Effect of doping with H and W on the properties of V2O5 and VO2 derived from V2O5 gel has been studied. It is shown that the treatment of V2O5 in low-temperature RF hydrogen plasma for 1 to 10 min. leads to either hydration of vanadium pentoxide or its reduction (depending on the treatment conditions) to lower vanadium oxides. For some samples, which are subject to plasma treatment in the discharge active zone, a non-ordinary temperature dependence of resistance, with a maxi-mum at T ~ 100 K, is observed. For W-doped VO2 films, it is shown that substitution of V4+ with W6+ results in a decrease of the temperature of metal-insulator transition. Also, it has been shown that the doping of the initial films with ~3 at.% of W reduces the statistical scatter in the thresh-old parameters of the switching devices with S-shaped I-V characteristics on the basis of V2O5 gel films.
This paper discusses questions of synthesizing and pressing vanadium oxides to create film-forming materials that can be used in producing optical coatings. Based on the film-forming materials thus created, technological processes have been developed for fabricating coatings from vanadium dioxide by two methods of producing thin films: vacuum evaporation and magnetron sputtering. Questions of using films made from vanadium oxide in optical instrumentation are considered.
We measured the optical properties of mixed valent vanadium oxide nanoscrolls and their metal exchanged derivatives in order to investigate the charge dynamics in these compounds. In contrast to the prediction of a metallic state for the metal exchanged derivatives within a rigid band model, we find that the injected charges in Mn$^{2+}$ exchanged vanadium oxide nanoscrolls are pinned. A low-energy electronic excitation associated with the pinned carriers appears in the far infrared and persists at low temperature, suggesting that the nanoscrolls are weak metals in their bulk form, dominated b…
Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metal- insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth c…
The work function is the parameter of greatest interest in many technological applications involving charge exchange mechanisms at the interface. The possibility to produce samples with a controlled work function is then particularly interesting, albeit challenging. We synthetized nanostructured vanadium oxides films by a room temperature Supersonic Cluster Beam Deposition method, obtaining samples with tunable stoichiometry and work function (3.7-7 eV). We present an investigation of the electronic structure of several vanadium oxides films as a function of the oxygen content via in-situ Auge…
Electrical and optical properties of amorphous vanadium oxide thin films obtained by electrochemical anodic oxidation are studied. It is shown that under cathodic polarization the hydrogen insertion into vanadium oxide from an electrolyte occurs. Metal-insulator transition in amorphous HxVO2 is found to be preserved up to high concentration (x ~ 1.5) of hydrogen. Memory switching with the N-type negative differential resistance, associated with the H+ ionic transfer, is observed in "V/hydrated amorphous vanadium oxide/Au" sandwich structures.
Vanadium oxide films and fibers have been fabricated by the acetylacetonate sol-gel method followed by annealing in wet nitrogen. The samples are characterized by X-ray diffraction and electrical conductivity measurements. The effects of a sol aging, the precursor decomposition and the gas atmosphere composition on the annealing process, structure and properties of the films are discussed. The two-stage temperature regime of annealing of amorphous films in wet nitrogen for formation of the well crystallized VO2 phase is chosen: 1) 25-550 C and 2) 550-600 C. The obtained films demonstrate the m…
Electrostatic control of the metal-insulator transition (MIT) in an oxide semiconductor could potentially impact the emerging field of oxide electronics. Vanadium dioxide is of particular interest due to the fact that the MIT happens in the vicinity of room temperature and it is considered to exhibit the Mott transition. We present a detailed account of our experimental investigation into three-terminal field effect transistor-like devices using thin film VO2 as the channel layer. The gate is separated from the channel through an insulating gate oxide layer, enabling true probing of the field …
Vanadium oxides are strongly correlated materials which display metal-insulator transitions as well as various structural and magnetic properties that depend heavily on oxygen stoichiometry. Therefore, it is crucial to precisely control oxygen stoichiometry in these materials, especially in thin films. This work demonstrates a high-vacuum gas evolution technique which allows for the modification of oxygen concentration in VOX thin films by carefully tuning thermodynamic conditions. We were able to control the evolution between VO2, V3O5, and V2O3 phases on sapphire substrates, overcoming the n…
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…
Electrical switching and rectifying properties of the metal-VO2-Si structures, on both p-type and n-type silicon, with vanadium dioxide films obtained by an acetylacetonate sol-gel method, are studied. The switching effect is shown to be due to the semiconductor-to-metal phase transition (SMPT) in vanadium dioxide. The shift of the switching threshold voltage, accompanied by the memory effect, in forward bias of the p-Si-VO2 anisotype heterojunction is observed. To explain this effect, a model is proposed which suggests the existence of an additional series resistance associated with a channel…
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…
An electrical study of thin $VO_{2}$ films in the vicinity of the structural phase transition at $68^{0}C$ shows (a) that the electrical resistance $R$ follows $log (R)$ $\propto$ $-T$ over the $T$-range, $20 < T < 80 ^{0}C$ covering both sides of the structural transition, and (b) a history dependent hysteresis loop in $R$ upon thermal cycling. These features are attributed here to transport through a granular network.
