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 in the magnetic susceptibility. The V spins that do not form dimers order in a canted antiferromagnetic state. The magnetic susceptibility of LuV4O8 shows a sharp peak at ~ 50 K. The magnetic entropies calculated from heat capacity versus temperature measurements indicate bulk magnetic transitions below 90 K for both YV4O8 and LuV4O8.
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.
We have synthesized a new spinel oxide LiRh2O4 with a mixed-valent configuration of Rh3+ and Rh4+. At room temperature it is a paramagnetic metal, but on cooling, a metal-insulator transition occurs and a valence bond solid state is formed below 170 K. We argue that the formation of valence bond solid is promoted by a band Jahn-Teller transition at 230 K and the resultant confinement of t2g holes within the xy band. The band Jahn-Teller instability is also responsible for the observed enhanced thermoelectric power in the orbital disordered phase above 230 K.
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.
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.
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…
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 …
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…
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…
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 …
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 study the importance of inter-site coherences and quantum interference effects in the x-ray absorption spectroscopy (XAS) of mixed-valent systems. We demonstrate its importance, first for a simple diatomic mixed-valent molecule to elucidate the physics involved, and finally for mixed-valent Ti oxides, using a model calculation including full spin and orbital multiplicities. Our calculations demonstrate the inefficacy of conventional approaches of describing the XAS from mixed-valent systems as incoherent combinations of XAS from the pure-valent end members, and that multiplets forbidden in …
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…
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 …
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…
We have investigated the electronic structure of the high oxidation state material YCrO$_4$ within the framework of the Zaanen-Sawatzky-Allen phase diagram. While Cr$^{4+}$-based compounds like SrCrO$_3$/CaCrO$_3$ and CrO$_2$ can be classified as small-gap or metallic negative-charge-transfer systems, we find using photoelectron spectroscopy that YCrO$_4$ is a robust insulator despite the fact that its Cr ions have an even higher formal valence state of 5+. We reveal using band structure calculations that the tetrahedral coordination of the Cr$^{5+}$ ions in YCrO$_4$ plays a decisive role, nam…
We study magnetic excitations in vanadium spinel oxides AV$_2$O$_4$ (A=Zn, Mg, Cd) using two models: first one is a superexchange model for vanadium S=1 spins, second one includes in addition spin-orbit coupling, and crystal anisotropy. We show that the experimentally observed magnetic ordering can be obtained in both models, however the orbital ordering is different with and without spin-orbit coupling and crystal anisotropy. We demonstrate that this difference strongly affects the spin-wave excitation spectrum above the magnetically ordered state, and argue that the neutron measurement of su…
Motivated by recent theoretical and experimental controversy, we present a theoretical study to clarify the orbital symmetry of the ground state of vanadium spinel oxides AV$_2$O$_4$ (A=Zn, Mg, Cd). The study is based on an effective Hamiltonian with spin-orbital superexchange interaction and a local spin-orbit coupling term. We construct a classical phase-diagram and prove the complex orbital nature of the ground state. Remarkably, with our new analysis we predict correctly also the coherent tetragonal flattening of oxygen octahedra. Finally, through analytical considerations as well as numer…
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…
We present the results of our theoretical study on the effects of geometrical frustration and the interplay between spin and orbital degrees of freedom in vanadium spinel oxides $A$V$_2$O$_4$ ($A$ = Zn, Mg or Cd). Introducing an effective spin-orbital-lattice coupled model in the strong correlation limit and performing Monte Carlo simulation for the model, we propose a reduced spin Hamiltonian in the orbital ordered phase to capture the stabilization mechanism of the antiferromagnetic order. Orbital order drastically reduces spin frustration by introducing spatial anisotropy in the spin exchan…
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…
LiV2O4, a frustrated mixed valent metal (d^1 <-> d^2), is argued to undergo two spin-screening processes. The first quenches the effective spin to produce the spin 1/2 behavior seen below room temperature[1], while the second produces the heavy fermi liquid character seen at low temperatures[2]. We present here a preliminary discussion of a t-J model with strong Hund's coupling of the strongly correlated d-electrons. Valence fluctuations of the Hubbard operators (S = {1/2} <-> 1) combined with the frustration of the underlying corner-shared tetrahedral vanadium lattice are the essential compon…
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）
Crystal and electronic structure, lattice dynamics and thermodynamic stability of little known mixed valent diamagnetic AgIAgIIIF4 beta form of AgF2 is thoroughly examined for the first time and compared with well known antiferromagnetic AgIIF2 alpha form within the framework of Density Functional Theory based methods, phonon direct method and quasiharmonic approximation. Computed equations of state, bulk moduli, electronic densities of states, electronic and phonon band structures including analysis of optically active modes and p T phase diagram of the alpha/beta system are presented. This s…
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…
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 …
