Structural,morphological, and optical properties of W-doped VO2 thin films prepared by sol-gel spin coating method

Thermochromic VO₂ thin films were deposited on soda-lime glass via sol-gel method. Doping was done through adding tungstic acid solution to the vanadium solution precursor. Grazing incidence x-ray diffractometer (GIXRD) results showed that VO₂ and V₆O₁₃ phases were formed together in the heat-treated sample. According to the GIXRD result of the W-doped sample, only VO₂ remained. Field-emission scanning electron microscopy (FESEM) micrographs showed that the VO₂ grain size decreased from about 70 to about 25 nm for undoped film and 2 wt% W-doped films, respectively. Atomic force microscopy (AFM) results showed that the root mean square roughness for the film with 180 nm thickness was about 18 nm, and 2 wt% W-doped film had a smoother surface. Diffuse reflectance spectroscopy (DRS) results showed that the band gap energy for undoped, 1 wt% W- doped, and 2 wt% W-doped VO₂ thin films was 1.7, 1.3, and 0 eV, respectively. Four-point probe resistivity measurements showed a significant decrement, from approximately 1 MΩ at 15°C to <100 Ω at 80°C. Regarding Vis-NIR spectroscopy results, maximum optical transmission for undoped and W-doped films was approximately 75% and 35%, respectively.     

Low metal–insulator transition temperature of Ni-doped vanadium oxide films

Elemental doping is the main means to regulate the phase transition of vanadium oxide (VO₂); however, the effects of low valence elemental (<4+) doping on the phase transition of VO₂ are still controversial. In the present work, Ni-doped VO₂ films were prepared on quartz glass by direct current reactive magnetron sputtering and subsequent annealing. With the increase of the Ni doping content, the phase transition temperature of heating (T_H) of the VO₂ films decreased from 73.4 °C to 52.4 °C. The temperature required for the occurrence of phase transition (T_b) was lower than T_MIT. Different from the undoped VO₂ film, the Ni-doped VO₂ films had a T_b of around 30 °C. XRD and Raman results revealed that some rutile VO₂ microcrystals appeared in the vanadium oxide films because of the lattice distortion by incorporated Ni. Hence, rutile VO₂ micro-crystallinities significantly facilitated the phase transition of monoclinic VO₂ to rutile one.     

An in-situ Reduction/Oxidation XAS Study on the EL10V8 VO x /TiO2(Anatase) Powder Catalyst

The structural changes of the supported vanadium oxide in the V₂O₅/TiO₂(anatase) EUROCAT EL10V8 powder catalyst during reduction and oxidation at 420 and 490 °C were studied with in-situ X-ray absorption spectroscopy (XAS). The Vanadium K-edge XAS results are compared with pure bulk V₂O₅. For the reduction–oxidation cycle at 420 °C, similar structural changes as for bulk V₂O₅ were observed for the supported vanadium oxide: a reduction to the VO₂ structure and re-oxidation back to V₂O₅. After reduction at 490 °C however, a different structure was obtained: very regular “VO₆” octahedra with a V^2.8+ valence. This may point to a structural support effect.     

Near room temperature tunability of thermochromic VO2 thin films prepared via thermal oxidation method,influence of CO2:N2 gas flux ratios

In this study, we have investigated the thermochromic characterizations of VO₂ thin films synthesized by the thermal oxidation method. The oxidation process of a DC sputtered metallic vanadium layer on glass substrates, at 450 °C for 1 h, was carried out in the presence of CO₂:N₂ gases with different flux ratios of 30:70, 40:60, 50:50, 60:40, and 70:30, respectively. Using CO₂, as the oxidizing gas, provides an easy control route for obtaining the VO₂ phase among various vanadium oxide phases. The layers were characterized by FESEM, XRD & Raman spectra, sheet resistance vs. temperature (20–120 °C), and UV–Vis–NIR spectra at 25 and 90 °C. The XRD and Raman spectra confirmed all prepared layers have a VO₂ polycrystalline structure in monoclinic phase. We found among the studied samples CN30-70 and CN50-50 having desirable optical characteristics of peak visible transmittance of about 55%, with low transition temperatures (T_cr) of ∼42 and 31 °C, and also relatively high amounts of ΔT_1700nm, ΔT_sol and T_lum,av are good candidates for thermochromic smart windows, both from optical properties and economical fabrication method points of view.     