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 …
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 …
Monoclinic scheelite bismuth vanadate (BiVO4) is a promising photoanode for water splitting yet the PEC performance is limited due to its relatively higher (2.4 eV) band gap. Here, we successfully decreased its the band gap to 1.72 eV by controlled antimony alloying. Low bandgap antimony alloyed bismuth vanadium oxide (Sb:BiVO4) thin film was prepared by RF sputtering of high purity homemade target, fabricated by solid-state reaction using a mixture of Sb2O3, Bi2O3, and V2O5 powders with desired stoichiometric ratios. Several growth parameters, powder crystallography, post-deposition effects, …
Metal-oxide-metal devices based on amorphous VOx are shown to exhibit one of two distinct negative differential resistance (NDR) characteristics depending on the maximum current employed for electroforming. For low compliance currents they exhibit a smooth S-type characteristic and have a temperature-dependent device resistance characterised by an activation energy of 0.25 eV, consistent with conduction in polycrystalline VO2, while for high-compliance currents they exhibit an abrupt snap-back characteristic and a resistance characterised by an activation energy of 0.025 eV, consistent with co…
We observe remarkably strong room temperature ferromagnetism (~1.5 Bohr Magneton/Mn) in optically transparent Mn(II)-doped indium tin oxide (ITO) films. The nanocrystalline films with average grain size 10-22 nm and thickness 150-350 nm are prepared by sol-gel coating technique on sodalime silica glass substrate. The ferromagnetic property is, of course, weak for films deposited on pure silica glass substrate. The structural parameters of the films appear to be governing the magnetic property strongly which vary appreciably depending on the substrate. The observation of room temperature ferrom…
We propose that the topological semimetal features can co-exist with ferromagnetic ground state in vanadium-phosphorous-oxide $β$-V$_2$OPO$_4$ compound from first-principles calculations. In this magnetic system with inversion symmetry, the direction of magnetization is able to manipulate the symmetric protected band structures from a node-line type to a Weyl one in the presence of spin-orbital-coupling. The node-line semimetal phase is protected by the mirror symmetry with the reflection-invariant plane perpendicular to magnetic order. Within mirror symmetry breaking due to the magnetization …
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 report the development of indium oxide (In2O3) transistors via a single step laser-induced photochemical conversion process of a sol-gel metal oxide precursor. Through careful optimization of the laser annealing conditions we demonstrated successful conversion of the precursor to In2O3 and its subsequent implementation in n-channel transistors with electron mobility up to 13 cm2/Vs. Importantly, the process does not require thermal annealing making it compatible with temperature sensitive materials such as plastic. On the other hand, the spatial conversion/densification of the sol-gel layer…
Sparse matter is characterized by regions with low electron density and its understanding calls for methods to accurately calculate both the van der Waals (vdW) interactions and other bonding. Here we present a first-principles density functional theory (DFT) study of a layered oxide (V2O5) bulk structure which shows charge voids in between the layers and we highlight the role of the vdW forces in building up material cohesion. The result of previous first-principles studies involving semilocal approximations to the exchange-correlation functional in DFT gave results in good agreement with exp…
Chemical transformation of MgH2/V2O5 composite to Mg-V-O rock salt and its influence on the electrochemical Li conversion and hydrogen storage characteristics of MgH2
University of Aveiro（阿威罗大学）；LASI - Intelligent Systems Associate Laboratory（智能系统联合实验室）；International Iberian Nanotechnology Laboratory (INL)（伊比利亚纳米技术国际实验室）
