Growth of b-axis oriented VO2 thin films on glass substrates using ZnO buffer layer

VO₂ thin films are grown on glass substrates by pulsed laser deposition using vanadium metal as a target. In this study, a ZnO thin film was used as a buffer layer for the growth of VO₂ thin films on glass substrates. X-ray diffraction studies showed that the VO₂ thin film had b-axis preferential orientation on a c-axis oriented ZnO buffer layer. The thickness of the ZnO buffer layer and the oxygen pressure during VO₂ deposition were optimized to grow highly b-axis oriented VO₂ thin films. The metal-insulator transition properties of the VO₂ film samples were investigated in terms of infrared reflectance and electrical resistance with varying temperatures.     

Vanadium-Al2O3 nanostructured thin films prepared by pulsed laser deposition: Optical switching

The formation and optical response of VO_x nanoparticles embedded in amorphous aluminium oxide (Al₂O₃) thin films by pulsed laser deposition is studied. The thin films have been grown by alternate laser ablation of V and Al₂O₃ targets, which has resulted in a multilayer structure with embedded nanoparticles. The V content has been varied by changing the number of pulses on the V target. It is found that VO_x nanoparticles with dimensions around 5 nm have been formed. The structural analysis shows that the vanadium nanoparticles are oxidized, although probably there is not a unique oxide phase for each sample. The films show a different optical response depending on their vanadium content. Optical switching as a function of temperature has been observed for the two films with the highest vanadium content, at transition temperatures of about −20 °C and 315 °C thus suggesting the presence of nanoparticles with compositions V₄O₇ and V₂O₅, respectively.     

Synthesis and study of electrical and magnetic properties of vanadium oxide micro and nanosized rods grown using pulsed laser deposition technique

Vanadium oxide micro and nanosized rods were grown using pulsed laser deposition technique under different oxygen pressures. X-ray diffractogram shows a predominant mixture of vanadium dioxide, VO₂ and Magneli phase, V₃O₇. The diameters of the rods were found to increase from 300 nm to 2.3 μm with increase in oxygen pressure from 0.1 mbar to 0.5 mbar as seen from high resolution scanning electron microscope images. Raman spectra of the rods show peaks at all the characteristic vibrations corresponding to that of V O_x phase. The 0.5 mbar oxygen deposited sample shows a semiconducting behavior from 300 to 77 K and is paramagnetic down to 5 K. Using versatile pulsed laser deposition we have established the tunability of the dimensions of V O_x nanorods which can find numerous potential applications in electrochemistry, catalysis, etc.     

Direct comparison of the electrical,optical, and structural phase transitions of VO2 on ZnO nanostructures

We examined the temperature-dependent electrical, optical, and structural properties of VO₂ on ZnO nanorods with different lengths in the temperature range from 30 to 100 °C. ZnO nanorods with a uniform length were grown on Al₂O₃ substrates using a metal organic chemical vapor deposition, and subsequently, VO₂ was ex-situ deposited on ZnO nanorods/Al₂O₃ templates using a sputtering deposition. The optical properties of the VO₂/ZnO nanorods were measured simultaneously with direct current (DC) resistance using the reflectivity of an infrared (IR) laser beam with a wavelength of 790 nm. The local structural properties around V atoms of VO₂/ZnO nanorods were simultaneously measured with the DC resistance using x-ray absorption fine structure at the V K edge. Direct comparison of the temperature-dependent resistance, IR reflectivity, and local structure reveals that an optical phase transition first occurs, a structural phase transition follows, and an insulator-to-metal transition finally appears during heating.     

High-temperature heat capacity of orthovanadates Ce<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>Bi<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>VO<Subscript>4</Subscript>

Orthovanadates Ce_1–xBi_xVO₄ (1 ≥ x ≥ 0) have been produced by solid-phase synthesis from initial oxides CeO₂, Bi₂O₃, and V₂O₅ upon step-by-step burning. The high-temperature heat capacity of Ce_1–xBi_xVO₄ has been measured by differential scanning calorimetry. The experimental data on C_p = f(T) were used to calculate the thermodynamic properties (the enthalpy changes, the entropy changes, and the Gibbs energy).     