Facile hydrothermal synthesis of vanadium oxides nanobelts by ethanol reduction of peroxovanadium complexes

V₃O₇·H₂O and VO₂(B) nanobelts were successfully synthesized by a one-pot hydrothermal approach using peroxovanadium (V) complexes, ethanol and water as the starting materials. Some parameters, such as the ratio of ethanol/water, the reaction temperature and the reaction time, were briefly discussed to reveal the formation of vanadium oxides nanobelts. It was found that the ethanol was oxidized to aldehyde confirmed by the silver mirror reaction and gas chromatography. V₃O₇·H₂O and VO₂(B) nanobelts could be selectively synthesized by controlling the quantity of ethanol. The possible formation mechanism of the synthesis of vanadium oxides nanobelts was proposed. The electrochemical properties of V₃O₇·H₂O and VO₂(B) nanobelts were studied, and they exhibited a high initial discharge capacity of 350 mAh/g and 190 mAh/g, respectively. VO₂(M) nanobelts were prepared by the irreversible transformation of VO₂(B) nanobelts at 700 °C for 2 h under the inert atmosphere. The phase transition properties of VO₂(M) nanobelts were investigated by DSC and variable-temperature IR, which revealed that the as-obtained VO₂(M) nanobelts could be applied to the optical switching devices.     

Phase Equilibria of the SiO2–V2O5 system

The SiO₂–V₂O₅ system is one of the key systems for vanadium extraction and applications of vanadium oxides in the ceramic industries. However, only limited data in this system and contradictive results were reported from preceding studies. In the present study, high-temperature phase equilibrium experiments were conducted to construct the phase diagram of SiO₂–V₂O₅ system at temperature range of 660–1100 °C. Electron probe X-ray micro-analyzer (EPMA) was used to analyze the microstructure and composition of the phases presented in quenched samples. The liquidus temperatures in both SiO₂ and V₂O₅ primary phase field were determined. The eutectic temperature is confirmed to be within 670–680 °C and the eutectic composition comprises 1.9 wt% SiO₂. SiO₂ phase contains up to 1.4 wt% V₂O₅ in the temperature range investigated.     

The novel preparation method of thermochromic VO2 films with a low phase transition temperature by thermal oxidation of V–Mo cosputtered alloy films

Vanadium dioxide (VO₂) has been studied extensively for its unique insulator-metal transition characteristics and potential applications in thermochromic smart windows, switching devices, and infrared detectors. However, how to balance the metal-insulator transition temperature, luminous transmittance (T_lum) and solar modulation ability (ΔT_sol) of VO₂ thin films remains a challenge. In this work, high-quality thermochromic VO₂ thin films were prepared by a two-step method of magnetron sputtering and thermal oxidation annealing. Metallic and alloyed V–Mo layers were first deposited by direct-current reactive magnetron sputtering, and then a thermal oxidation annealing process was used to obtain pure and Mo-doped VO₂ thin films. The Mo content in the films was regulated by changing the sputtering power of the vanadium target, and the effect of Mo doping on the crystallinity, microstructure, phase transition temperature and optical properties of VO₂ thin films was studied. The shift of the VO₂(011) peak to a lower 2θ angle in the XRD patterns showed that Mo was successfully diffused into vanadium dioxide films. The phase transition temperatures were decreased continuously from 57.4 to 32.7 °C by decreasing the sputtering power of vanadium. The thinner Mo-doped VO₂ thin films showed higher luminous transmittance and lower transition temperature. Our results were shown to be an innovative preparation method to fabricate thermochromic VO₂ films with a low phase transition temperature, balanced luminous transmittance and solar modulation ability by thermal oxidation of V–Mo cosputtered alloy films.     

Design of an X‐Ray Powder Diffraction Probe for Multi‐Channel Application: Proof of Principle

The design of an X‐ray powder diffraction probe and its integration with a multi‐channel reactor system for potential application in high‐throughput experimentation is presented. The working principle of the apparatus is exemplified by measurements of corundum and of the phase change observed when oxidizing vanadium(III) oxide (V₂O₃) in air during heating up to 450 °C. The phase transformations of the parent material were monitored by phase identification of the crystalline intermediate vanadium(IV) oxide (VO₂) and the final product vanadium(V) oxide (V₂O₅).     

Oxidative dehydrogenation of ethane to ethylene over V2O5/Nb2O5 catalysts

V₂O₅/Nb₂O₅ catalysts with various V₂O₅ contents were prepared by impregnation and characterized by various techniques in detail. Oxidative dehydrogenation of ethane was carried out in a fixed bed quartz reactor at 500–600 °C. XPS analysis indicated a clear enrichment of vanadium on the near-surface-region and UV–vis diffuse reflectance spectroscopy revealed the nature of VO_x structures formed. 10 wt.% V₂O₅/Nb₂O₅ catalyst has displayed the best performance (X = 28%, S = 38% at 600 °C) due to enrichment of vanadium in the near-surface-region and formation of optimum amount of monomeric/oligomeric VO_x species.     

