Light-induced insulator-metal transition in Sr2IrO4 reveals the nature of the insulating ground state.

Sr2IrO4 has attracted considerable attention due to its structural and electronic similarities to La2CuO4, the parent compound of high-Tc superconducting cuprates. It was proposed as a strong spin-orbit-coupled Jeff = 1/2 Mott insulator, but the Mott nature of its insulating ground state has not been conclusively established. Here, we use ultrafast laser pulses to realize an insulator-metal transition in Sr2IrO4 and probe the resulting dynamics using time- and angle-resolved photoemission spectroscopy. We observe a gap closure and the formation of weakly renormalized electronic bands in the gap region. Comparing these observations to the expected temperature and doping evolution of Mott gaps and Hubbard bands provides clear evidence that the insulating state does not originate from Mott correlations. We instead propose a correlated band insulator picture, where antiferromagnetic correlations play a key role in the gap opening. More broadly, our results demonstrate that energy-momentum-resolved nonequilibrium dynamics can be used to clarify the nature of equilibrium states in correlated materials.

Crystal structure, properties and pressure-induced insulator-metal transition in layered kagome chalcogenides.

Layered materials with kagome lattice have attracted a lot of attention due to the presence of nontrivial topological bands and correlated electronic states with tunability. In this work, we investigate a unique van der Waals (vdW) material system,A2M3X4(A= K, Rb, Cs;M= Ni, Pd;X= S, Se), where transition metal kagome lattices, chalcogen honeycomb lattices and alkali metal triangular lattices coexist simultaneously. A notable feature of this material is that each Ni/Pd atom is positioned in the center of four chalcogen atoms, forming a local square-planar environment. This crystal field environment results in a low spin stateS= 0 of Ni2+/Pd2+. A systematic study of the crystal growth, crystal structure, magnetic and transport properties of two representative compounds, Rb2Ni3S4and Cs2Ni3Se4, has been carried out on powder and single crystal samples. Both compounds exhibit nonmagneticp-type semiconducting behavior, closely related to the particular chemical environment of Ni2+ions and the alkali metal intercalated vdW structure. Additionally, Cs2Ni3Se4undergoes an insulator-metal transition (IMT) in transport measurements under pressure up to 87.1 GPa without any structural phase transition, while Rb2Ni3S4shows the tendency to be metalized.

Recent Advances of VO2 in Sensors and Actuators.

Vanadium dioxide (VO2) stands out for its versatility in numerous applications, thanks to its unique reversible insulator-to-metal phase transition. This transition can be initiated by various stimuli, leading to significant alterations in the material's characteristics, including its resistivity and optical properties. As the interest in the material is growing year by year, the purpose of this review is to explore the trends and current state of progress on some of the applications proposed for VO2 in the field of sensors and actuators using literature review methods. Some key applications identified are resistive sensors such as strain, temperature, light, gas concentration, and thermal fluid flow sensors for microfluidics and mechanical microactuators. Several critical challenges have been recognized in the field, including the expanded investigation of VO2-based applications across multiple domains, exploring various methods to enhance device performance such as modifying the phase transition temperature, advancing the fabrication techniques for VO2 structures, and developing innovative modelling approaches. Current research in the field shows a variety of different sensors, actuators, and material combinations, leading to different sensor and actuator performance input ranges and output sensitivities.

Pressure-Driven Polymorphic Transition, Emergent Insulator-To-Metal Transition, and Photoconductivity Switching in Violet Phosphorus.

Polymorphic phase transition is an essential phenomenon in condensed matter that the physical properties of materials may undergo significant changes due to the structural transformation. Phase transition has thus become an important means and dimension for regulating material properties. Herein, this study demonstrates the pressure-induced multi-transition of both structure and physical properties in violet phosphorus, a novel phosphorus allotrope. Under compression, violet phosphorus undergoes sequential polymorphic phase transitions. Concomitant with the first phase transition, violet phosphorus exhibits emergent insulator-metal transition, superconductivity, and dramatic switching from positive to negative photoconductivity. Remarkably, the resistance of violet phosphorus shows a sudden drop of around 107 along with the phase transition. In addition, piezochromism from translucent red to opaque black and suppression of photoluminescence are observed upon compression. Of particular interest is that the sample irreversibly transforms into black phosphorus with a pronounced discrepancy in physical properties from the pristine violet phosphorus after decompression. The abundant polymorphic transitions and property changes in violet phosphorus have significant implications for designing novel pressure-responsive electronic/optoelectronic devices and exploring concealed polymorphic transition materials.

