Materials with strong electronic Coulomb interactions play an increasing role in modern materials applications. "Thermochromic" systems, which exhibit thermally induced changes in their optical response, provide a particularly interesting case. The optical switching associated with the metal-insulator transition of vanadium dioxide (VO2), for example, has been proposed for use in "intelligent" windows, which selectively filter radiative heat in hot weather conditions. In this work, we develop the theoretical tools for describing such a behavior. Using a novel scheme for the calculation of the optical conductivity of correlated materials, we obtain quantitative agreement with experiments for both phases of VO2. On the example of an optimized energy-saving window setup, we further demonstrate that theoretical materials design has now come into reach, even for the particularly challenging class of correlated electron systems.
The thermal radiative near field transport between vanadium dioxide and silicon oxide at submicron distances is expected to exhibit a strong dependence on the state of vanadium dioxide which undergoes a metal-insulator transition near room temperature. We report the measurement of near field thermal transport between a heated silicon oxide micro-sphere and a vanadium dioxide thin film on a titanium oxide (rutile) substrate. The temperatures of the 15 nm vanadium dioxide thin film varied to be below and above the metal-insulator-transition, the sphere temperatures were varied in a range between…
The effects of the spin and lattice degrees of freedom on the electronic structure of M1 vanadium dioxide are explored using a quasiparticle description. Contraction of the inter-vanadium spacing of the Peierls pairings stabilizes bonding electrons, reducing polarizability and thus widening the band gap. Increases of this inter-vanadium spacing of as little as 1 \% reduce this stabilization, resulting in a crossover to ferromagnetic behaviour accomplished by half of the valence electrons inhabiting the leading edge of the conduction band in localized atomic-like orbitals, as the antiferromagne…
The low temperature monoclinic, insulating phase of vanadium dioxide is ordinarily considered nonmagnetic, with dimerized vanadium atoms forming spin singlets, though paramagnetic response is seen at low temperatures. We find a nonlocal spin Seebeck signal in VO2 films that appears below 30 K and which increases with decreasing temperature. The spin Seebeck response has a non-hysteretic dependence on in-plane external magnetic field. This paramagnetic spin Seebeck response is discussed in terms of prior findings on paramagnetic spin Seebeck effects and expected magnetic excitations of the mono…
Vanadium dioxide undergoes a first order metal-insulator transition at 340 K. In this work, we develop and carry out state of the art linear scaling DFT calculations refined with non-local dynamical mean-field theory. We identify a complex mechanism, a Peierls-assisted orbital selection Mott instability, which is responsible for the insulating M$_1$ phase, and furthermore survives a moderate degree of disorder.
The metal-insulator transition and unconventional metallic transport in vanadium dioxide (VO$_2$) are investigated with a combination of spectroscopic ellipsometry and reflectance measurements. The data indicates that electronic correlations, not electron-phonon interactions, govern charge dynamics in the metallic state of VO$_2$. This study focuses on the frequency and temperature dependence of the conductivity in the regime of extremely short mean free path violating the Ioffe-Regel-Mott limit of metallic transport. The standard quasiparticle picture of charge conduction is found to be unten…
Vanadium dioxide is currently considered as one of the most promising metarials for oxide elcteronics. Both planar and sandwich thin-film MOM devices based on VO2 exhibit electrical switching with an S-shaped I-V characteristic, and this switching effect is associated with the metal-insulator transition (MIT). In an electrical circuit containing such a switching device, relaxation oscillations are observed if the load line intersects the I-V curve at a unique point in NDR region. All these effects are potentially prospective for designing various devices of oxide electronics, particularly, ele…
The influence of Coulomb correlation on magnetic and spectral properties in metallic rutile phase of vanadium dioxide is studied by state of the art LDA+DMFT method. Calculation results in strongly correlated metallic state with an effective mass renormalization $m^*/m\approx2$. Uniform magnetic susceptibility shows Curie-Weiss temperature dependence with effective magnetic moment, $p_{eff}^{theor} = 1.54 μ_B$, in a good agreement with the experimental value $p_{eff}^{exp} = 1.53 μ_B$ that is close to ideal value for V$^{4+}$ ion with the spin $S=1/2$, $p_{eff} = 1.73 μ_B$. Calculated spectral…
