Advantages of inductively coupled plasma-assisted sputtering for preparation of stoichiometric VO2 films with metal-insulator transition

Inductively coupled plasma (ICP)-assisted sputtering with an internal coil enabled deposition of stoichiometric crystalline vanadium dioxide (VO₂) films on a sapphire (Al₂O₃) (001) substrate under widely various deposition conditions. The films showed a metal-insulator (M-I) transition around temperatures of 68 °C with several orders of change in resistivity. Particularly, low-temperature (250 °C) growth of VO₂ film with two orders transition decade was achieved in ICP-assisted sputtering, in contrast with conventional sputtering, which required 400 °C for VO₂ growth. Rutherford back scattering (RBS) measurements revealed that the VO₂ film prepared by ICP-assisted sputtering was exactly stoichiometric, containing no impurity atoms from the inserted coil material. The ICP-assisted sputtering was examined in comparison to conventional sputtering in view of plasma characteristics.     

Oxidation potential control of VO2 thin films by metal oxide co-sputtering

For metal-to-insulator transition (MIT) in vanadium oxide thin film, a thermodynamically stable vanadium dioxide (VO₂) phase is essential. In VO₂ films sputter-deposited on a quartz substrate from a V₂O₅ target, a radio-frequency (RF) magnetron sputter system at working pressure of 7 mTorr is used. Due to the lower sputtering yield of oxygen compared to vanadium leading to oxygen-ion deficiency, the reduction of V ions is resulted to compensate charge with the oxygen ions. Under lower working pressures, the deposition rate increases, but a simultaneous oxygen-ion deficiency causes the destabilization of VO₂. To prevent this, titanium oxide co-deposition is suggested to enrich the oxygen source. When TiO₂ is used, it is found that the Ti ion has a stable +4 charge state so that the use of extra oxygen in sputtering prevents the destabilization of VO₂. However, this is not the case for TiO. For the latter, Ti ions are oxidized from the +2 state to the +3 and +4 states, and V ions with less oxidation potential are reduced to +3 or so. Pure VO₂ thin film exhibits MIT at 66 °C and a large resistivity ratio of four orders of magnitude from 30 to 90 °C. The (V₂O₅ + TiO₂) system under working pressure as low as 5 mTorr yields fairly good films comparable to pure VO₂ deposited at 7 mTorr, whereas the use of TiO yields films with MIT absent or considerably weakened.     

Structural, electrical and optical properties of thermochromic VO2 thin films obtained by reactive electron beam evaporation

We present the structural and physical characterization of vanadium dioxide (VO₂) thin films prepared by reactive electron beam evaporation from a vanadium target under oxygen atmosphere. We correlate the experimental parameters (substrate temperature, oxygen flow) with the films structural properties under a radiofrequency incident power fixed to 50 W. Most of the obtained layers exhibit monocrystalline structures matching that of the monoclinic VO₂ phase. The temperature dependence of the electrical resistivity and optical transmission for the obtained films show that they present thermoelectric and thermochromic properties, with a phase transition temperature around 68 °C. The results show that for specific experimental conditions the VO₂ layers exhibit sharp changes in electrical and optical properties across the phase transition.     

Thermochromic VO2 nanorods and other vanadium oxides nanostructures

Thermochromic VO₂ nanorods were prepared via thermal conversion of the metastable VO₂–B phase synthesized by hydrothermal methods. We observe an increased thermochromic transition temperature to ∼75–80 °C by variable-temperature infrared spectroscopy. Nano- and sub-micron structures of other vanadium oxides (V₃O₇, (NH₄)_0.5V₂O₅, and V₂O₅) were obtained simply by varying the starting materials in the hydrothermal synthesis. We also obtained nanostructures of the high temperature tetragonal rutile phase of VO₂ by thermolysis of single-source vanadium (IV) precursors.     

Synthesis,characterization, and thermodynamic parameters of vanadium dioxide

A novel process was developed for synthesizing pure thermochromic vanadium dioxide (VO₂) by thermal reduction of vanadium pentoxide (V₂O₅) in ammonia gas. The process of thermal reduction of V₂O₅ was optimized by both experiments and modeling of thermodynamic parameters. The product VO₂ was characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). The experimental results indicated that pure thermochromic VO₂ crystal particles were successfully synthesized. The phase transition temperature of the VO₂ is approximately 342.6 K and the enthalpy of phase transition is 44.90 J/g.     

