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 in both of these vanadium oxides. We observe a sharp optical transition with possible final state (exciton) effects in the insulating phase of VO2. This sharp optical transition occurs between narrow a1g bands that arise from the quasi-one-dimensional chains of vanadium dimers. Electronic correlations in the metallic phases of both VO2 and V2O3 lead to reduction of the kinetic energy of the charge carriers compared to band theory values, with paramagnetic metallic V2O3 showing evidence of stronger correlations compared to rutile metallic VO2.
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…
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 …
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…
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 …
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.
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 …
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.
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…
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.
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…
Filling-control metal-insulator transitions (MITs) and related electronic phase diagrams have been investigated for hole-doped vanadium oxides, Pr_{1-x}Ca_xVO_3, Nd_{1-x}Sr_xVO_3 and Y_{1-x}Ca_xVO_3, with perovskite structure. The increase of the doping level x causes the melting of the G-type (and C-type) orbital order, prior to or concomitantly with the MIT, due partly to the doped-hole motion and partly to the ramdom potential arising from the quenched disorder. In particular, the G-type spin- and C-type orbital-ordered phase present in Y_{1-x}Ca_xVO_3 disappears immediately upon hole dopin…
Recent photoemission experiments have shown strong surface modifications in the spectra from vanadium oxides as (V,Cr)_2O_3 or (Sr,Ca)VO_3. The effective mass is enhanced at the surface and the coherent part of the surface spectrum is narrowed as compared to the bulk. The quasiparticle weight is more sensitive at the surface than in the bulk against bandwidth variations. We investigate these effects theoretically considering the single-band Hubbard model for a film geometry. A simplified dynamical mean-field scheme is used to calculate the main features of the interacting layer-dependent spect…
Generic low-energy spectral features related to $d$-$d$ excitations in nearly cubic vanadium perovskites are predicted for the expected $L$-edge resonant inelastic X-ray scattering (RIXS) measurements. Model Hamiltonian describing local electronic properties, including crystal-field effects, of vanadium 3d orbitals in the basic $t_{2g}^2$ configuration is formulated with the help of complementary {\it ab initio} quantum-chemical cluster calculations. In the presence of 2p-core hole, the local Hamiltonian includes strong 2p-3d electron interactions. As a prerequisite for evaluating RIXS transit…
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…
We present our theoretical results on the mechanism of two transitions in vanadium spinel oxides $A$V$_2$O$_4$ ($A$=Zn, Mg, or Cd) in which magnetic V cations constitute a geometrically-frustrated pyrochlore structure. We have derived an effective spin-orbital-lattice coupled model in the strong correlation limit of the multiorbital Hubbard model, and applied Monte Carlo simulation to the model. The results reveal that the higher-temperature transition is a layered antiferro-type orbital ordering accompanied by tetragonal Jahn-Teller distortion, and the lower-temperature transition is an antif…
Nine of the known vanadium oxides, VO$_{2-1/n}$ (n - a positive or negative integer) with n=2 - 6, 8, 9, $\infty$ and -6, undergo metal-insulator transitions accompanied by structural transitions, at various temperatures T$_{MIT}$ (V$_7$O$_{13}$ is metallic above T=0). Among the persistent efforts to determine the driving force(s) of these transitions, electron-electron (Mott-like) and electron-phonon (Peierls-like) interactions, there were several attempts to find systematics in T$_{MIT}$ as function of n. Here we present an unexpectedly simple and illuminating systematics that holds for posi…
LV4O8 (L = Yb, Y, Lu) compounds are reported to crystallize in a structure similar to that of the orthorhombic CaFe2O4 structure-type, and contain four inequivalent V sites arranged in zigzag chains. We confirm the structure and report the magnetic, thermal, and transport properties of polycrystalline YV4O8 and LuV4O8. A first-order like phase transition is observed at 50 K in both YV4O8 and LuV4O8. The symmetry remains the same with the lattice parameters changing discontinously. The structural transition in YV4O8 leads to partial dimerization of the V atoms resulting in a sudden sharp drop i…
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 …
We have theoretically studied successive transitions in vanadium spinel oxides with (t_2g)^2 electron configuration. These compounds show a structural transition at ~ 50K and an antiferromagnetic transition at ~ 40K. Since threefold t_2g orbitals of vanadium cations are occupied partially and vanadiums constitute a geometrically-frustrated pyrochlore lattice, the system provides a particular example to investigate the interplay among spin, orbital and lattice degrees of freedom on frustrated lattice. We examine the models with the Jahn-Teller coupling and/or the spin-orbital superexchange inte…
Bulk-sensitive high-resolution photoemission was carried out on a prototype 3d1 metallic Sr1-xCaxVO3. In a strong contrast to so far reported results, the bulk spectral functions are revealed to be insensitive to x. The conservation of the density of states at the Fermi level in spite of the electron correlation is clarified by the successful suppression and deconvolution of the surface contribution. Our study has demonstrated the importance of high-energy and high-resolution photoemission spectroscopy for revealing detailed bulk electronic states of transition metal oxides.