VO2 is a much-discussed material for oxide electronics and neuromorphic computing applications. Here, heteroepitaxy of vanadium dioxide (VO2) was realized on top of oxide nanosheets that cover either the amorphous silicon dioxide surfaces of Si substrates or X-ray transparent silicon nitride membranes. The out-of-plane orientation of the VO2 thin films was controlled at will between (011)M1/(110)R and (-402)M1/(002)R by coating the bulk substrates with Ti0.87O2 and NbWO6 nanosheets, respectively, prior to VO2 growth. Temperature dependent X-ray diffraction and automated crystal orientation map…
Vanadium dioxide (VO2) as a phase-change material controls the transferred heat during phase transition process between metal and insulator states. At temperature above 68C, the rutile structure VO2 keeps the heat out and increases the IR radiation reflectivity, while at the lower temperature the monoclinic structure VO2 acts as the transparent material and increase the transmission radiation. In this paper, we first present the metal-insulator phase transition (MIT) of the VO2 in high and low temperatures. Then we simulate the meta-surface VO2 of metamaterial reflector by Ansys HFSS to show t…
A novel sol-gel route to c-axis orientated undoped and Co, Fe, Mn and V doped ZnO films is reported. Sols were prepared from a hydrated zinc acetate precursor and dimethyl formamide (DMF) solvent. Films were spin-coated on to hydrophilic sapphire substrates then dried, annealed and post-annealed, producing almost purely uniaxial ZnO crystallites and a high degree of long-range structural order. Specific orientation of hexagonal crystallites is demonstrated both perpendicular and parallel to the substrate surface. Cobalt doping resulted in the formation of columnar ZnO nanocrystals. Vanadium do…
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…
Visualizing Crystallization Dynamics and Transformation Pathways of Disordered Rocksalt Oxides During Thermally Activated Sol-Gel Synthesis
Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）；Brazilian Synchrotron Light Laboratory (LNLS), Brazilian Center for Research in Energy and Materials (CNPEM)（巴西同步辐射光源实验室（LNLS），巴西能源与材料研究中心（CNPEM））；University of California, Berkeley（加州大学伯克利分校）
Vanadium oxides have been highly attractive for over half a century since the discovery of the metal insulator transition near room temperatures. Here NaxVO2 is studied through a systematic comparison with other layered sodium metal oxides with early 3d transition metals, first disclosing a unified evolution pattern of Na density waves through in situ XRD analysis. Combining ab-initio simulations and theoretical modelings, a sodium-modulated Peierls-like transition mechanism is then proposed for the bonding formation of metal ion dimers. More importantly, the unique trimer structure in NaxVO2 …
In this article, we address the issue of vanadium dissolution pertinent in the layered Fe5V15O39(OH)9.9H2O using the solubility limit approach. This layered oxide is prepared via a low-cost solution phase synthesis route and crystallizes in the Kazakhstanite phase (Space Group: C2/m), confirmed using selected area electron diffraction and x-ray diffraction.The layered oxide exhibits the 2 electron redox reaction of vanadium (V5+ to V3+) along with the 1 electron redox reaction of iron within the voltage window of 1.5-3.8V. This results in a high specific capacity of ~350mAhg-1 which can be ext…
Hydrogen sensors have been prepared using nickel oxide (NiO) and lithium-doped nickel oxide (NiO:Li) thin films, deposited on glass substrates by the sol-gel spin coating technique. The surface morphology, structure, optical and electrical properties of the obtained films were studied. Hydrogen sensing results are presented for three operating temperatures (140, 160, and 180 °C) and for hydrogen concentrations ranging from 1000 to 15000 ppm in synthetic air. The NiO and NiO:Li (2% and 8% doping concentrations) sensors show maximum responses for the operating temperature of 180 °C. When tested …