Coexistent VO2 (M) and VO2 (B) Polymorphous Thin Films with Multiphase-Driven Insulator-Metal Transition.

Reversible insulator-metal transition (IMT) and structure phase change in vanadium dioxide (VO2) remain vital and challenging with complex polymorphs. It is always essential to understand the polymorphs that coexist in desired VO2 materials and their IMT behaviors. Different electrical properties and lattice alignments in VO2 (M) and VO2 (B) phases have enabled the creation of versatile functional devices. Here, we present polymorphous VO2 thin films with coexistent VO2 (M) and VO2 (B) phases and phase-dependent IMT behaviors. The presence of VO2 (B) phases may induce lattice distortions in VO2 (M). The plane spacing of (011)M in the VO2 (M) phase becomes widened, and the V-V and V-O vibrations shift when more VO2 (B) phase exists in the VO2 (M) matrix. Significantly, the coexisting VO2 (B) phases promote the IMT temperature of the polymorphous VO2 thin films. We expect that such coexistent polymorphs and IMT variations would help us to understand the microstructures and IMT in the desired VO2 materials and contribute to advanced electronic transistors and optoelectronic devices.

Reversible Entropy-Driven Defect Migration and Insulator-Metal Transition Suppression in VO2 Nanostructures for Phase-Change Electronic Switching.

Oxygen defects are among essential issues and required to be manipulated in correlated electronic oxides with insulator-metal transition (IMT). Besides, surface and interface control are necessary but challenging in field-induced electronic switching towards advanced IMT-triggered transistors and optical modulators. Herein, we demonstrated reversible entropy-driven oxygen defect migrations and reversible IMT suppression in vanadium dioxide (VO2 ) phase-change electronic switching. The initial IMT was suppressed with oxygen defects, which is caused by the entropy change during reversed surface oxygen ionosorption on the VO2 nanostructures. This IMT suppression is reversible and reverts when the adsorbed oxygen extracts electrons from the surface and heals defects again. The reversible IMT suppression observed in the VO2 nanobeam with M2 phase is accompanied by large variations in the IMT temperature. We also achieved irreversible and stable IMT by exploiting an Al2 O3 partition layer prepared by atomic layer deposition (ALD) to disrupt the entropy-driven defect migration. We expected that such reversible modulations would be helpful for understanding the origin of surface-driven IMT in correlated vanadium oxides, and constructing functional phase-change electronic and optical devices.

Enhancement of temperature-modulated NbO2-based relaxation oscillator via interfacial and bulk treatments.

This work demonstrates oscillation frequency modulation in a NbO2-based relaxation oscillator device, in which the oscillation frequency increases with operating temperature and source voltage, and decreases with load resistance. An annealing-induced oxygen diffusion at 373 K was carried out to optimize the stoichiometry of the bulk NbO2to achieve consistent oscillation frequency shift with device temperature. The device exhibits stable self-sustained oscillation in which the frequency can be modulated between 2 and 33 MHz, and a wider operating voltage range can be obtained. An additional surface treatment step was employed during fabrication to reduce the surface roughness of the bottom electrode and to remove surface contaminants that affect the interfacial properties of the device. The device frequency tunability coupled with high oscillating frequency and high endurance capability of more than 1.5 × 108cycles indicates that the Pt/NbO2/Pt device is particularly suitable for applications in an oscillatory neural network.

Linear Frequency Modulation of NbO2-Based Nanoscale Oscillator With Li-Based Electrochemical Random Access Memory for Compact Coupled Oscillatory Neural Network.

