Ultrafast generation of hidden phases via energy-tuned electronic photoexcitation in magnetite.

Phase transitions occurring in nonequilibrium conditions can evolve through high-energy intermediate states inaccessible via equilibrium adiabatic conditions. Because of the subtle nature of such hidden phases, their direct observation is extremely challenging and requires simultaneous visualization of matter at subpicoseconds and subpicometer scales. Here, we show that a magnetite crystal in the vicinity of its metal-to-insulator transition evolves through different hidden states when controlled via energy-tuned ultrashort laser pulses. By directly monitoring magnetite's crystal structure with ultrafast electron diffraction, we found that upon near-infrared (800 nm) excitation, the trimeron charge/orbital ordering pattern is destroyed in favor of a phase-separated state made of cubic-metallic and monoclinic-insulating regions. On the contrary, visible light (400 nm) activates a photodoping charge transfer process that further promotes the long-range order of the trimerons by stabilizing the charge density wave fluctuations, leading to the reinforcement of the monoclinic insulating phase. Our results demonstrate that magnetite's structure can evolve through completely different metastable hidden phases that can be reached long after the initial excitation has relaxed, breaking ground for a protocol to control emergent properties of matter.

Finite-Size and Composition-Driven Topological Phase Transition in (Bi1-xInx)2Se3 Thin Films.

In a topological insulator (TI), if its spin-orbit coupling (SOC) strength is gradually reduced, the TI eventually transforms into a trivial insulator beyond a critical point of SOC, at which point the bulk gap closes: this is the standard description of the topological phase transition (TPT). However, this description of TPT, driven solely by the SOC (or something equivalent) and followed by closing and reopening of the bulk band gap, is valid only for infinite-size samples, and little is known how TPT occurs for finite-size samples. Here, using both systematic transport measurements on interface-engineered (Bi1-xInx)2Se3 thin films and theoretical simulations (with animations in the Supporting Information), we show that description of TPT in finite-size samples needs to be substantially modified from the conventional picture of TPT due to surface-state hybridization and bulk confinement effects. We also show that the finite-size TPT is composed of two separate transitions, topological-normal transition (TNT) and metal-insulator transition (MIT), by providing a detailed phase diagram in the two-dimensional phase space of sample size and SOC strength.

Vacancy-Induced Semiconductor-Insulator-Metal Transitions in Nonstoichiometric Nickel and Tungsten Oxides.

Metal-insulator transitions in strongly correlated oxides induced by electrochemical charging have been attributed to formation of vacancy defects. However, the role of native defects in affecting these transitions is not clear. Here, we report a new type of phase transition in p-type, nonstoichiometric nickel oxide involving a semiconductor-to-insulator-to-metal transition along with the complete reversal of conductivity from p- to n-type at room temperature induced by electrochemical charging in a Li+-containing electrolyte. Direct observation of vacancy-ion interactions using in situ near-infrared photoluminescence spectroscopy show that the transition is a result of passivation of native nickel (cationic) vacancy defects and subsequent formation of oxygen (anionic) vacancy defects driven by Li+ insertion into the lattice. Changes in the oxidation states of nickel due to defect interactions probed by X-ray photoemission spectroscopy support the above conclusions. In contrast, n-type, nonstoichiometric tungsten oxide shows only insulator-to-metal transition, which is a result of oxygen vacancy formation. The defect-property correlations shown here in these model systems can be extended to other oxides.

Electrochemically Induced Transformations of Vanadium Dioxide Nanocrystals.

Vanadium dioxide (VO2) undergoes significant optical, electronic, and structural changes as it transforms between the low-temperature monoclinic and high-temperature rutile phases. Recently, alternative stimuli have been utilized to trigger insulator-to-metal transformations in VO2, including electrochemical gating. Here, we prepare and electrochemically reduce mesoporous films of VO2 nanocrystals, prepared from colloidally synthesized V2O3 nanocrystals that have been oxidatively annealed, in a three-electrode electrochemical cell. We observe a reversible transition between infrared transparent insulating phases and a darkened metallic phase by in situ visible-near-infrared spectroelectrochemistry and correlate these observations with structural and electronic changes monitored by X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and conductivity measurements. An unexpected reversible transition from conductive, reduced monoclinic VO2 to an infrared-transparent insulating phase upon progressive electrochemical reduction is observed. This insulator-metal-insulator transition has not been reported in previous studies of electrochemically gated epitaxial VO2 films and is attributed to improved oxygen vacancy formation kinetics and diffusion due to the mesoporous nanocrystal film structure.