We use optical-pump terahertz-probe spectroscopy to investigate the near-threshold behavior of the photoinduced insulator-to-metal (IM) transition in vanadium dioxide thin films. Upon approaching Tc a reduction in the fluence required to drive the IM transition is observed, consistent with a softening of the insulating state due to an increasing metallic volume fraction (below the percolation limit). This phase coexistence facilitates the growth of a homogeneous metallic conducting phase following superheating via photoexcitation. A simple dynamic model using Bruggeman effective medium theory …
The complex interplay between several active degrees of freedom (charge, lattice, orbtial and spin order) is thought to determine the electronic properties of many oxides, but the respective role of the various contributions is often extremely difficult to determine. Vanadium dioxide (VO$_2$) is a particularly notorious example. Here we report on combined ultrafast electron diffraction (UED) and infrared transmissivity experiments in which we directly watch and separate the lattice and charge density reorganizations that are associated with the optically-induced semiconductor-metal transition …
Recent progress in growth and characterization of thin-film VO$_2$ has shown its electronic properties can be significantly modulated by epitaxial matching. To throw new light on the concept of `Mott engineering', we develop a symmetry-consistent approach to treat structural distortions and electronic correlations in epitaxial VO$_2$ films under strain, and compare our design with direct experimental probes. We find strong evidence for the emergence of correlation-driven charge order deep in the metallic phase, and our results indicate that exotic phases of VO$_2$ can be controlled with epitax…
Vanadium dioxide(VO$_2$) is a paradigmatic example of a strongly correlated system that undergoes a metal-insulator transition at a structural phase transition. To date, this transition has necessitated significant post-hoc adjustments to theory in order to be described properly. Here we report standard state-of-the-art first principles quantum Monte Carlo (QMC) calculations of the structural dependence of the properties of VO$_2$. Using this technique, we simulate the interactions between electrons explicitly, which allows for the metal-insulator transition to naturally emerge, importantly wi…
The physics of the metal-insulator transition (MIT) in vanadium dioxide remains a subject of intense interest. Because of the complicating effects of elastic strain on the phase transition, there is interest in comparatively strain-free means of examining VO2 material properties. We report contact-free, low-strain studies of the MIT through an inductive bridge approach sensitive to the magnetic response of VO2 powder. Rather than observing the expected step-like change in susceptibility at the transition, we argue that the measured response is dominated by an analog of the Barkhausen effect, d…
We present structural studies of V$_{1-x}$Cr$_x$O$_2$ (pure, 0.7% and 2.5% Cr doped) compounds at room temperature in a diamond anvil cell for pressures up to 20 GPa using synchrotron x-ray powder diffraction. All the samples studied show a persistence of the monoclinic $M_1$ symmetry between 4 and 12 GPa. Above 12 GPa, the monoclinic $M_1$ symmetry changes to isostructural $M_x$ phase (space group $P2_1/c$) with a significant anisotropy in lattice compression of the $b$-$c$ plane of the $M_{1}$ phase. This behavior can be reconciled invoking the pressure induced charge-delocalization.
We report modulation of a reversible phase transition in VO2 films by hydrogen doping. A metallic phase and a new insulating phase are successively observed at room temperature as the doping concentration increases. It is suggested that the polarized charges from doped hydrogens play an important role. These charges gradually occupy V3d-O2p hybridized orbitals and consequently modulate the filling of the VO2 crystal conduction band-edge states, which eventually evolve into new valence band-edge states. This demonstrates the exceptional sensitivity of VO2 electronic properties to electron conce…
We investigate the electronic and structural changes at the nanoscale in vanadium dioxide (VO2) in the vicinity of its thermally driven phase transition. Both electronic and structural changes exhibit phase coexistence leading to percolation. In addition, we observe a dichotomy between the local electronic and structural transitions. Nanoscale x-ray diffraction reveals local, non-monotonic switching of the lattice structure, a phenomenon that is not seen in the electronic insulator-to-metal transition mapped by near-field infrared microscopy.