VO2 thin films deposited on silicon substrates from V2O5 target: Limits in optical switching properties and modeling

Thermochromic VO₂ thin films presenting a phase change at T_c = 68 °C and having variable thickness were deposited on silicon substrates (Si-001) by radio-frequency sputtering. These thin films were obtained from optimized reduction of low cost V₂O₅ targets. Depending on deposition conditions, a non-thermochromic metastable VO₂ phase might also be obtained. The thermochromic thin films were characterized by X-ray diffraction, atomic force microscopy, ellipsometry techniques, Fourier transform infrared spectrometry and optical emissivity analyses. In the wavelength range 0.3 to 25 μm, the optical transmittance of the thermochromic films exhibited a large variation between 25 and 100 °C due to the phase transition at T_c: the contrast in transmittance (difference between the transmittance values to 25 °C and 100 °C) first increased with film thickness, then reached a maximum value. A model taking into account the optical properties of both types of VO₂ film fully justified such a maximum value. The n and k optical indexes were calculated from transmittance and reflectance spectra. A significant contrast in emissivity due to the phase transition was also observed between 25 and 100 °C.     

Na0.25Cu0.75VO3: A New Perovskite-like Vanadium Bronze

A new cubic perovskite-like vanadium bronze of composition Na_0.25Cu_0.75VO₃, with a lattice parameter of 7.2517(1) Å, is obtained by reacting NaVO₃, V₂O₅, and Cu₂O at 1100°C and 8 GPa. It exhibits metallic conduction, with a sharp change in resistivity above 200°C, and, presumably, undergoes a phase transition near 280°C. The thermal properties of the new vanadium bronze are studied in air and helium at normal pressure.     

The large modification of phase transition characteristics of VO2 films on SiO2/Si substrates

The vanadium oxide (VO₂) films have been prepared on SiO₂/Si substrates by using a modified Ion Beam Enhanced Deposition (IBED) method. During the film deposition, high doses of Ar⁺ and H⁺ ions have been implanted into the deposited films from the implanted beam. The resistance change of the VO₂ films with temperature has been measured and the phase transition process has been observed by using the X-ray Diffraction technique. The phase transition of the IBED VO₂ films starts at a low temperature of 48 °C and ends at a high temperature of 78 °C. It is found that the phase transition characteristics can be adjusted by changing the annealing temperature or the time and the phase transition characteristics of the IBED VO₂ films depend on the quantity and location of argon atoms in the film matrix.     

Effect of growth temperature on the structural and transport properties of magnetite thin films prepared by pulse laser deposition on single crystal Si substrate

Magnetite (Fe₃O₄) thin films are prepared by pulsed laser deposition using an α-Fe₂O₃ target on silicon (111) substrate in the substrate temperature range of 350 °C to 550 °C. X-ray diffraction (XRD) measurement shows that the film deposited at 450 °C is a single phase Fe₃O₄ film oriented along [111] direction. However, the film grown at 350 °C reveals mixed oxide phases (FeO and Fe₃O₄), while the film deposited at 550 °C is a polycrystalline Fe₃O₄. X-ray photoelectron spectroscopy study confirms the XRD findings. Raman measurements reveal identical spectra for all the films deposited at different substrate temperatures. We observe abrupt increase in the resistivity behavior of all the films around Verwey transition temperature (T_V) (125 K-120 K) though the transition is broader in the film deposited at 350 °C. We observe that the optimized temperature for the growth of Fe₃O₄ film on Si is 450 °C. The electrical transport behavior follows Shklovskii and Efros variable range hopping type conduction mechanism below T_V for the film deposited at 450 °C possibly due to the granular growth of the film.     

Synthesis and optical properties of vanadium dioxide nanoparticles in nanoporous glasses

A method for the synthesis of vanadium dioxide (VO₂) nanoparticles in nanoporous silicate glass matrices with a pore size of 17 and 7 nm has been developed. According to this, vanadium pentoxide (V₂O₅) nanoparticles are initially grown in the pores, and then V₂O₅ is reduced to VO₂ in hydrogen. The optical transmission spectra of 1-mm-thick VO₂-modified glass samples have been measured. The temperature dependence of the transmission coefficient has been studied in the course of the semiconductor-metal phase transition in VO₂ nanoparticles.     