CaBaFe4O7 is a mixed-valent transition metal oxide having both Fe2+ and Fe3+ ions in tetrahedral coordination. Here we characterize its magnetic properties by magnetization measurements and investigate its local electronic structure using soft x-ray absorption spectroscopy at the Fe L2,3 edges, in combination with multiplet cluster and spin-resolved band structure calculations. We found that the Fe2+ ion in the unusual tetrahedral coordination is Jahn-Teller active with the high-spin e^2 (up) t2^3 (up) e^1 (down) configuration having a x^2-y^2-like electron for the minority spin. We deduce tha…
Since electronic and magnetic properties of many transition-metal oxides can be efficiently controlled by external factors such as the temperature, pressure, electric or magnetic field, they are regarded as promising materials for various applications. From the viewpoint of electronic structure, these phenomena are frequently related to the behavior of a small group of states close to the Fermi level. The basic idea of this project is to construct a low-energy model for the states near the Fermi level on the basis of first-principles density functional theory, and to study this model by modern…
Charge and spin order is intimately related to superconductivity in copper oxide superconductors. To elucidate the competing orders in various nickel oxide compounds are crucial given the fact that superconductivity has been discovered in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$ films. Herein, we report structural, electronic transport, magnetic, and thermodynamic characterizations on single crystals of La$_3$Ni$_2$O$_7$ and La$_3$Ni$_2$O$_6$. La$_3$Ni$_2$O$_7$ is metallic with mixed Ni$^{2+}$ and Ni$^{3+}$ valent states. Resistivity measurements yield two transition-like kinks at $\sim$110 and 153 K, resp…
Phase competition in correlated oxides offers tantalizing opportunities as many intriguing physical phenomena occur near the phase transitions. Owing to a sharp metal-insulator transition (MIT) near room temperature, correlated vanadium dioxide (VO2) exhibits a strong competition between insulating and metallic phases that is important for practical applications. However, the phase boundary undergoes strong modification when strain is involved, yielding complex phase transitions. Here, we report the emergence of the nanoscale M2 phase domains in VO2 epitaxial films under anisotropic strain rel…
The transition--metal oxide CaCu$_3$Ru$_4$O$_{12}$ with perovskite--type structure shows characteristic properties of an intermediate--valence system. The temperature--dependent susceptibility exhibits a broad maximum around $150 - 160$ K. At this temperature, neutron powder diffraction reveals a small but significant volume change whereby the crystal structure is preserved. Moreover, the temperature--dependent resistivity changes its slope. NMR Knight shift measurements of Ru reveal a cross--over from high temperature paramagnetic behavior of localized moments to itinerant band states at low …
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…
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 …
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.
We present magnetic susceptibility measurements on MgV$_2$O$_5$, a compound in which the vanadium oxide planes have the same topology as in CaV$_2$O$_5$. The most striking property is that there is an energy gap of about 15 K, much smaller than in CaV$_2$O$_5$, where the values reported are of the order of 500 K. We show that this may be understood naturally in terms of the phase diagram of the frustrated, coupled ladder system. This analysis leads to the prediction that MgV$_2$O$_5$ should have incommensurate dynamic spin fluctuations.
The complex oxide Pb(0.55)Cd(0.45)V(2)O(5) was synthesized and investigated by means of X-ray powder diffraction, electron diffraction, magnetic susceptibility measurements and band structure calculations. Its structure is similar to that of MV(2)O(5) compounds (M = Na, Ca) giving rise to a spin system of coupled S=1/2 two-leg ladders. Magnetic susceptibility measurements reveal a spin gap-like behavior with Δ~ 270 K and a spin singlet ground state. Band structure calculations suggest Pb(0.55)Cd(0.45)V(2)O(5) to be a system of weakly coupled dimers in perfect agreement with the experimental da…
The pressure dependence of phase transitions in the quasi one-dimensional vanadium oxide $β$-Na$_{1/3}$V$_2$O$_5$ has been studied by magnetic susceptibility and electrical resistivity measurements. The pressure dependence of the various transition temperatures is quite differently. The transition at T=240 K, previously reported and attributed to ordering on Na sites, and a second transition at $T \approx 222$ K, reported here for the first time and attributed to a further increase of order on Na sites, are almost independent of pressure. On the other hand, the metal-insulator (MI) transition …
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…
We report structural, magnetization, electrical resistivity and nuclear- and electron spin resonance data of the complex transition metal oxide In_2VO_5 in which structurally well-defined V-O chains are realized. An itinerant character of the vanadium d-electrons and ferromagnetic correlations, revealed at high temperatures, are contrasted with the insulating behavior and predominantly antiferromagnetic exchange between the localized V^{4+} S = 1/2-magnetic moments which develop below a certain characteristic temperature T* ~ 120 K. Eventually the compound exhibits short-range magnetic order a…
CaBaCo4O7 represents a new class of ferrimagnets whose structure is built up of CoO4 tetrahedra only, similarly to other members LnBaCo4O7 of the 114 series, forming an alternate stacking of kagome and triangular layers. Neutron powder diffraction reveals, that this compound exhibits the largest distortion within the 114 series, characterized by a strong buckling of the kagome layers. Differently from all other members it shows charge ordering, with Co2+ sitting on two sites (Co2, Co3) and mixed valent cobalt Co3+/Co2+L sitting on two other sites (Co1, Co4). The unique ferrimagnetic structure …