Vanadium dioxide (VO2) undergoes a phase transition at a temperature of 340 K between an insulating monoclinic M1 phase and a conducting rutile phase. Accurate measurements of possible anisotropy of the electronic properties and phonon features of VO2 in the insulating monoclinic M1 and metallic rutile phases are a prerequisite for understanding the phase transition in this correlated system. Recently, it has become possible to grow single domain untwinned VO2 microcrystals which makes it possible to investigate the true anisotropy of VO2. We performed polarized transmission infrared micro-spe…
We combine ultrafast electron diffraction and time-resolved terahertz spectroscopy measurements to unravel the connection between structure and electronic transport properties during the photoinduced insulator-metal transitions in vanadium dioxide. We determine the structure of the metastable monoclinic metal phase, which exhibits anti-ferroelectric charge order arising from a thermally activated, orbital-selective phase transition in the electron system. The relative contribution of this photoinduced monoclinic metal (which has no equilibrium analog) and the photoinduced rutile metal (known f…
Insulator-to-metal (MI) phase transition in vanadium dioxide (VO2) thin films with controlled lattice distortion was investigated by thermopower measurements. VO2 epitaxial films with different crystallographic orientations, grown on (0001) alpha-Al2O3, (11-20) alpha-Al2O3, and (001) TiO2 substrates, showed significant decrease of absolute value of Seebeck coefficient (S) from ~200 to 23 microV K-1, along with a sharp drop in electrical resistivity (rho), due to the transition from an insulator to a metal. The MI transition temperatures observed both in rho (Trho) and S (TS) for the VO2 films …
In this work, we experimentally and theoretically explore voltage controlled oscillations occurring in micro-beams of vanadium dioxide. These oscillations are a result of the reversible insulator to metal phase transition in vanadium dioxide. Examining the structure of the observed oscillations in detail, we propose a modified percolative-avalanche model which allows for voltage-triggering. This model captures the periodicity and waveshape of the oscillations as well as several other key features. Importantly, our modeling shows that while temperature plays a critical role in the vanadium diox…
Surface plasmon polaritons can substantially reduce the sizes of optical devices, since they can concentrate light to (sub)wavelength scales. However, (sub)wavelength-scale electro-optic plasmonic switches or modulators with high efficiency, low insertion loss, and high extinction ratios remain a challenge due to their small active volumes. Here, we use the insulator-metal phase transition of a correlated-electron material, vanadium dioxide, to overcome this limitation and demonstrate compact, broadband, and efficient plasmonic switches with integrated electrical control. The devices are micro…
We present a detailed infrared study of the insulator-to-metal transition (IMT) in vanadium dioxide (VO2) thin films. Conventional infrared spectroscopy was employed to investigate the IMT in the far-field. Scanning near-field infrared microscopy directly revealed the percolative IMT with increasing temperature. We confirmed that the phase transition is also percolative with cooling across the IMT. We present extensive near-field infrared images of phase coexistence in the IMT regime in VO2. We find that the coexisting insulating and metallic regions at a fixed temperature are static on the ti…
We present the first comprehensive broadband optical spectroscopy data on two insulating phases of vanadium dioxide (VO2): monoclinic M2 and triclinic. The main result of our work is that the energy gap and the electronic structure are essentially unaltered by the first-order structural phase transition between the M2 and triclinic phases. Moreover, the optical interband features in the M2 and triclinic phases are remarkably similar to those observed in the well-studied monoclinic M1 insulating phase of VO2. As the energy gap is insensitive to the different lattice structures of the three insu…
Using an \textit{ab initio} approach based on the GW approximation which includes strong local \textbf{k}-space correlations, the Metal-Insulator Transition of M$_2$ vanadium dioxide is broken down into its component parts and investigated. Similarly to the M$_{1}$ structure, the Peierls pairing of the M$_{2}$ structure results in bonding-antibonding splitting which stabilizes states in which the majority of the charge density resides on the Peierls chain. This is insufficient to drop all of the bonding states into the lower Hubbard band however. An antiferroelectric distortion on the neighbor…