We perform density functional theory plus dynamical mean field theory calculations to investi- gate internal charge transfer in an artificial superlattice composed of alternating layers of vanadate and manganite perovskite and Ruddlesden-Popper structure materials. We show that the elec- tronegativity difference between vanadium and manganese causes moderate charge transfer from VO2 to MnO2 layers in both perovskite and Ruddlesden-Popper based superlattices, leading to hole doping of the VO2 layer and electron doping of the MnO2 layer. Comparison of the perovskite and Ruddlesden-Popper based h…
Ultrafast optical pump - optical probe and optical pump - terahertz probe spectroscopy were performed on vanadium dioxide (VO2) and vanadium sesquioxide (V2O3) thin films over a wide temperature range. A comparison of the experimental data from these two different techniques and two different vanadium oxides, in particular a comparison of the electronic oscillations generated by the photoinduced longitudinal acoustic modulation, reveals the strong electron-phonon coupling that exists in the metallic state of both materials. The low energy Drude response of V2O3 appears more susceptible than VO…
Unveiling the critical role of interfacial strain in adjusting electronic phase transitions in correlated vanadium dioxide
Key Laboratory of Magnetic Molecules and Magnetic Information Materials of Ministry of Education & School of Materials Science and Engineering, Shanxi Normal University（山西师范大学 磁性分子与磁信息材料教育部重点实验室 & 材料科学与工程学院）；Research Institute of Materials Science, Shanxi Key Laboratory of Advanced Magnetic Materials and Devices, Shanxi Normal University（山西师范大学 材料科学研究所 & 山西省先进磁性材料与器件重点实验室）
V2O3 thin films about 10 nm thick were grown on Al2O3 (0001) by pulsed laser deposition. The XRD analysis is in agreement with R-3c space group. Some of them exhibit the metal / insulator transition characteristic of V2O3 bulk material and others samples exhibit a metallic behavior. For the latter, the XPS analysis indicates an oxidation state of +III for vanadium. There is no metal / insulator transition around 150 K in this sample and a strongly correlated Fermi liquid rho = AT2 behavior of the resistivity at low temperature is observed, with a value of A of 1.2 10-4 ohm cm, 3 times larger t…
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 present our theoretical results on the electronic state in vanadium spinel oxide AlV$_2$O$_4$. The material is a mixed-valent system with the average valence V$^{2.5+}$, and V cations constitute a frustrated pyrochlore structure. It shows a structural transition at $\sim 700$ K, leading to the formation of seven V-sites clusters -- heptamers. We study the electronic state of the heptamer by explicitly taking account of orbital degree of freedom as well as electron correlations. We show that the ground state of the heptamer for realistic parameters becomes spin-singlet because of strong $σ$-…
We present our theoretical and numerical results on thermodynamic properties and the microscopic mechanism of two successive transitions in vanadium spinel oxides $A$V$_2$O$_4$ ($A$=Zn, Mg, or Cd) obtained by Monte Carlo calculations of an effective spin-orbital-lattice model in the strong correlation limit. Geometrical frustration in the pyrochlore lattice structure of V cations suppresses development of spin and orbital correlations, however, we find that the model exhibits two transitions at low temperatures. First, a discontinuous transition occurs with an orbital ordering assisted by the …
Materials with strong electronic Coulomb correlations 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, for example, has been proposed for use in numerous applications, ranging from anti-laser shields to "intelligent" windows, which selectively filter radiative heat in hot weather conditions. Are present-day electronic structure techniques able to describe, or -- eve…