Charge transfer and metal-insulator transition in (CrO2)m/(TaO2)nsuperlattices.

Various interfacial emergent phenomena have been discovered in tunable nanoscale materials, especially in artificially designed epitaxial superlattices. In conjunction, the atomically fabricated superlattices have exhibited a plethora of exceptional properties compared to either bulk materials separately. Here, the (CrO2)m/(TaO2)nsuperlattices composed of two lattice-matched metallic metal oxides are constructed. With the help of first-principle density-functional theory calculations, a computational and theoretical study of (CrO2)m/(TaO2)nsuperlattices manifests the interfacial electronic properties in detail. The results suggest that emergent properties result from the charge transfer from the TaO2to CrO2layers. At two special ratios of1:1and1:2betweenmandn, the superlattices undergo metal-to-insulator transition. Additionally, the bands below the Fermi level become narrower with the increasing thickness of the CrO2and TaO2layers. The study reveals that the electronic reconstruction at the interface of two metallic materials can generate interesting physics, which points the direction for the manipulation of functionalities in artificial superlattices or heterostructures within a few atomic layers.

Effects of Oxygen Flow Rate on Metal-to-Insulator Transition Characteristics in NbOx-Based Selectors.

In this work, NbOx-based selector devices were fabricated by sputtering deposition systems. Metal-to-insulator transition characteristics of the device samples were investigated depending on the oxygen flow rate (3.5, 4.5, and 5.5 sccm) and the deposition time. The device stack was scanned by transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The yields, including MIT, nonlinear, and Ohmic, in working devices with different deposition conditions were also evaluated. Moreover, we observed the trend in yield values as a function of selectivity. In addition, the current-voltage (I-V) curves were characterized in terms of DC and pulse endurance. Finally, the switching speed and operating energies were obtained by applying a triangular pulse on the devices, and the recovery time and drift-free characteristics were obtained by the paired pulses.

Dimensionality-Controlled Evolution of Charge-Transfer Energy in Digital Nickelates Superlattices.

Fundamental understanding and control of the electronic structure evolution in rare-earth nickelates is a fascinating and meaningful issue, as well as being helpful to understand the mechanism of recently discovered superconductivity. Here the dimensionality effect on the ground electronic state in high-quality (NdNiO3 ) m /(SrTiO3 )1 superlattices is systematically studied through transport and soft X-ray absorption spectroscopy. The metal-to-insulator transition temperature decreases with the thickness of the NdNiO3 slab decreasing from bulk to 7 unit cells, then increases gradually as m further reduces to 1 unit cell. Spectral evidence demonstrates that the stabilization of insulating phase can be attributed to the increase of the charge-transfer energy between O 2p and Ni 3d bands. The prominent multiplet feature on the Ni L3 edge develops with the decrease of NdNiO3 slab thickness, suggesting the strengthening of the charge disproportionate state under the dimensional confinement. This work provides convincing evidence that dimensionality is an effective knob to modulate the charge-transfer energy and thus the collective ground state in nickelates.

X-ray photoemission and absorption study of the pyrochlore iridates (Eu1-xBix)2Ir2O7, 0 ⩽x ⩽ 1.

The pyrochlore iridates (Eu1-xBix)2Ir2O7(0⩽x⩽1) undergo an anomalous negative lattice expansion for small Bi-doping (x⩽0.035) (region I) and a normal lattice expansion forx⩾0.1(region II); this is accompanied by a transition from an insulating (and magnetically ordered) to a metallic (and with no magnetic ordering) ground state. Here, we investigate (Eu1-xBix)2Ir2O7(0⩽x⩽1) using hard x-ray photoemission spectroscopy and x-ray absorption fine structure (XAFS) spectroscopy. By analyzing the Eu-L3, Ir-L3and Bi-L2&L3edges x-ray absorption near edge structure spectra and Eu-3dcore-level XPS spectra, we show that the metal cations retain their nominal valence, namely, Ir4+, Bi3+and Eu3+, respectively, throughout the series. The Ir-4fand Bi-4fcore-level XPS spectra consist of screened and unscreened doublets. The unscreened component is dominant In the insulating range (x⩽0.035), and in the metallic region (x⩾0.1), the screened component dominates the spectra. The Eu-3dcore-level spectra remain invariant under Bi doping. The extended XAFS data show that the coordination around the Ir remains well preserved throughout the series. The evolution of the valence band spectra near the Fermi energy with increasing Bi doping indicates the presence of strong Ir(5d)-Bi(6p) hybridization which drives the metal-to-insulator transition.