Soft chemistry synthesis and crystal structure of MgxCu3−xV2O6(OH)4·2H2O

Mg_xCu_3−xV₂O₆(OH)₄·2H₂O (x ∼ 1), with similar crystal structure as volborthite Cu₃V₂O₇(OH)₂·2H₂O, was successfully prepared by a soft chemistry technique. The method consists of mixing magnesium nitrate and copper nitrate with a boiling solution of vanadium oxide (obtained by reacting V₂O₅ with few mL of 30 vol.% H₂O₂ followed by addition of distilled water). When ammonium hydroxide NH₄OH 10% was added (pH 7.8), a green yellowish precipitate was obtained. Using X-ray powder diffraction data, its crystal structure has been determined by Rietveld refinement. Compared to volborthite, the vanadium coordination changes from tetrahedral VO₄ to trigonal bipyramidal VO₅, and magnesium replaces copper, preferably, in the less distorted octahedron. At 300 °C, the phase formed is similar to the high pressure (HP) monoclinic Cu₃V₂O₈ phase. However at higher temperature, 600 °C, the phase obtained is different from known Cu₃V₂O₈ phases.     

Electrical and magnetic properties of Mg0.85Co0.15Fe2O4 ceramics with V2O5 additives

In this study, magnesium-cobalt ferrite (Mg_0.85Co_0.15Fe₂O₄) powder was synthesized using a solid-state synthesis method, followed by the liquid sintering using 0.50–3.00 wt% vanadium oxide (V₂O₅) at 1050 °C for 2 h. X-ray diffraction (XRD) studies confirmed the formation of spinel ferrite. Microstructure studies revealed that by increasing the amount of V₂O₅ from 0.50 to 3.00 wt%, the average grain size was reduced from 15.9?±?5.9 to 7.0?±?2.5 μm and the samples were highly densified. V₂O₅ promoted the sintering process and reduced the dielectric constant (ε′), loss tangent (tanδ), and increased electrical resistivity. A magnesium-cobalt ferrite sample with 25.4 dielectric constant, 0.078 loss tangent, and 9.0?×?10⁵ Ω.cm resistivity at 1 MHz was achieved using 3.00 wt% V₂O₅. Increasing V₂O₅ content caused increasing coercivity (Hc) from 89 to 129 Oe. Moreover, the maximum saturation magnetization (Ms) value of 26.8 emu/g was obtained for the sample containing 1.50 wt% V₂O₅. The small dielectric loss tangent of the samples at 1 MHz suggests applications of these ceramics in microwave devices.

     

Phase evolution during synthesis of vanadium carbide (V8C7) nanopowders by thermal processing of the precursor

The phase and structure evolution during synthesis of vanadium carbide (V₈C₇) nanopowders by thermal processing of the precursor were investigated using X-ray diffraction (XRD). The morphology of the reactant was characterized by transmission electron microscopy (TEM). Simultaneous thermogravimetric and differential thermal analysis (TG-DTA) were made on the precursor. The results indicate phase evolution sequences are NH₄VO₃→V₂O₅→VO₂→V₅O₉+V₄O₇→V₂O₃→VC_1−X→V₈C₇. The single phase V₈C₇ powders can be prepared at ∼1100 °C for 1 h, and the powders show good dispersion and are mainly composed of uniformly sized spherical particles with the majority diameters of 20-50 nm.     

Study on optical and electrical switching properties and phase transition mechanism of Mo6+-doped vanadium dioxide thin films

In the present work using V₂O₅ and MoO₃ powders as precursors, a novel method, the inorganic sol-gel method, was developed to synthesize Mo⁶⁺ doped vanadium dioxide (VO₂) thin films. The structure, valence state, phase transition temperature, magnitude of resistivity change and change in optical transmittance below and above the phase transition of these films are determined by XRD, XPS, four-point probe equipment and spectrophotometer. The results showed that the main chemical composition of the films was VO₂, the structure of MoO₃ in the films didn't change, and the phase transition temperature of the VO₂ was obviously lowered with increasing MoO₃ doped concentration. The magnitude of resistivity change and change in optical transmittance below and above phase transition were also decreased, of which the magnitude of resistivity change was more distinct. However, when the MoO₃ concentration was 5 wt%, the magnitude of resistivity change of doped thin films still reached more than 2 orders, and the change in optical transmittance below and above phase transition was maintained. Analysis showed that the VO₂ doped films formed local energy level, and then reduced the forbidden band gap of VO₂ as the donor defect changing its optical and electrical properties and lowering the phase transition temperature.     