Infrared spectroscopy has emerged as a premier experimental technique to probe enigmatic effects arising from strong correlations in solids. Here we report on recent advances in this area focusing on common patterns in correlated electron systems including transition metal oxides, intermetallics and organic conductors. All these materials are highly conducting substances but their electrodynamic response is profoundly different from the canonical Drude behavior observed in simple metals. These unconventional properties can be attributed in several cases to the formation of spin and/or charge o…
Correlated electron materials (CEMs) host a rich variety of condensed matter phases. Vanadium dioxide (VO2) is a prototypical CEM with a temperature-dependent metal-to-insulator (MIT) transition with a concomitant crystal symmetry change. External control of MIT in VO2 - especially without inducing structural changes - has been a long-standing challenge. In this work, we design and synthesize modulation-doped VO2-based thin film heterostructures that closely emulate a textbook example of filling control in a correlated electron insulator. Using a combination of charge transport, hard x-ray pho…
We review studies of the electromagnetic response of various classes of correlated electron materials including transition metal oxides, organic and molecular conductors, intermetallic compounds with $d$- and $f$-electrons as well as magnetic semiconductors. Optical inquiry into correlations in all these diverse systems is enabled by experimental access to the fundamental characteristics of an ensemble of electrons including their self-energy and kinetic energy. Steady-state spectroscopy carried out over a broad range of frequencies from microwaves to UV light and fast optics time-resolved tec…
The magnetic susceptibility of a new one-dimensional, S=1 system, the vanadium oxide LiVGe2O6, has been measured. Contrary to previous S=1 chains, it exhibits an abrupt drop at 22 K typical of a spin-Peierls transition, and it is consistent with a gapless spectrum above this temperature. We propose that this behaviour is due to the presence of a significant biquadratic exchange interaction, a suggestion supported by quantum chemistry calculations that take into account the quasi-degeneracy of the t2g levels.
Using optical spectroscopy, we investigated the electrodynamic properties of Nb:SrTiO3/SrTiO3 superlattices. In these superlattices, a large enhancement of the Seebeck coefficient (S) has been reported with decreasing Nb:SrTiO3 layer thickness [refer to H. Ohta et al., Nature Mater. 6, 129 (2007)]. By analyzing the optical spectra, we found that the polaron plays an important role in determining the electrodynamic properties of the superlattices. With decreasing Nb:SrTiO3 layer thickness from eleven to one unit cell, we observed a threefold enhancement of the polaron effective mass and relaxat…
Vanadium sesquioxide V2O3 is considered a textbook example of Mott-Hubbard physics. In this paper we present an extended optical study of its whole temperature/doping phase diagram as obtained by doping the pure material with M=Cr or Ti atoms (V1-xMx)2O3. We reveal that its thermodynamically stable metallic and insulating phases, although macroscopically equivalent, show very different low-energy electrodynamics. The Cr and Ti doping drastically change both the antiferromagnetic gap and the paramagnetic metallic properties. A slight chromium content induces a mesoscopic electronic phase separa…
Charge doping is an effective way to induce metal-insulate transition (MIT) in correlated materials for many important utilizations, which is however practically limited by problem of low stability. In this study, we have achieved pronounced phase modulation and stabilized the metallic state of monoclinic vanadium dioxide (VO2) at room temperature, via a novel electron-proton co-doping mechanism driven by surface absorption of self-assembled L-ascorbic acid (AA) molecules. The ionized AA- species in solution donate effective electrons to the adsorbed VO2 surface, which then electrostatically a…