Strain-Mediated High Conductivity in Ultrathin Antiferromagnetic Metallic Nitrides.

Strain engineering provides the ability to control the ground states and associated phase transition in epitaxial films. However, the systematic study of the intrinsic character and strain dependency in transition-metal nitrides remains challenging due to the difficulty in fabricating stoichiometric and high-quality films. Here the observation of an electronic state transition in highly crystalline antiferromagnetic CrN films with strain and reduced dimensionality is reported. By shrinking the film thickness to a critical value of ≈30 unit cells, a profound conductivity reduction accompanied by unexpected volume expansion is observed in CrN films. The electrical conductivity is observed surprisingly when the CrN layer is as thin as a single unit cell thick, which is far below the critical thickness of most metallic films. It is found that the metallicity of an ultrathin CrN film recovers from insulating behavior upon the removal of the as-grown strain by the fabrication of freestanding nitride films. Both first-principles calculations and linear dichroism measurements reveal that the strain-mediated orbital splitting effectively customizes the relatively small bandgap at the Fermi level, leading to an exotic phase transition in CrN. The ability to achieve highly conductive nitride ultrathin films by harnessing strain-control over competing phases can be used for utilizing their exceptional characteristics.

Structural Phase Transition and In-Situ Energy Storage Pathway in Nonpolar Materials: A Review.

Benefitting from exceptional energy storage performance, dielectric-based capacitors are playing increasingly important roles in advanced electronics and high-power electrical systems. Nevertheless, a series of unresolved structural puzzles represent obstacles to further improving the energy storage performance. Compared with ferroelectrics and linear dielectrics, antiferroelectric materials have unique advantages in unlocking these puzzles due to the inherent coupling of structural transitions with the energy storage process. In this review, we summarize the most recent studies about in-situ structural phase transitions in PbZrO3-based and NaNbO3-based systems. In the context of the ultrahigh energy storage density of SrTiO3-based capacitors, we highlight the necessity of extending the concept of antiferroelectric-to-ferroelectric (AFE-to-FE) transition to broader antiferrodistortive-to-ferrodistortive (AFD-to-FD) transition for materials that are simultaneously ferroelastic. Combining discussion of the factors driving ferroelectricity, electric-field-driven metal-to-insulator transition in a (La1-xSrx)MnO3 electrode is emphasized to determine the role of ionic migration in improving the storage performance. We believe that this review, aiming at depicting a clearer structure-property relationship, will be of benefit for researchers who wish to carry out cutting-edge structure and energy storage exploration.

Spectroscopic Evidence of a Dimensionality-Induced Metal-to-Insulator Transition in the Ruddlesden-Popper Lan+1NinO3n+1 Series.

Perovskite-based heterostructures have recently gained remarkable interest, thanks to atomic-scale precision engineering. These systems are very susceptible to small variations of control parameters, such as two-dimensionality, strain, lattice polarizability, and doping. Focusing on the rare-earth nickelate diagram, LaNiO3 (LNO) catches the eye, being the only nickelate that does not undergo a metal-to-insulator transition (MIT). Therefore, the ground state of LNO has been studied in several theoretical and experimental papers. Here, we show by means of infrared spectroscopy that an MIT can be driven by dimensionality control in ultrathin LNO films when the number of unit cells drops to 2. Such a dimensionality tuning can eventually be tailored when a physically implemented monolayer in the ultrathin films is replaced by a digital single layer embedded in the Ruddlesden-Popper Lan+1NinO3n+1 series. We provide spectroscopic evidence that the dimensionality-induced MIT in Ruddlesden-Popper nickelates strongly resembles that of ultrathin LNO films. Our results can pave the way to the employment of Ruddlesden-Popper Lan+1NinO3n+1 to tune the electronic properties of LNO through dimensional transition without the need of physically changing the number of unit cells in thin films.