Oscillatory neural network (ONN)-based classification of clustered data relies on frequency synchronization to injected signals representing input data, showing a more efficient structure than a conventional deep neural network. A frequency tunable oscillator is a core component of the network, requiring energy-efficient, and area-scalable characteristics for large-scale hardware implementation. From a hardware viewpoint, insulator-metal transition (IMT) device-based oscillators are attractive owing to their simple structure and low power consumption. Furthermore, by introducing non-volatile analog memory, non-volatile frequency programmability can be obtained. However, the required device characteristics of the oscillator for high performance of coupled oscillator have not been identified. In this article, we investigated the effect of device parameters of IMT oscillator with non-volatile analog memory on coupled oscillators network for classification of clustered data. We confirmed that linear conductance response with identical pulses is crucial to accurate training. In addition, considering dispersed clustered inputs, a wide synchronization window achieved by controlling the hold voltage of the IMT shows resilient classification. As an oscillator that satisfies the requirements, we evaluated the NbO2-based IMT oscillator with non-volatile Li-based electrochemical random access memory (Li-ECRAM). Finally, we demonstrated a coupled oscillator network for classifying spoken vowels, achieving an accuracy of 85%, higher than that of a ring oscillator-based system. Our results show that an NbO2-based oscillator with Li-ECRAM has the potential for an area-scalable and energy-efficient network with high performance.

Reversible Insulator-Metal Transition by Chemical Doping and Dedoping of a Mott Insulator.

The chemical carrier doping of molecular Mott insulators has been poorly investigated to date due to its difficulty. In this study, iodine doping of a molecular Mott insulator, lithium phthalocyanine crystallized in the x-form (x-LiPc), was performed to obtain metallic x-LiPcI. Crystal structure analysis revealed that iodine atoms penetrated channels of x-LiPc and formed one-dimensional chains. The Raman spectroscopy of x-LiPcI indicated the existence of linear I5 - , demonstrating a transition from a half-filled band of the Mott insulating state to a 2/5-filled band of the metallic state. Electrical resistivity measurements confirmed the metallic nature of x-LiPcI, whereas a thermally activated behavior was observed for pristine x-LiPc. Furthermore, the x-LiPc Mott insulator was reproduced by dedoping iodine from x-LiPcI, suggesting that the electronic state can be reversibly tuned between the Mott insulating and metallic states by chemical doping and dedoping.

Atomic Layer Deposited Ti2 O3 Thin Films.

Ti2 O3 thin films have been prepared through atomic layer deposition and subjected to electrical resistivity measurements as a function of temperature. The as-prepared films were stable for up to three weeks. In Ti2 O3 thin films, the insulator-metal transition is observed at ∼80 K, with nearly 3-4 orders of magnitude change in resistivity. The anomalous increase in electrical resistivity in the films is in accordance with the two-band model. However, the energy interval between the bands depending on the crystallographic c/a ratio leads to a change in electrical resistivity as a function of temperature.

Pressure-Induced Superconductivity in Iron-Based Spin-Ladder Compound BaFe2+δ(S1-xSex)3.

The iron-based superconductors had a significant impact on condensed matter physics. They have a common structural motif of a two-dimensional square iron lattice and exhibit fruitful physical properties as a strongly correlated electron system. During the extensive investigations, quasi-one-dimensional iron-based spin-ladder compounds attracted much attention as a platform for studying the interplay between magnetic and orbital ordering. In these compounds, BaFe2S3 and BaFe2Se3 were found to exhibit superconductivity under high pressure, having a different crystal and magnetic structure at low temperature. We report a brief review of the iron-based spin-ladder compound and recent studies for BaFe2+δ(S1-xSex)3. BaFe2(S0.75 Se0.25)3 is in the vicinity of the boundary of two different magnetic phases and it is intriguing to perform high pressure experiments for studying superconductivity, since effects of large magnetic fluctuations on superconductivity are expected. The effect of iron stoichiometry on the interplay between magnetism and superconductivity is also studied by changing the iron concentration in BaFe2+δSe3.

Inherent stochasticity during insulator-metal transition in VO2.