Metal-insulator transition was microscopically investigated by orbital-resolved nuclear magnetic resonance (OR-NMR) spectroscopy in a single crystal of vanadium dioxide VO$_2$. Observations of the anisotropic $^{51}$V Knight shift and the nuclear quadrupole frequency allow us to evaluate orbital-dependent spin susceptibility and $d$ orbital occupations. The result is consistent with the degenerated $t_{2g}$ orbitals in a correlated metallic phase and the $d$ orbital ordering in a nonmagnetic insulating phase. The predominant orbital pointing along the chain facilitates a spin-singlet formation…
The metal-insulator transition (MIT) in vanadium dioxide (VO2) has the potential to lead to a number of disruptive technologies, including ultra-fast data storage, optical switches, and transistors which move beyond the limitations of silicon. For applications, VO2 films are deposited on crystalline substrates to prevent cracking observed in bulk VO2 crystals across the thermally driven MIT. Near the MIT, VO2 films exhibit nanoscale coexistence between metallic and insulating phases, which opens up further potential applications such as memristors, tunable capacitors, and optically engineered …
In vanadium dioxide, the interplay between coherent lattice transformation and electronic correlation drives an insulator-to-metal transition (IMT). This phase commutation can be triggered by temperature, pressure, doping or deposition of optical energy. Here we demonstrate that an atomically-strong terahertz electric field initiates a metastable ultrafast IMT in vanadium dioxide without a concomitant lattice transformation. The free-space terahertz field acts as off-resonant excitation with photon energy below the lattice phonons and the interband transitions. Differently from optical and inf…
Oxygen vacancies (VO), a common type of point defects in metal oxides materials, play important roles on the physical and chemical properties. To obtain stoichiometric oxide crystal, the pre-existing VO is always removed via careful post-annealing treatment at high temperature in air or oxygen atmosphere. However, the annealing conditions is difficult to control and the removal of VO in bulk phase is restrained due to high energy barrier of VO migration. Here, we selected VO2 crystal film as the model system and developed an alternative annealing treatment aided by controllable hydrogen doping…
Measurements of the static magnetic susceptibility and of the nuclear magnetic resonance of multiwalled vanadium-oxide nanotubes are reported. In this nanoscale magnet the structural low-dimensionality and mixed valency of vanadium ions yield a complex temperature dependence of the static magnetization and the nuclear relaxation rates. Analysis of the different contributions to the magnetism allows to identify individual interlayer magnetic sites as well as strongly antiferromagnetically coupled vanadium spins (S = 1/2) in the double layers of the nanotube's wall. In particular, the data give …
Many strongly correlated electronic materials, including high-temperature superconductors, colossal magnetoresistance and metal-insulator-transition (MIT) materials, are inhomogeneous on a microscopic scale as a result of domain structure or compositional variations. An important potential advantage of nanoscale samples is that they exhibit the homogeneous properties, which can differ greatly from those of the bulk. We demonstrate this principle using vanadium dioxide, which has domain structure associated with its dramatic MIT at 68 degrees C. Our studies of single-domain vanadium dioxide nan…
The nature of a puzzling high temperature ferromagnetism of doped mixed-valent vanadium oxide nanotubes reported earlier by Krusin-Elbaum et al., Nature 431 (2004) 672, has been addressed by static magnetization, muon spin relaxation, nuclear magnetic and electron spin resonance spectroscopy techniques. A precise control of the charge doping was achieved by electrochemical Li intercalation. We find that it provides excess electrons, thereby increasing the number of interacting magnetic vanadium sites, and, at a certain doping level, yields a ferromagnetic-like response persisting up to room te…
We report on local probe measurements of current-voltage and electrostatic force-voltage characteristics of electric-field-induced insulator to metal transition in VO2 thin film. In conducting AFM mode, switching from the insulating to metallic state occurs for electric-field threshold E~6.5\times10^7 Vm-1 at 300K. Upon lifting the tip above the sample surface, we find that the transition can also be observed through a change in electrostatic force and in tunneling current. In this noncontact regime, the transition is characterized by random telegraphic noise. These results show that electric …