Comparative study of annealing and gold dopant effect on DC sputtered vanadium oxide films for bolometer applications

Vanadium oxide (VO_x) thin film has been widely used for IR detectors and it is one of the promising materials for THz detectors due to its high temperature coefficient of resistance (TCR) values. VO_x films with proper TCR values have also high resistance and it restricts bolometer performance especially for uncooled bolometers. To overcome this problem, deposition at elevated temperatures or annealing approach has been accepted and used but gold co-deposition approach has been proposed recently. In this study, vanadium oxide films were fabricated on high resistivity silicon substrates by reactive direct current magnetron sputtering in different O₂/Ar atmosphere at room temperature. We investigated influence of oxygen partial pressure during deposition process and fabricated VO_x thin films with sufficient TCR values for bolometer applications. In order to decrease resistivity of the deposited films, post annealing and gold doping approaches were performed separately. Effect of both post annealing process and gold doping process on structural and electrical properties of VO_x thin films deposited at room temperature were investigated and detailed comparison between these methods were presented. We obtained the best possible approach to obtain optimum conditions for the highly reproducible VO_x thin films which have the best resistivity and suitable TCR value for bolometer applications.     

Improved electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> cathode material with fast ionic conductor Li<Subscript>3</Subscript>VO<Subscript>4</Subscript> coating

Layered lithium-enriched nickel manganese oxides Li_1.2Ni_0.2Mn_0.6O₂ have been synthesized and coated by fast ionic conductor Li₃VO₄ with varying amounts (1, 3, and 5 wt%) in this paper. The effect of Li₃VO₄ on the physical and electrochemical properties of Li_1.2Ni_0.2Mn_0.6O₂ has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability, and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulomb efficiency of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved after Li₃VO₄ coating. And, the 3 wt% Li₃VO₄-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best discharge capacity (246.8 mAh g^?1), capacity retention (97.3 % for 50 cycles), and rate capability (90.4 mAh g^?1 at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after Li₃VO₄ coating, which is due to high lithium ion diffusion coefficient of Li₃VO₄, is responsible for superior rate capability.     

Structural characterisation of ultra-thin VOx films on TiO2(1 1 0)

The normal incidence X-ray standing wave (NIXSW) technique has been applied to investigate the structure of ultra-thin VO_x films grown on TiO₂(1 1 0) and pre-characterised by core level photoemission. For a film composed of a sub-monolayer coverage of V deposited in ultra-high vacuum the local structure of two coexistent species, labelled ‘oxidic’ and ‘metallic’, has been investigated independently through the use of chemical-shift-NIXSW. The ‘oxidic’ state is shown to be consistent with a mixture of epitaxial or substitutional sites and chemisorption into sites coordinated to three surface O atoms. The metallic V atoms also involve a mixture of chemisorption and second-layer sites above the substrate surface consistent with the formation of small V clusters. VO_x films up to ∼6 atomic layers were also grown by post-oxidation (sequential V deposition and annealing in oxygen) and by reactive evaporation in a partial pressure of oxygen. While films of around one monolayer or less are consistent with epitaxial VO₂ growth, the film quality deteriorates rapidly with increasing thickness and is worse for reactive evaporation. A possible interpretation of the NIXSW data is increasing contributions of V₂O₃ crystallites. The inferior quality of the reactively evaporated films may be due to an insufficient supply of oxygen.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

磁控溅射法制备二氧化钒薄膜最佳参量的研究

用X射线电子能谱仪(XPS)对不同条件下用磁控溅射法制备的VO₂薄膜进行测试,得到VO₂薄膜内部组成成份的信息.研究了获得高含量VO₂薄膜的最佳制备参量.同时还观察到V₂O₃、VO₂、V₂O₅以接近含量共存的现象,这与以前研究所给出的薄膜几乎只由V₂O₃、VO₂、V₂O₅中的两种组成的结论有所不同.     