Vanadium dioxide (VO2), which exhibits a near-room-temperature insulator-metal transition, has great potential in applications of neuromorphic computing devices. Although its volatile switching property, which could emulate neuron spiking, has been studied widely, nanoscale studies of the structural stochasticity across the phase transition are still lacking. In this study, using in situ transmission electron microscopy and ex situ resistive switching measurement, we successfully characterized the structural phase transition between monoclinic and rutile VO2 at local areas in planar VO2/TiO2 device configuration under external biasing. After each resistive switching, different VO2 monoclinic crystal orientations are observed, forming different equilibrium states. We have evaluated a statistical cycle-to-cycle variation, demonstrated a stochastic nature of the volatile resistive switching, and presented an approach to study in-plane structural anisotropy. Our microscopic studies move a big step forward toward understanding the volatile switching mechanisms and the related applications of VO2 as the key material of neuromorphic computing.

Electronic structure of ternary palladates and effect of hole doping: a valence band photoemission spectroscopic study.

We investigate the electronic structure of ternary palladatesAPd3O4(A= Sr, Ca) using valence band photoemission spectroscopy and band structure calculations. Energy positions of various features and overall width of the experimental valence band spectra are well captured by band structure calculations using hybrid functional. Band structure calculations within local density approximations lead to metallic ground state while the calculations using hybrid functional provide band gap of 0.25 eV and 0.22 eV for CaPd3O4and SrPd3O4respectively, suggesting moderate to strong electron correlation strength in these narrow band gap semiconducting palladates. High resolution spectra reveal negligibly small intensity at Fermi level,EF, for parent compounds, while hole doped SrPd3O4(by 15% Li substitution at Sr site) exhibits a Fermi cut-off suggesting metallic character in contrast to semiconducting transport. These observations reveal the importance of localization of electrons in case where the Fermi edge falls in the mobility edge.

Electron-phonon-driven three-dimensional metallicity in an insulating cuprate.

The role of the crystal lattice for the electronic properties of cuprates and other high-temperature superconductors remains controversial despite decades of theoretical and experimental efforts. While the paradigm of strong electronic correlations suggests a purely electronic mechanism behind the insulator-to-metal transition, recently the mutual enhancement of the electron-electron and the electron-phonon interaction and its relevance to the formation of the ordered phases have also been emphasized. Here, we combine polarization-resolved ultrafast optical spectroscopy and state-of-the-art dynamical mean-field theory to show the importance of the crystal lattice in the breakdown of the correlated insulating state in an archetypal undoped cuprate. We identify signatures of electron-phonon coupling to specific fully symmetric optical modes during the buildup of a three-dimensional (3D) metallic state that follows charge photodoping. Calculations for coherently displaced crystal structures along the relevant phonon coordinates indicate that the insulating state is remarkably unstable toward metallization despite the seemingly large charge-transfer energy scale. This hitherto unobserved insulator-to-metal transition mediated by fully symmetric lattice modes can find extensive application in a plethora of correlated solids.

Electronic structure of dense solid oxygen from insulator to metal investigated with X-ray Raman scattering.

Electronic structures of dense solid oxygen have been investigated up to 140 GPa with oxygen K-edge X-ray Raman scattering spectroscopy with the help of ab initio calculations based on density functional theory with semilocal metageneralized gradient approximation and nonlocal van der Waals density functionals. The present study demonstrates that the transition energies (Pi*, Sigma*, and the continuum) increase with compression, and the slopes of the pressure dependences then change at 94 GPa. The change in the slopes indicates that the electronic structure changes at the metallic transition. The change in the Pi* and Sigma* bands implies metallic characteristics of dense solid oxygen not only in the crystal a-b plane but also parallel to the c axis. The pressure evolution of the spectra also changes at ∼40 GPa. The experimental results are qualitatively reproduced in the calculations, indicating that dense solid oxygen transforms from insulator to metal via the semimetallic transition.

Localized Triggering of the Insulator-Metal Transition in VO2 Using a Single Carbon Nanotube.