The optical/infrared properties of films of vanadium dioxide (VO2) and vanadium sesquioxide (V2O3) have been investigated via ellipsometry and near-normal incidence reflectance measurements from far infrared to ultraviolet frequencies. Significant changes occur in the optical conductivity of both VO2 and V2O3 across the metal-insulator transitions at least up to (and possibly beyond) 6 eV. We argue that such changes in optical conductivity and electronic spectral weight over a broad frequency range is evidence of the important role of electronic correlations to the metal-insulator transitions …
Vanadium dioxide, an archetypal correlated-electron material, undergoes an insulator-metal transition near room temperature that exhibits electron-correlation-driven and structurally-driven physics. Using ultrafast optical spectroscopy and x-ray scattering we show that these processes can be disentangled in the time domain. Specifically, following intense sub-picosecond electric-field excitation, a partial collapse of the insulating gap occurs within the first ps. Subsequently, this electronic reconfiguration initiates a change in lattice symmetry taking place on a slower timescale. We identif…
A common method of adjusting the metal-insulator transition temperature of M$_{1}$ VO$_{2}$ is via disruption of the Peierls pairing by doping, or inputting stress or strain. However, since adding even small amounts of dopants will change the band structure, it is unclear how doped VO$_{2}$ retains its insulating character observed in experiments. While strong correlations may be responsible for maintaining a gap, theoretical evidence for this has been very difficult to obtain due to the complexity of the many-body problem involved. In this work we use GW calculations modified to include stron…
Amorphous vanadium dioxide (VO$_{2}$) films deposited by atomic layer deposition (ALD) were crystallized with an ex situ anneal at 660-670 $°$C for 1-2 hours under a low oxygen pressure (10$^{-4}$ to 10$^{-5}$ Torr). Under these conditions the crystalline VO$_{2}$ phase was maintained, while formation of the V$_{2}$O$_{5}$ phase was suppressed. Electrical transition from the insulator to the metallic phase was observed in the 37-60 $°$C range, with a R$_{ON}$/R$_{OFF}$ ratio of up to about 750 and critical transition temperature of 7-10 $°$C. Electric field applied across two-terminal device s…
We use apertureless scattering near-field optical microscopy (SNOM) to investigate the nanoscale optical response of vanadium dioxide (VO2) thin films through a temperature-induced insulator-to-metal transition (IMT). We compare images of the transition at both mid-infrared (MIR) and terahertz (THz) frequencies, using a custom-built broadband THz-SNOM compatible with both cryogenic and elevated temperatures. We observe that the character of spatial inhomogeneities in the VO2 film strongly depends on the probing frequency. In addition, we find that individual insulating (or metallic) domains ha…
We use polarization- and temperature-dependent x-ray absorption spectroscopy, in combination with photoelectron microscopy, x-ray diffraction and electronic transport measurements, to study the driving force behind the insulator-metal transition in VO2. We show that both the collapse of the insulating gap and the concomitant change in crystal symmetry in homogeneously strained single-crystalline VO2 films are preceded by the purely-electronic softening of Coulomb correlations within V-V singlet dimers. This process starts 7 K (+/- 0.3 K) below the transition temperature, as conventionally defi…
Vanadium dioxide is one of the most studied strongly correlated materials. Nonetheless, the intertwining between electronic correlation and lattice effects has precluded a comprehensive description of the rutile metal to monoclinic insulator transition, in turn triggering a longstanding "the chicken or the egg" debate about which comes first, the Mott localisation or the Peierls distortion. Here, we suggest that this problem is in fact ill-posed: the electronic correlations and the lattice vibrations conspire to stabilise the monoclinic insulator, and so they must be both considered not to mis…
We present results from an experimental study of the equilibrium and non-equilibrium transport properties of vanadium oxide nanobeams near the metal-insulator transition (MIT). Application of a large electric field in the insulating phase across the nanobeams produces an abrupt MIT and the individual roles of thermal and non-thermal effects in driving the transition are studied. Transport measurements at temperatures ($T$) far below the critical temperature ($T_c$) of MIT, in several nanoscale vanadium oxide devices, show that both $T$ and electric field play distinctly separate, but critical …
The effect of doping with hydrogen on the electrical properties of vanadium oxide is studied. For vanadium oxide films, subject to cold hydrogen plasma treatment, the temperature dependence of resistance with a maximum at T ~ 100 K is observed. Also, the dependence of the a.c. resistance on frequency is studied. A strategy for fabrication new superconducting materials is discussed.