Strain-Engineered Metal-to-Insulator Transition and Orbital Polarization in Nickelate Superlattices Integrated on Silicon.

Epitaxial growth of SrTiO3 (STO) on silicon greatly accelerates the monolithic integration of multifunctional oxides into the mainstream semiconductor electronics. However, oxide superlattices (SLs), the birthplace of many exciting discoveries, remain largely unexplored on silicon. In this work, LaNiO3 /LaFeO3 SLs are synthesized on STO-buffered silicon (Si/STO) and STO single-crystal substrates, and their electronic properties are compared using dc transport and X-ray absorption spectroscopy. Both sets of SLs show a similar thickness-driven metal-to-insulator transition, albeit with resistivity and transition temperature modified by the different amounts of strain. In particular, the large tensile strain promotes a pronounced Ni 3 d x 2 - y 2 orbital polarization for the SL grown on Si/STO, comparable to that reported for LaNiO3 SL epitaxially strained to DyScO3 substrate. Those results illustrate the ability to integrate oxide SLs on silicon with structure and property approaching their counterparts grown on STO single crystal, and also open up new prospects of strain engineering in functional oxides based on the Si platform.

Digital- to Analog-Type Terahertz Modulation Controlled by Mosaicity of the Substrate Template in Rare-Earth Nickelate Thin Films.

The extreme sensitivity of the metal-insulator (M-I) transition in RNiO3 (R = rare-earth ion) nickelates to various extrinsic and intrinsic factors rely on mechanisms driving structure-property relations. Here, we demonstrate a unique way to control the M-I transition of epitaxial Pr0.5Sm0.5NiO3 thin films using a mosaic template of the LaAlO3(100) substrate; two sets of epitaxial films were deposited on highly oriented crystals and mosaic (with multiple crystallites) crystals. While the former films exhibit a robust and sharp M-I transition, the films on the mosaic substrate show distinctively much more subtle and broad transition, albeit same factors suggesting compositional purity. Terahertz (THz) dynamic conductivity too behaves very differently for the two types of films; Drude dynamics dominate the conductivity of highly crystalline films, whereas disorder-driven Drude-Smith conductivity prevails in mosaic films. Using this mosaic structure-controlled M-I transition and conductivity dynamics, we propose to implement these two templates of films for digital and analog THz transmission amplitude modulators.

Metal-to-Semiconductor Transition and Electronic Dimensionality Reduction of Ca2N Electride under Pressure.

The discovery of electrides, in particular, inorganic electrides where electrons substitute anions, has inspired striking interests in the systems that exhibit unusual electronic and catalytic properties. So far, however, the experimental studies of such systems are largely restricted to ambient conditions, unable to understand their interactions between electron localizations and geometrical modifications under external stimuli, e.g., pressure. Here, pressure-induced structural and electronic evolutions of Ca2N by in situ synchrotron X-ray diffraction and electrical resistance measurements, and density functional theory calculations with particle swarm optimization algorithms are reported. Experiments and computation are combined to reveal that under compression, Ca2N undergoes structural transforms from R 3 ¯ m symmetry to I 4 ¯ 2d phase via an intermediate Fd 3 ¯ m phase, and then to Cc phase, accompanied by the reductions of electronic dimensionality from 2D, 1D to 0D. Electrical resistance measurements support a metal-to-semiconductor transition in Ca2N because of the reorganizations of confined electrons under pressure, also validated by the calculation. The results demonstrate unexplored experimental evidence for a pressure-induced metal-to-semiconductor switching in Ca2N and offer a possible strategy for producing new electrides under moderate pressure.

Electrically Driven Reversible Phase Changes in Layered In2 Se3 Crystalline Film.