The influence of precursors and additives on the hydrothermal synthesis of VO2: A route for tuning the metal–insulator transition temperature

Thermochromic materials have attracted the attention of scientific and technological researchers due to their ability to change color depending on the temperature. Vanadium dioxide (VO₂) is capable of considerable polymorphs and has aroused interest mainly because its metal–insulator transition (MIT) presents a thermochromic characteristic at a relatively low temperature. This work aimed to obtain vanadium oxide nanostructures using hydrothermal synthesis to tune the MIT temperature. Ammonium metavanadate or vanadium pentoxide was used as a precursor of vanadium, oxalic acid as a reducing agent, and sodium molybdate as an additive. The starting materials were homogenized and inserted in a hydrothermal reactor at 180 °C. After 24 h of synthesis, part of the resulting product was heat-treated at 400 °C for 3 h. The powders obtained were characterized by their structure, morphology, and thermal properties. The results showed a fiber/rod-shaped VO₂ (M) morphology. Distinct strategies were used to obtain the crystalline phase of interest (VO₂(M)), and the presence of a reversible change occurring at ~68 °C was evaluated according to the parameters from the VO₂ phase transition. The addition of sodium molybdate favored a 22% reduction in the MIT temperature when the precursor used was vanadium pentoxide, indicating possible doping in the structure increased the effects of smaller crystallite size and the presence of crystalline phases. This work opens new perspectives for applications of the vanadium oxides obtained, such as in thermal sensors and/or intelligent materials.     

Piezo-ferroelectric response of bismuth ferrite based thin films and their related photo/piezocatalytic performance

Bismuth ferrite based thin films were grown by RF magnetron sputtering under different experimental conditions. The effects of substrate temperature, Ar:O₂ mass flow ratio and gas mixture pressure on the films’ microstructure, phase evolution, optic, ferroelectric and magnetic properties were systematically investigated. The structural analysis results revealed an amorphous phase for the films deposited at a substrate temperature below 500 °C, while for the thin films deposited at 700 °C, a ε-Fe₂O₃ secondary phase was detected. The diffraction lines of the samples deposited at 600 °C were associated with Bi₂Fe₄O₉ and Bi₂₅FeO₄₀ phases. The increase in the mixture gas pressure up to 1 Pa showed an improved crystallinity of the deposited films, while, at higher working gas pressures, the films were found to be amorphous. The use of low O₂ to Ar mass flow ratio during the deposition led to a phase transformation process. EDX and RBS measurements exposed a uniform distribution of the main elements, revealing some stoichiometry changes induced by the pressure variation. The optical band gap values were influenced by the substrate temperature and pressure of the Ar:O₂ gas. The magnetic properties were correlated with the structural features, the highest magnetic response being observed for the sample deposited at 600 °C, 1 Pa and 3:1 Ar:O₂ gas pressure. According to the PFM results, the film deposited at 700 °C, Ar:O₂ ratio 3:1 and total gas pressure 1 Pa clearly outperformed the others due to their excellent ferroelectric properties and outstanding piezo-response. The sample deposited at 700 °C showed both visible light-driven degradation and piezodegradation activities. The piezocatalytic and photocatalytic activities were ascribed to the high piezoresponse and to a more efficient separation of electrons and holes induced by a built-in electric field that is caused by the larger remnant polarization of Bi₂Fe₄O₉ and Bi₂Fe₄O₉/ε-Fe₂O₃ hetero-junction.     

Reversible,repeatable and low phase transition behaviour of spin coated nanostructured vanadium oxide thin films with superior mechanical properties

Smooth, uniform and crystalline vanadium oxide thin films were deposited on quartz by spin coating technique with four different rpm i.e., 1000, 2000, 3000 and 4000 and subsequently post annealed at 350, 450 and 550?°C in vacuum. Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques were utilized for microstructural characterizations and phase analysis, respectively, for vanadium oxide powder and deposited film. Nanorods were observed to be grown after vacuum annealing. X-ray photoelectron spectroscopy (XPS) technique was utilized to study the elemental oxidation state of deposited vanadium oxide films. Thermo-optical and electrical properties such as solar transmittance (τ_s), reflectance (ρ_s), absorptance (α_s), infrared (IR) emittance (ε_ir) and sheet resistance (R_s) of different thin films were evaluated. Based on the optical characteristics the optimized condition of the film processing was identified to be spin coated at 3000?rpm. Subsequently, the nanoindentation technique was utilized to measure hardness and Young's modulus of the optimized film. The measured nanomechanical properties were found to be superior to those reported for sputtered vanadium oxide films. Finally, temperature dependent phase transition characteristics of optimized vanadium oxide films were studied by differential scanning calorimetry (DSC) technique. Reversible and repeatable phase transition was found to occur in the range of 44–48?°C which was significantly lower than the phase transition temperature (i.e., 68?°C) of bulk VO₂.     