Effects of temperature and oxygen pressure on binary oxide growth using aperture-controlled combinatorial pulsed-laser deposition

In pulsed-laser deposition (PLD), there are many processing parameters that influence film properties such as substrate-target distance, background reactive gas pressure, laser energy, substrate temperature and composition in multi-component systems. By introducing a 12.7-mm diameter circular aperture in front of a 76.2-mm silicon wafer and rotating the substrate while changing conditions during the PLD process, these parameters may be studied in a combinatorial fashion, discretely as a function of processing conditions. We demonstrate the use of the aperture technique to systematically study the effects of oxygen partial pressure on the film stoichiometry and growth rate of VO_x, using Rutherford backscattering spectrometry (RBS). In another example, we discuss the effect of growth temperature on TiO₂ films characterized by X-ray diffraction and Fourier transform far-infrared (Terahertz) absorption spectroscopy. We demonstrate that we have considerable combinatorial control of other processing variables besides composition in our combi-PLD system. These may be used to systematically study film growth and properties.     

Oxygen pressure induced structure,morphology and phase-transition for VO2/c-sapphire films by PLD

To investigate the effects of oxygen pressure on the structural and phase transition properties for VO₂/c-sapphire, highly orientated VO₂ thin films were grown on (0001) sapphire substrates by pulsed laser deposition (PLD) with different oxygen pressures. The crystal structure, morphology and component of the films were systematically investigated. The temperature-dependent resistance (R-T) measurement was conducted, which showed the distinct phase transition characteristic for the prepared films. The results indicate that the oxygen pressure plays an important role for the VO₂ film preparation. The film grown at 1.7 Pa has lower phase transition temperature, higher film strain, and smaller grain size than that at 5.4 Pa, while no obvious crystal phase transition is observed. The experiment suggests that even a small change in oxygen pressure can influence the structure, morphology and phase-transition behavior of VO₂ films obviously, and its potential causes are mainly attributed to the reduction of the kinetic energy to the substrate for target atoms caused by the oxygen pressure, the resulting grain aggregation and interfacial stress.     

Spectral Studies of Vanadyl-Doped Cadmium–Strontium Borosilicate Glass System

Glasses with composition CdO–(20-x) SrO–B₂O₃–SiO₂–x V₂O₅ (CdSBSi) (x = 0.5, 1, 1.5, 2, 2.5 mol%) were prepared by melt quenching technique. The amorphous nature of prepared glasses is confirmed by X-ray diffraction. Optical absorption spectra, electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) measurements were also carried out for the prepared glass samples. The optical band gap energy (E _opt) and Urbach energy (?E) were calculated from their ultraviolet edges. The theoretical values of optical basicity (Λ _th) of glasses have been evaluated. The optical absorption spectrum exhibits two band characteristic of VO²⁺ ions in tetragonally distorted octahedral site symmetry. The two bands have been assigned to the transitions ²B₂ → ²B₁ and ²B₂ → ²E in the decreasing order of energy. The spin–Hamiltonian parameters (g and A), bonding parameters (β*² and $ \varepsilon_{\pi }^{*2} $ ), Fermi contact interaction parameter (K) have been evaluated from the EPR spectra. The VO²⁺ site symmetry is ascribed to a tetragonally (C_4v) distorted octahedron. FTIR spectra of these glasses were analyzed in order to identify the contribution of each component to the local structure. The physical properties of these glasses were also evaluated.     

Absorption spectra of vanadyl ion doped in MgNH4PO4·6H2O (struvite) crystal

Results of Electron Paramagnetic Resonance (EPR) and optical absorption studies of VO²⁺ ion doped in struvite at room liquid nitrogen temperatures are reported. Three preferential V=O bond directions in the crystal have been identified. The optical and EPR data have shown the formation of NH₄(PO₄VO(H₂O)₅ complex in the crystal as a result of VO²⁺ doping. Correlating the optical and EPR data the molecular orbital coefficients are also obtained and discussed.     