We demonstrate spatial modification of the optical properties of thin-film metal oxides, zinc oxide and vanadium dioxide as representatives, using a commercial focused ion beam (FIB) system. Using a Ga+ FIB and thermal annealing, we demonstrated variable doping of a band semiconductor, zinc oxide (ZnO), achieving carrier concentrations from 10^18 cm-3 to 10^20 cm-3. Using the same FIB without subsequent thermal annealing, we defect-engineered a correlated semiconductor, vanadium dioxide (VO2), locally modifying its insulator-to-metal transition (IMT) temperature by range of ~25 degrees C. Such…
NaBH4 is a very cheap and hydrogen rich material and a potential hydrogen store. However, high temperature of its thermal decomposition (above 530°C) renders it inapplicable in practical use. Here, we have studied the effect of addition of diverse V containing catalysts on thermal hydrogen desorption. It turns out that mechanochemical doping of NaBH4 with vanadium metal, its oxides or nanoparticles lowers the temperature of pyrolysis significantly. Notably, NaBH4 milled for 3 hrs with 25 wt.% of V2O5 or VO2 releases ca. 70 % of stored hydrogen in the temperature range from ca. 370°C to 450°C. …
We study the transport properties in SrVO3/LaVO3 (SVO/LVO) superlattices deposited on SrTiO3 (STO) substrates. We show that the electronic conduction occurs in the metallic LVO layers with a galvanomagnetism typical of a 2D Fermi surface. In addition, a Kondo-like component appears in both the thermal variation of resistivity and the magnetoresistance. Surprisingly, in this system where the STO interface does not contribute to the measured conduction, the Kondo correction is strongly anisotropic. We show that the growth temperature allows a direct control of this contribution. Finally, the key…
Novel 2D Altermagnetic Vanadium Oxide with a Buckled Lieb Structure
UNAM - National Nanotechnology Research Center and Institute of Materials Science and Nanotechnology, Bilkent University（比尔肯特大学纳米技术与材料科学研究所）；Linköping University（林雪平大学）；Uppsala University（乌普萨拉大学）；University of Iowa（爱荷华大学）
基于密度泛函理论第一性原理计算，发现单层V₂O晶体在翘曲Lieb晶格中是一种二维交变磁性材料，具有负泊松比、面外易磁化轴、1.2 eV动量依赖自旋劈裂以及大贝里曲率和约40 (ℏ/e) S cm⁻¹的自旋霍尔电导率。
Vanadium dioxide is a complex oxide material, which shows large resistivity and optical reflectance change while transitioning from the insulator to metal phase at ~68 °C. In this work, we use a modified atmospheric thermal oxidation method to oxidize RF-sputtered Vanadium films. Structural, surface-morphology and phase-transition properties of the oxidized films as a function of oxidation duration are presented. Phase-pure VO2 films are obtained by oxidizing ~130 nm Vanadium films in short oxidation duration of ~30 seconds. Compared to previous reports on VO2 synthesis using atmospheric oxida…
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 …
High-entropy perovskite thin films, as the prototypical representative of the high-entropy oxides with novel electrical and magnetic features, have recently attracted great attention. Here, we reported the electronic structure and charge transport properties of sol-gel-derived high-entropy Ba(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3 thin films annealed at various temperatures. By means of X-ray photoelectron spectroscopy and absorption spectrum, it is found that the conduction-band-minimum shifts downward and the valence-band-maximum shifts upward with the increase of annealing temperature, leading to the…
Iron oxide nanoparticles were prepared by sol -gel process. Insitu polymerization of pyrrole monomer in the presence of oxygen in iron oxide ethanol suspension resulted in a iron oxide - polypyrrole nanocomposite. The structure and magnetic properties were investigated for varying pyrrole concentrations. The presence of the gamma - iron oxide phase and polypyrrole were confirmed by XRD and FTIR respectively. Agglomeration was found to be comparatively much reduced for the coated samples, as shown by TEM. AC susceptibility measurements confirmed the superparamagnetic behaviour. Numerical simula…
Spin coating technique was employed to fabricate CuO films at different spin speeds for different time duration, and they were annealed at different temperatures for different time durations in air. These thin films were characterized using UV Visible spectrometer and solar cell simulator. As the spinning rate increases, the corresponding band gap energy of the thin film increases. However, the annealing temperature does not affect the optical band gap. Moreover, the optical band gap does not depend on the annealing time and spin time. It was observed that the optical band gap decreases with t…