Revealing the high sensitivity in the metal toinsulator transition properties of the pulsed laser deposited VO2 thin films

Vanadium dioxide (VO₂) is known as a typical 3d-orbital transition metal oxide exhibiting the metal-to-insulator-transition (MIT) property near room temperature. However, their electronic applications have been challenged by the quality and uniformity of VO₂ thin films. In this work, we demonstrate the high sensitivity in the valence charge of vanadium and the MIT properties of the VO₂ thin films to the deposition temperature. This observation indicates the necessity to eliminate the inhomogeneity in the temperature distribution of substrate during the vacuum-deposition process of VO₂. In addition, a high thermoelectric power factor (PF, e.g., exceeding 1 μWcm⁻¹K⁻²) was achieved in the metallic phase of the VO₂ thin films and this value is comparable to typical organic or oxide thermoelectric materials. We believe this high PF enriches the potential functionality in thermoelectric energy conversions beyond the existing electronic applications of the current vacuum-grown VO₂ thin films.     

Dielectric and ferroelectric properties of multilayer BaTiO3/NiFe2O4 thin films prepared by solution deposition technique

In this work different lead-free multilayered structures, composed of perovskite BaTiO₃ and spinel NiFe₂O₄ thin layers, were obtained by solution deposition method. Structural characterization of the sintered thin films confirmed the well-defined layered structure with overall thickness from 160 to 600 nm, crystalline nature of perovskite BaTiO₃ and spinel NiFe₂O₄ phases without secondary phases (after sintering below 900 °C) and grains on nanometer scale. Dielectric properties of the multiferroic multilayer BaTiO₃/NiFe₂O₄ thin films were analyzed in temperature and frequency range from 30 °C to 200 °C and 100 Hz to 1 MHz, respectively. In comparison to the pure BaTiO₃ films, the introduction of ferrite layer reduces dielectric response and increases low frequency permittivity dispersion of the multilayer thin films. The multilayer samples have shown relatively low dielectric loss with stronger contribution of conductivity at higher temperatures, and characteristic broad peak representing “relaxation” of the interface charge accumulation.     

Chemical reactions in the course of curing of organosilicate composites and aging of organosilicate coatings

The chemical processes occurring in organosilicate composites at temperatures ranging from 20 to 1100°C are considered. The polycondensation reaction of silanol groups of modified polydimethylphenylsiloxane (PDMPS) at a temperature of 250–300°C is complicated by the interaction with vanadium oxide V₂O₅. The BaO₂ peroxide has an effect on the thermooxidative destruction of the composite. It is revealed that new glass-ceramic phases, as well as vanadium-containing and barium-containing phases, are formed in the “PDMPS-muscovite-chrysotile asbestos-aluminoborosilicate glass-ZrO₂-V₂O₅-BaO₂” system at temperatures in the range 660–1000°C.     

Influence of deposition temperature on luminescent efficiency of Y2O3:Eu3+ thin films deposited on quartz fabric by EBE

Y₂O₃:Eu³⁺ thin films were grown on quartz fabric substrate by electron beam evaporation (EBE) at different deposition temperatures. It was found that an increase of deposition temperature from room temperature (R.T.) to 250 °C results in improved morphologies of the films, such as reduced defects, spherical particle shape and dense surface topography. A change in the predominant orientation of Y₂O₃:Eu³⁺ thin films was detected from (222) at low temperatures of R.T.–150 °C to (400) at higher temperatures of 200–250 °C. The luminescent intensity of the films was gradually improved with an increase in deposition temperature and the optimal brightness was observed when the films were grown at 250 °C and improved by 32.67% in comparison with that of the films grown at R.T. The results reveal that the improved morphologies and effective crystallization can contribute to the enhanced luminescent properties of the Y₂O₃:Eu³⁺ thin films.     