An unconventional phase-change memory (PCM) made of In2 Se3 , which utilizes reversible phase changes between a low-resistance crystalline ß phase and a high-resistance crystalline γ phase is reported for the first time. Using a PCM with a layered crystalline film exfoliated from In2 Se3 crystals on a graphene bottom electrode, it is shown that SET/RESET programmed states form via the formation/annihilation of periodic van der Waals' (vdW) gaps (i.e., virtual vacancy layers) in the stack of atomic layers and the concurrent reconfiguration of In and Se atoms across the layers. From density functional theory calculations, ß and γ phases, characterized by octahedral bonding with vdW gaps and tetrahedral bonding without vdW gaps, respectively, are shown to have energy bandgap value of 0.78 and 1.86 eV, consistent with a metal-to-insulator transition accompanying the ß-to-γ phase change. The monolithic In2 Se3 layered film reported here provides a novel means to achieving a PCM based on melting-free, low-entropy phase changes in contrast with the GeTe-Sb2 Te3 superlattice film adopted in interfacial phase-change memory.

Modulation of Metal and Insulator States in 2D Ferromagnetic VS2 by van der Waals Interaction Engineering.

2D transition-metal dichalcogenides (TMDCs) are currently the key to the development of nanoelectronics. However, TMDCs are predominantly nonmagnetic, greatly hindering the advancement of their spintronic applications. Here, an experimental realization of intrinsic magnetic ordering in a pristine TMDC lattice is reported, bringing a new class of ferromagnetic semiconductors among TMDCs. Through van der Waals (vdW) interaction engineering of 2D vanadium disulfide (VS2 ), dual regulation of spin properties and bandgap brings about intrinsic ferromagnetism along with a small bandgap, unravelling the decisive role of vdW gaps in determining the electronic states in 2D VS2 . An overall control of the electronic states of VS2 is also demonstrated: bond-enlarging triggering a metal-to-semiconductor electronic transition and bond-compression inducing metallization in 2D VS2 . The pristine VS2 lattice thus provides a new platform for precise manipulation of both charge and spin degrees of freedom in 2D TMDCs availing spintronic applications.

Metal-to-Insulator Transition in Au Chains on Si(111)-5×2-Au by Band Filling: Infrared Plasmonic Signal and Ab Initio Band Structure Calculation.

The Si(111)-5×2-Au surface is increasingly of interest because it is one of the rare atomic chain systems with quasi-one-dimensional properties. For the deposition of 0.7 monolayers of Au, these chains are metallic. Upon the evaporation of an additional submonolayer amount of gold, the surface becomes insulating but keeps the 5×2 symmetry. This metal-to-insulator transition was in situ monitored based on the infrared plasmonic signal change with coverage. The phase transition is theoretically explained by total-energy and band-structure calculations. Accordingly, it can be understood in terms of the occupation of the originally half-filled one-dimensional band at the Fermi level. By annealing the system, the additional gold is removed from the surface and the plasmonic signal is recovered, which underlines the stability of the metallic structure. So, recent results on the infrared plasmonic signals of the Si(111)-5 × 2-Au surface are supported. The understanding of potential one-dimensional electrical interconnects is improved.

Photoluminescence response of colloidal quantum dots on VO2 film across metal to insulator transition.

We have proposed a method to probe metal to insulator transition in VO2 measuring photoluminescence response of colloidal quantum dots deposited on the VO2 film. In addition to linear luminescence intensity decrease with temperature that is well known for quantum dots, temperature ranges with enhanced photoluminescence changes have been found during phase transition in the oxide. Corresponding temperature derived from luminescence dependence on temperature closely correlates with that from resistance measurement during heating. The supporting reflectance data point out that photoluminescence response mimics a reflectance change in VO2 across metal to insulator transition. Time-resolved photoluminescence study did not reveal any significant change of luminescence lifetime of deposited quantum dots under metal to insulator transition. It is a strong argument in favor of the proposed explanation based on the reflectance data. PACS: 71.30. + h; 73.21.La; 78.47.jd.

The memristive properties of a single VO2 nanowire with switching controlled by self-heating.

A two-terminal memristor memory based on a single VO2 nanowire is reported that can not only provide switchable resistances in a large range of about four orders of magnitude but can also maintain the resistances by a low bias voltage. The phase transition of the single VO2 nanowire was driven by the bias voltage of 0.34 V without using any heat source. The memristive behavior of the single VO2 nanowire was confirmed by observing the switching and non-volatile properties of resistances when voltage pulses and low bias voltage were applied, respectively. Furthermore, multiple retainable resistances in a large range of about four orders of magnitude can be utilized by controlling the number and the amount of voltage pulses under the low bias voltage. This is a key step towards the development of new low-power and two-terminal memory devices for next-generation non-volatile memories.