Melt synthesis and structural properties of opal-V2O5 and opal-VO2 nanocomposites

A method has been proposed for filling bulk and film opals with V₂O₅ and V₂O₅: W melts under the action of capillary forces. The VO₂ and VO₂: W (1.8 mol %) compounds have been synthesized from the V₂O₅ and V₂O₅: W precursors in opal pores. The phase composition and morphology of the nanocomposites prepared have been investigated. It has been revealed that, in the opal-V₂O₅ composite, the filler compound has a texture formed by the directional crystallization of the melt in pores of the opal film. The tunable photonic crystal heterostructure opal/opal-VO₂ has been synthesized using liquid chemical etching.     

Experimental study of the electronic and lattice contributions to the VO2 transition

The contributions of electronic and crystallographic components to the semiconductor → metal transition in VO₂ have been estimated from resistivity, E.P.R., and calorimetric measurements of the electronic and thermodynamic properties of Ga_xV_?xO₂, where 0 < x < 0.0130. E.P.R. and resistivity measurements indicate a decrease in the metallic character of the high-temperature R phase with increasing x, and calorimetric measurements of the energetics of the transition show a decrease in the enthalpy and entropy of the transition with increasing levels of doping. This concomitant decrease in enthalpy and metallic character with increasing x implies a strong contribution of the electronic entropy to the transition. An extrapolation of the combined electronic and calorimetric data for Ga_xV_?xO₂ to pure VO₂ suggest that the electronic entropy comprises about 60% of the total entropy of transition in VO₂.     

The influence of PEO on the synthesis and electrochemical properties of VO2 and V3O7·nH2O nanobelts as a cathode for lithium battery

In this paper, we report the hydrothermal synthesis of VO₂, poly(ethylene oxide) (PEO)/VO₂,V₃O₇·nH₂O and PEO/V₃O₇·nH₂O nanobelts by using 1,2-propylene carbonate (1,2-PC (C₄H₆O₃)) and poly(ethylene glycol) (PEG) as templates, respectively. Structure and morphology of the samples were investigated by XRD, FTIR, SEM, and TEM. The vanadium oxide (VO₂) nanobeltcomposite show the initial specific capacity 152?mA?h?g^?1, whereas PEO/VO₂ shows 182?mA?h?g^?1. The pure V₃O₇·nH₂O nanobelts shows the initial specific capacity 192?mA?h?g^?1, while PEO/V₃O₇·nH₂O nanobelts show 297?mA?h?g^?1. It was found that PEO/VO₂ and PEO/V₃O₇·nH₂O nanocomposites show better cyclic performance and high discharge stability compared to pure vanadium oxide nanomaterials. The role of the polymeric PEO component of the hybrid material seems to be the stabilization and improvement of the specific capacity due to probable homogeneous distribution between the nanobelts. The TEM images indicate that PEO works as a surfactant to decrease the dimensions of nanobelts.     

Formation mechanisms and crystallographic characteristics of metastable VO2(A) nanofiber hydrothermally synthesised in V2O5–H2C2O4–H2O system

There are many similarities between VO₂(B) and VO₂(A) from crystallographic view. However, missing of VO₂(A) during the preparation of VO₂ polymorph confused many researchers. Here, the preparation of VO₂(A) was studied systemically via a hydrothermal method in V₂O₅–H₂C₂O₄–H₂O system. As a metastable phase, it can be transferred from VO₂(B) by assembling process. Usually, poly-crystal VO₂(A) nano-fibers are formed by this process. On contrast, owing to the small energy gap between meta-stable VO₂(A) and stable VO₂(R), single crystal VO₂(A) with regular shape can also be obtained by exfoliating some parts of VO₂(R) during non-equilibrium cooling process. VO₂(A) has higher phase transition temperature than stable VO₂(R). The hysteresis in this phase transition can be observed by DSC measurement and the phase transition temperature of VO₂(A) can be tuned down by tungsten doping.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w