Phase competition in correlated oxides offers tantalizing opportunities as many intriguing physical phenomena occur near the phase transitions. Owing to a sharp metal-insulator transition (MIT) near room temperature, correlated vanadium dioxide (VO2) exhibits a strong competition between insulating and metallic phases that is important for practical applications. However, the phase boundary undergoes strong modification when strain is involved, yielding complex phase transitions. Here, we report the emergence of the nanoscale M2 phase domains in VO2 epitaxial films under anisotropic strain rel…
We report on the magnetic susceptibility and electron spin resonance measurements on polycrystalline samples of the vanadium oxide VOSb$_{2}$O$_{4}$, a quasi-one dimensional S=1/2 Heisenberg system. We show that the susceptibility vanishes at zero temperature, as in a gapped system, and we argue that this is due to a spin-Peierls transition with strong structural fluctuations.
Motivated by recent reports (Phys. Rev. B\textbf{80}, 241102) of room-temperature ferromagnetism in vanadium-oxide based superlattices, a single-site dynamical mean field study of the dependence of the paramagnetic-ferromagnetic phase boundary on superlattice geometry was performed. An examination of variants of the experimentally determined crystal structure indicate that ferromagnetism is found only in a small and probably inaccessible region of the phase diagram. Design criteria for increasing the range over which ferromagnetism might exist are proposed.
Long regarded as a model system for studying insulator-to-metal phase transitions, the correlated electron material vanadium dioxide (VO$_2$) is now finding novel uses in device applications. Two of its most appealing aspects are its accessible transition temperature ($\sim$341 K) and its rich phase diagram. Strain can be used to selectively stabilize different VO$_2$ insulating phases by tuning the competition between electron and lattice degrees of freedom. It can even break the mesoscopic spatial symmetry of the transition, leading to a quasi-periodic ordering of insulating and metallic nan…
The conditions under which ferromagnetism may occur in transition metal oxides with partially filled $t_{2g}$ shells such as vanadium-based perovskites are studied using a combination of density functional and single-site dynamical mean field methods. For reasonable values of the correlation strength, rotations of the VO$_6$ octahedra play an important role in enabling ferromagnetism, with ferromagnetism typically occurring for rotations larger than a nonzero critical value. Ferromagnetism is suppressed near the Mott insulating phase but the phase boundary is otherwise only weakly dependent on…
The paper presents the results of a study of electron-beam modification (EBM) of VO2-switch I-V curve threshold parameters and the self-oscillation frequency of a circuit containing such a switching device. EBM in vacuum is reversible and the parameters are restored when exposed to air at pressure of 150 Pa. At EBM with a dose of 3 C/cm2, the voltages of switching-on (Vth) and off (Vh), as well as the OFF-state resistance Roff, decrease down to 50% of the initial values, and the oscillation frequency increases by 30% at a dose of 0.7 C/cm2. Features of physics of EBM of an oscillator are outli…
We show that the recently proposed S=2 bond model with orbital degrees of freedom for insulating V$_{2}$O$_{3}$ not only explains the anomalous magnetic ordering, but also other mysteries of the magnetic phase transition. The model contains an additional orbital degree of freedom that exhibits a zero temperature quantum phase transtion in the Ising universality class.
Electronic correlations and fluctuating lattice distortions in vanadium dioxide
Collège de France, PSL Research University（法兰西学院，PSL研究大学）；Institute of Theoretical Physics, University of Hamburg（汉堡大学理论物理研究所）；The Hamburg Centre for Ultrafast Imaging（汉堡超快成像中心）；RWTH Aachen University（亚琛工业大学）；Institut für Theoretische Physik und Astrophysik and Würzburg-Dresden Cluster of Excellence ct.qmat, Universität Würzburg（维尔茨堡大学理论物理与天体物理研究所及维尔茨堡-德累斯顿卓越集群ct.qmat）
