the evaluation of anisotropy and relative thermophysical property distribution. However, accurately evaluating thermal diffusivity is difficult due to the influence of temperature wave reflection from the whole surface of the sample. This study proposes a method to derive thermal diffusivity using a parameter table based on heat transfer equations using the concept of optimum distance between heating-point and measurement point. This method considers finite sample size, sensitivity distribution of infrared ray detector, intensity distribution of heating laser and sample thickness. In these results, the obtained thermal diffusivity of pure copper corresponded well with previous literature values. In conclusion, this method is considered highly effective in evaluating the thermal diffusivity in the horizontal direction.

Thermoelectric properties of a semicrystalline polymer doped beyond the insulator-to-metal transition by electrolyte gating.

Conducting polymer thin films containing inherent structural disorder exhibit complicated electronic, transport, and thermoelectric properties. The unconventional power-law relation between the Seebeck coefficient (S) and the electrical conductivity (σ) is one of the typical consequences of this disorder, where no maximum of the thermoelectric power factor (P = S 2σ) has been observed upon doping, unlike conventional systems. Here, it is demonstrated that a thiophene-based semicrystalline polymer exhibits a clear maximum of P through wide-range carrier doping by the electrolyte gating technique. The maximum value appears around the macroscopic insulator-to-metal transition upon doping, which is firmly confirmed by the temperature dependence of σ and magnetoresistance measurements. The effect of disorder on charge transport is suppressed in the metallic state, resulting in the conventional S-σ relation described by the Mott equation. The present results provide a physical background for controlling the performance of conducting polymers toward the application to thermoelectric devices.

Phase Instability amid Dimensional Crossover in Artificial Oxide Crystal.

Artificial crystals synthesized by atomic-scale epitaxy provide the ability to control the dimensions of the quantum phases and associated phase transitions via precise thickness modulation. In particular, the reduction in dimensionality via quantized control of atomic layers is a powerful approach to revealing hidden electronic and magnetic phases. Here, we demonstrate a dimensionality-controlled and induced metal-insulator transition (MIT) in atomically designed superlattices by synthesizing a genuine two-dimensional (2D) SrRuO_{3} crystal with highly suppressed charge transfer. The tendency to ferromagnetically align the spins in an SrRuO_{3} layer diminishes in 2D as the interlayer exchange interaction vanishes, accompanying the 2D localization of electrons. Furthermore, electronic and magnetic instabilities in the two SrRuO_{3} unit cell layers induce a thermally driven MIT along with a metamagnetic transition.

Arbitrary control of the diffusion potential between a plasmonic metal and a semiconductor by an angstrom-thick interface dipole layer.

Localized surface plasmon resonances (LSPRs) are gaining considerable attention due to the unique far-field and near-field optical properties and applications. Additionally, the Fermi energy, which is the chemical potential, of plasmonic nanoparticles is one of the key properties to control hot-electron and -hole transfer at the interface between plasmonic nanoparticles and a semiconductor. In this article, we tried to control the diffusion potential of the plasmonic system by manipulating the interface dipole. We fabricated solid-state photoelectric conversion devices in which gold nanoparticles (Au-NPs) are located between strontium titanate (SrTiO3) as an electron transfer material and nickel oxide (NiO) as a hole transport material. Lanthanum aluminate as an interface dipole layer was deposited on the atomic layer scale at the three-phase interface of Au-NPs, SrTiO3, and NiO, and the effect was investigated by photoelectric measurements. Importantly, the diffusion potential between the plasmonic metal and a semiconductor can be arbitrarily controlled by the averaged thickness and direction of the interface dipole layer. The insertion of an only one unit cell (uc) interface dipole layer, whose thickness was less than 0.5 nm, dramatically controlled the diffusion potential formed between the plasmonic nanoparticles and surrounding media. This is a new methodology to control the plasmonic potential without applying external stimuli, such as an applied potential or photoirradiation, and without changing the base materials. In particular, it is very beneficial for plasmonic devices in that the interface dipole has the ability not only to decrease but also to increase the open-circuit voltage on the order of several hundreds of millivolts.

Ferroelectric Oxide Thin Film with an Out-of-Plane Electrical Conductivity.

Ferroelectricity and electrical conductivity are two fundamentally incompatible properties that are difficult to simultaneously achieve in a material. Here, we combine these two contradictory properties by embedding conducting SrNbO3 micro/nanopillars into a ferroelectric SrNbO3.5 (i.e., Sr2Nb2O7) thin film. The high-Tc ferroelectric SrNbO3.5 thin film is epitaxially grown on a LaAlO3 substrate by pulsed laser deposition. The conducting SrNbO3 micro/nanopillars are introduced into the film via an electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation triggered by a focused electron beam. The sizes and distribution of the SrNbO3 micro/nanopillars can be accurately controlled through artificial manipulation of the electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation. The ferroelectric SrNbO3/SrNbO3.5 thin film with an in-plane polarization exhibits an electrical conductivity in the out-of-plane direction. Such conducting ferroelectric thin films may lead to the discovery of plentiful physical phenomena and have great potential for pyroelectric, photoelectric, and multiferroic applications.