Gamma - Iron Oxide prepared by sol -gel process was used to produce nanocomposites with polyaniline of varying aniline concentrations. TEM shows the presence of chain like structure for lower polyaniline concentration. The room temperature hysteresis curves show finite coercivity of 160 Oe for all the composites while the saturation magnetization was found to decrease with increasing polymer content. ZFC - FC magnetisation measurements indicate high blocking temperatures. It is believed that this indicates a strongly interacting system, which is also shown by our TEM results. Monte Carlo simul…
Vanadium pentoxide (V2O5), the most stable member of vanadium oxide family, exhibits interesting semiconductor to metal transition in the temperature range of 530-560 K. The metallic behavior originates because of the reduction of V2O5 through oxygen vacancies. In the present report, V2O5 nanorods in the orthorhombic phase with crystal orientation of (001) are grown using vapor transport process. Among three nonequivalent oxygen atoms in a VO5 pyramidal formula unit in V2O5 structure, the role of terminal vanadyl oxygen (OI) in the formation of metallic phase above the transition temperature i…
Topotactic phase transformation in correlated vanadium dioxide through oxygen vacancy ordering
Key Laboratory of Magnetic Molecules and Magnetic Information Materials of Ministry of Education & School of Chemistry and Materials Science, Shanxi Normal University（山西师范大学化学与材料科学学院、教育部磁性分子与磁性信息材料重点实验室）；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）
A comparative study of the physical properties of undoped Zinc Oxide (ZnO) and Al doped Zinc Oxide (AZO) thin films were performed as a function of annealing temperature. The structural properties were analyzed using X-ray diffraction and the recorded patterns indicated that the crystallinity of the films always enhanced with increasing annealing temperature while it degrades with Al doping. The topographical modification of the films due to heat treatment was examined by atomic force microscopy which revealed that annealing roughened the surface of all the films; however the AZO films always …
This work reports optical functionality contained in, as well as and produced by, thin film coatings. A sol-gel process, formulated with precursor active ingredients of erbium oxide and tetraethylorthosilicate (TEOS), was used for spin-coating thin (~130 nm) erbium-doped (~6 at. %) silica films on single-crystal silicon. Annealed films produce infrared emission in the 1.5-micron band from erbium ions in the film, as well as greatly enhancing (~100X) band-gap emission from the underlying silicon. The distinctly different mechanisms for the two modes of optical activities are interpreted in term…
Atomic models of quasi-one-dimensional 1D vanadium oxide nanostructures - nanotubes of various morphology (cylinder or scroll-like) formed by rolling (010) single layers of V2O5 are constructed and their electronic properties are studied using the tight-binding band theory. Compared to the cylindrical zigzag (n,0) and armchair (n,n)-like nanotubes, which are uniformly semi-conducting with the bang gap of about 2.5-2.7 eV, the band gap of the scroll-like tubes trends significantly to vanish (up to about 0.1 eV) depending on the atomic configurations of the tubes and inter-wall distances.
The possibility to segregate cobalt and iron in a single perovskite, at a nanoscale in the form of layers has been investigated, using sol gel technic synthesis. Quite remarkably, it is shown that such a nanoscale ordering, which can only be detected by a combined HAADF-STEM and EELS study, has a significant impact upon the magnetic properties of this SmFe0.5Co0.5O3 oxide. This suggests that careful nanoscale characterization of oxides will be necessary in the future before proceeding to a viable interpretation of their physical properties, at least in the field of magnetism.