Characterization of single crystalline a-TiO2 films on MgAl2O4(100) substrates by MOCVD

Anatase phase TiO₂ (a-TiO₂) films have been deposited on MgAl₂O₄(100) substrates at the substrate temperatures of 500–650 °C by the metal organic chemical vapor deposition (MOCVD) method using tetrakis-dimethylamino titanium (TDMAT) as the organometallic (OM) source. The structural analyses indicated that the TiO₂ film prepared at 600 °C had the best single crystalline quality with no twins. The out-of-plane and in-plane epitaxial relationships of the film were a-TiO₂(001)||MgAl₂O₄(100) and TiO₂[100]||MgAl₂O₄[100], respectively. A uniform and compact surface with stoichiometric composition was also obtained for the 600 °C-deposited sample. The average transmittance of all the TiO₂ films in the visible range exceeded 91% and the optical band gap of the films varied from 3.31 to 3.41 eV.     

Phase transformation and electrochemical charge storage properties of vanadium oxide/carbon composite electrodes synthesized via integration with dopamine

Chemically preintercalated dopamine (DOPA) molecules were used as both a reducing agent and a carbon precursor to prepare δ-V₂O₅·nH₂O/C, H₂V₃O₈/C, VO₂(B)/C, and V₂O₃/C nanocomposites via hydrothermal treatment or hydrothermal treatment followed by annealing under Ar flow. We found that the phase composition and morphology of the produced composites are influenced by the DOPA:V₂O₅ ratio used to synthesize (DOPA)_xV₂O₅ precursors through DOPA diffusion into the interlayer region of the δ-V₂O₅·nH₂O framework. The increase of DOPA concentration in the reaction mixture led to a more pronounced reduction of vanadium and a higher fraction of carbon in the composites’ structure, as evidenced by X-ray photoelectron spectroscopy and Raman spectroscopy measurements. The electrochemical charge storage properties of the synthesized nanocomposites were evaluated in Li-ion cells with nonaqueous electrolytes. δ-V₂O₅·nH₂O/C, H₂V₃O₈/C, VO₂(B)/C, and V₂O₃/C electrodes delivered high initial capacities of 214, 252, 279, and 637 mAh g^–1, respectively. The insights provided by this investigation open up the possibility of creating new nanocomposite oxide/carbon electrodes for a variety of applications, such as energy storage, sensing, and electrochromic devices.     

Critical evaluation and thermodynamic optimization of the VO–VO2.5 system

A critical evaluation, and thermodynamic optimization of phase equilibrium and thermodynamic properties of the VO–VO_2.5 system are presented. Optimized model parameters for all the oxide phases were obtained so as to reproduce all available and reliable experimental data within experimental error limits. Liquid oxide phase was modeled using the modified quasichemical model in the pair approximation with components representing various valences of vanadium (VO, VO_1.5, VO₂, and VO_2.5) in the liquid oxide. Solid VO and V₂O₃ phases were modeled using simple random mixing models, while all other solid phases were assumed to be stoichiometric compounds. Type of defects in the V₂O₃ solid solution was shown to be extended cluster type defect, based on the available experimental data. Using the presently optimized model parameters, most experimental data has been well reproduced, therefore, the present work can be further extended for the development of thermodynamic database for V oxide containing system.     

VO2(A) nanorods: One-pot synthesis,formation mechanism and thermal transformation to VO2(M)

The monoclinic VO₂(M) has promising applications in intelligent devices but its preparation still requires improvement to permit cost-effective mass production. In this work, we report a 2-stage approach for producing VO₂(M) nanorods by (1) hydrothermal reduction of vanadium pentoxide by sodium bisulfate at 220?°C to form VO₂(A), and (2) subsequent thermal activated phase transformation of VO₂(A) to VO₂(M) at 350–450?°C in vacuum. The obtained VO₂(M) nanorods showed a reversible phase transition temperature at about 62.5?°C and a narrow thermal hysteresis width of 10?°C. The mechanism of the hydrothermal reduction was studied by combined ex situ microscopic and diffraction characterization of cooled samples as well as in situ PXRD experiments, in which the hydrothermal synthesis was monitored in real time by time-resolved diffraction datasets. It was found that the hydrothermal synthesis of VO₂(A) is a 4-step process: (1) reduction of V₂O₅ to form VO₂(B) nanoparticles, (2) oriented attachment of VO₂(B) nanoparticles along the [110] direction, (3) formation of VO₂(B) nanorods as a results of oriented attachments, and (4) hydrothermal transformation of the metastable intermediate VO₂(B) nanorods to VO₂(A) nanorods. This clear understanding of the mechanism will help the further optimization of synthesis temperature and time for preparing VO₂(A). This method provides a low temperature thermal treatment alternative and hence helps the reduction of cost for the production of VO₂(M), bring the mass application of VO₂(M) one step closer.