Vanadium dioxide (VO2) has been widely studied for its rich physics and potential applications, undergoing a prominent insulator-metal transition (IMT) near room temperature. The transition mechanism remains highly debated, and little is known about the IMT at nanoscale dimensions. To shed light on this problem, here we use ∼1 nm-wide carbon nanotube (CNT) heaters to trigger the IMT in VO2. Single metallic CNTs switch the adjacent VO2 at less than half the voltage and power required by control devices without a CNT, with switching power as low as ∼85 µW at 300 nm device lengths. We also obtain potential and temperature maps of devices during operation using Kelvin probe microscopy and scanning thermal microscopy. Comparing these with three-dimensional electrothermal simulations, we find that the local heating of the VO2 by the CNT plays a key role in the IMT. These results demonstrate the ability to trigger IMT in VO2 using nanoscale heaters and highlight the significance of thermal engineering to improve device behavior.

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.

Stochastic IMT (Insulator-Metal-Transition) Neurons: An Interplay of Thermal and Threshold Noise at Bifurcation.

Artificial neural networks can harness stochasticity in multiple ways to enable a vast class of computationally powerful models. Boltzmann machines and other stochastic neural networks have been shown to outperform their deterministic counterparts by allowing dynamical systems to escape local energy minima. Electronic implementation of such stochastic networks is currently limited to addition of algorithmic noise to digital machines which is inherently inefficient; albeit recent efforts to harness physical noise in devices for stochasticity have shown promise. To succeed in fabricating electronic neuromorphic networks we need experimental evidence of devices with measurable and controllable stochasticity which is complemented with the development of reliable statistical models of such observed stochasticity. Current research literature has sparse evidence of the former and a complete lack of the latter. This motivates the current article where we demonstrate a stochastic neuron using an insulator-metal-transition (IMT) device, based on electrically induced phase-transition, in series with a tunable resistance. We show that an IMT neuron has dynamics similar to a piecewise linear FitzHugh-Nagumo (FHN) neuron and incorporates all characteristics of a spiking neuron in the device phenomena. We experimentally demonstrate spontaneous stochastic spiking along with electrically controllable firing probabilities using Vanadium Dioxide (VO2) based IMT neurons which show a sigmoid-like transfer function. The stochastic spiking is explained by two noise sources - thermal noise and threshold fluctuations, which act as precursors of bifurcation. As such, the IMT neuron is modeled as an Ornstein-Uhlenbeck (OU) process with a fluctuating boundary resulting in transfer curves that closely match experiments. The moments of interspike intervals are calculated analytically by extending the first-passage-time (FPT) models for Ornstein-Uhlenbeck (OU) process to include a fluctuating boundary. We find that the coefficient of variation of interspike intervals depend on the relative proportion of thermal and threshold noise, where threshold noise is the dominant source in the current experimental demonstrations. As one of the first comprehensive studies of a stochastic neuron hardware and its statistical properties, this article would enable efficient implementation of a large class of neuro-mimetic networks and algorithms.

Switching VO2 Single Crystals and Related Phenomena: Sliding Domains and Crack Formation.

VO2 is the prototype material for insulator-metal transition (IMT). Its transition at TIMT = 340 K is fast and consists of a large resistance jump (up to approximately five orders of magnitude), a large change in its optical properties in the visible range, and symmetry change from monoclinic to tetragonal (expansion by 1% along the tetragonal c-axis and 0.5% contraction in the perpendicular direction). It is a candidate for potential applications such as smart windows, fast optoelectronic switches, and field-effect transistors. The change in optical properties at the IMT allows distinguishing between the insulating and the metallic phases in the mixed state. Static or dynamic domain patterns in the mixed-state of self-heated single crystals during electric-field induced switching are in strong contrast with the percolative nature of the mixed state in switching VO2 films. The most impressive effect-so far unique to VO2-is the sliding of narrow semiconducting domains within a metallic background in the positive sense of the electric current. Here we show images from videos obtained using optical microscopy for sliding domains along VO2 needles and confirm a relation suggested in the past for their velocity. We also show images for the disturbing damage induced by the structural changes in switching VO2 crystals obtained for only a few current-voltage cycles.

Charge disproportionation and the pressure-induced insulator-metal transition in cubic perovskite PbCrO3.

The perovskite PbCrO3 is an antiferromagnetic insulator. However, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. We report a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. We argue that a charge disproportionation 3Cr(4+) → 2Cr(3+) + Cr(6+) in association with the 6s-p hybridization on the Pb(2+) is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT+U) calculations.