Microstructure and microhardness of vanadium oxides in the range VO<Subscript>0.57</Subscript>-VO<Subscript>1.29</Subscript>

X-ray diffraction and optical microscopy data are presented which demonstrate that substoichiometric vanadium oxide (VO_0.57-VO_0.97) consists of a cubic phase with the B1 structure (sp. gr. Fm \(\bar 3\) m) and an ordered monoclinic phase of composition V₁₄O₆ (sp. gr. C2/m). The content of the latter phase decreases with increasing oxygen content. The superstoichiometric vanadium oxide VO_1.29 is shown to contain trace amounts of V₅₂O₆₄. Vickers microhardness data for nonstoichiometric vanadium oxides in the range VO_0.57-VO_1.29 show that, with increasing oxygen content, their H _V has a tendency to decrease, from 18 to 12 GPa. Their microhardness is shown for the first time to have a maximum near the stoichiometric composition VO_1.00.     

A novel wet process for the preparation of vanadium dioxide thin film

Thin films of vanadium oxide have been prepared from an aqueous solution system of (V₂O₅–HF aq.) with the addition of aluminium metal by a novel wet-preparation process which is called liquid-phase deposition (LPD). From X-ray diffraction measurements, the as-deposited film was found to be amorphous and it was then crystallized to V₂O₅ by calcination at 400 °C under an air flow. In contrast, the monoclinic VO₂ phase was obtained when the deposited film was calcined under a nitrogen atmosphere. The deposited film showed excellent adherence to the substrate and was characterized by a homogeneous flat surface. The deposited VO₂ film exhibited a reversible semiconductor–metal phase transition around 70 °C and its transition behaviour depended on the way in which the film was prepared. This revised version was published online in November 2006 with corrections to the Cover Date.     

Controlled hydrothermal synthesis of VO2(B) nanobelts

Large-scale VO₂(B) nanobelts have been synthesized by hydrothermal strategy via one-step method using V₂O₅ as vanadium source and C₆H₅-(CH₂)_n-NH₂ with n = 2 and 4 (2-phenylethylamine and 4-phenylbutylamine) as structure-directing templates. The composition and morphology of the nanobelts were established by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The as-obtained VO₂(B) nanobelts have a length of 3-10 μm, a wideness of 100-375 nm and a thickness of 30-66 nm.     

Vanadium dioxide thin film with low phase transition temperature deposited on borosilicate glass substrate

A nanostructured vanadium dioxide (VO₂) thin film showing a low metal-insulator transition temperature of 30 °C has been fabricated through reactive ion beam sputtering followed by thermal annealing. The thin film was grown on borosilicate glass substrate at the temperature of 280 °C with a Si₃N₄ buffer layer. Both scanning electron microscopy and atomic force microscopy images have been taken to investigate the configuration of VO₂ thin film. The average height of the crystallite is 20 nm and the grain size ranges from 40 nm to 100 nm. The transmittance measured from low to high temperatures also reveals that the film possesses excellent switching property in infrared light at critical transition temperature, with switching efficiency of 52% at 2600 nm. This experiment paves the way of VO₂ thin film's application in smart windows.     

Processing,characterization, and bactericidal activity of undoped and silver-doped vanadium oxides

Vanadium oxide (V) and silver-doped vanadium oxide (Ag-V) powders were prepared via sol–gel processing. Structural evolution and bactericidal activity was examined as a function of temperature ranging from 250, 350, 450 and 550 °C. Powders were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Raman spectroscopy. Results from all techniques showed vanadium pentoxide (V₂O₅) is the predominant phase regardless of heat treatment temperature or the addition of silver (Ag). XRD analysis suggests Ag is present as AgCl in samples heat treated to 250, 350, and 450 °C and as AgV₆O₁₅ at 550 °C. Bactericidal activity was evaluated against Escherichia coli using the agar disk diffusion method considering both Ag-V and undoped, V powders. While the addition of Ag significantly increased bactericidal properties, the specific Ag valency, or crystal structure and morphology formed at higher temperatures, had little effect on functionality.     

Vanadium dioxide thin films prepared by chemical vapour deposition from vanadium(III) acetylacetonate

Vanadium dioxide thin films were prepared by an atmospheric-pressure chemical vapour deposition method. The raw material was vanadium(III) acetylacetonate. Polycrystalline thin films were obtained at a reaction temperature of 500°C. Slow post-deposition cooling of the deposits on a substrate of fused quartz or sapphire single crystal yields vanadium dioxide films which are not mixed with other phases, i.e. V₃O₇ or V₄O₉. Optical and electrical switching behaviours strongly depend on film thickness. At a film thickness of about 300 nm the transition temperature showed a minimum value of 44 °C.