Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

One-step ball-milling synthesis of cesium tungsten bronze nanoparticles and near-infrared shielding performance

Tungsten bronze (M_xWO₃) materials have been widely used as thermal insulation for architectural glass because of their higher near-infrared (NIR) light shielding capacity. To solve the problems encountered in solvothermal preparation with high costs and low yields, this study has developed a facile, eco-friendly, effective, but low-cost method, with no need for any annealing process, for promoting the large-scale fabrication of cesium tungsten bronze (Cs_xWO₃, x = 0.32) nanomaterials for potential thermal insulation windows applications. In the proposed ball-milling process, the tungstic acid material could be reduced to hydro tungsten bronze (H_xWO₃) by cellulose, while the cesium ions (Cs⁺) could be gradually incorporated into the interspace until the formation of Cs_0.32WO₃ (Cs/W atomic ratio = 0.32), with an average particle size of ∼33 nm after a 15 h ball-milling process. The reaction mechanism has been investigated in detail via particle structural analysis and optical performance characterization. The obtained Cs_0.32WO₃ nanoparticles are dispersed in a solution composed of surfactant (s) and polymer (s) which can form a thin film with a thickness of about 2 μm on a glass substrate, by a spinning coating or casting method, to exhibit high visible (Vis) light transmittance (T_566nm = 72.6%), and excellent NIR-shielding capability (T_1388nm = 5.3%), reflected by good heat-insulating performance in practice use. This work will pave a new path for large-scale production of Cs_0.32WO₃ nanomaterials with low costs and high performance, beneficial for practical applications in energy-saving glass coatings.     

Synthesis of high-performance electrochromic thin films by a low-cost method

Metal-doping is an effective method to adjust the physical and chemical properties of semiconductor metal oxides. This work adopts a simple solvothermal method to synthesize Mo-doped tungsten oxide nanoparticles. The high-performance electrochromic films can be homogenously formed on ITO glass without post-annealing. Compared with pure WO₃ films, the optimized Mo-doped WO₃ films show improved electrochromic properties with significant optical contrast (68.3% at 633 nm), the short response time (6.3 s and 3.9 s for coloring and bleaching, respectively), and excellent coloration efficiency (107.2 cm² C^?1). The improved electrochromic behavior is mainly due to the increasing diffusion rate of Li⁺ in Mo-doped WO₃ films (increased 20% than that of pure WO₃ films). The porous surface of Mo-doped WO₃ film shortens the diffusion path of Li⁺. Besides, Mo doping reduces the resistance and improves conductivity. Furthermore, 2at% Mo-doped WO₃ films indicate satisfactory energy-storage properties (the specific capacitance is 73.8 F g^?1), resulting from the enhanced electrochemical activity and fast electrical conductivity. This work presents a practical and economical way of developing high-performance active materials for bifunctional electrochromic devices.     

Glass formation area and characterization studies in the CdO–WO3–TeO2 ternary system

The glass formation area in the CdO–WO₃–TeO₂ ternary system was determined and thermal and structural features of the ternary glasses were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Raman scattering methods and the variation of the glass properties and structural transformations were discussed in terms of the glass composition comparing with the literature. For all ternary glass samples, the glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (ΔT), activation enthalpy for glass transition (ΔH^*) and fragility parameter (m) values were calculated from the DSC thermograms. Density (ρ), molar volume (V_M) and oxygen molar volume (V_O) values and the refractive indices (n) at a wavelength of 632 nm were measured. Raman spectra of the glasses were interpreted in terms of the structural transformations on the glass network resulted by the changing WO₃ + CdO/TeO₂ ratio.     

Self Assembly and Properties of C:WO3 Nano-Platelets and C:VO2/V2O5 Triangular Capsules Produced by Laser Solution Photolysis

Laser photolysis of WCl₆ in ethanol and a specific mixture of V₂O₅ and VCl₃ in ethanol lead to carbon modified vanadium and tungsten oxides with interesting properties. The presence of graphene’s aromatic rings (from the vibrational frequency of 1,600 cm⁻¹) together with C–C bonding of carbon (from the Raman shift of 1,124 cm⁻¹) present unique optical, vibrational, electronic and structural properties of the intended tungsten trioxide and vanadium dioxide materials. The morphology of these samples shows nano-platelets in WO _x samples and, in VO _x samples, encapsulated spherical quantum dots in conjunction with fullerenes of VO _x . Conductivity studies revealed that the VO₂/V₂O₅ nanostructures are more sensitive to Cl than to the presence of ethanol, whereas the C:WO₃ nano-platelets are more sensitive to ethanol than atomic C.     

Synthesis and characterization of mesostructured tungsten nitride by using tungstic acid as the precursor

Mesostructured tungsten nitride was firstly prepared from tungstic acid via the temperature programmed reaction with ammonia. The N₂ adsorption isotherm of as-synthesized tungsten nitride was of type IV with a type H-3 hysteresis loop. BJH pore size distribution was of bimodal distribution (2.5 and 3.5 nm), among which the latter was the main channel of tungsten nitride. The surface area of as-synthesized tungsten nitride was up to 89 m² g⁻¹. XRD pattern showed that the crystal phase of the product was β-W₂N. The effect of synthesis parameters on the surface area of tungsten nitride was investigated extensively. The nitridation mechanism was investigated by in-situ XRD and N₂ adsorption analysis. It was found that H₂WO₄ was initially transformed into WO₃ by eliminating the axial water molecules, and WO₃ retained the layered and porous structure of H₂WO₄. Below 773 K, WO₃ was just partially reduced to W₂₀O₅₈ and W₂₀O₄₀. Above 773 K, β-W₂N phase could be detected. It indicated that during nitridation, WO₃ was gradually reduced and then the homogeneous substitution of oxygen vacancies in the reduced oxides with nitrogen atoms occurred. Based on the experimental results, a reduction-nitridation mechanism was firstly proposed.     

Improving electrochromic behavior of spray pyrolised WO3 thin solid films by Mo doping

The effects of molybdenum [Mo] doping on the electrochromic behavior of spray pyrolised tungsten trioxide [WO₃] thin films have been studied. It has been observed that the color-bleaching kinetics, coloration efficiency, and stability of electrochromic WO₃ films are closely related to molybdenum doping concentration, apart from their microstructure and crystallinity. While a nominal 6.0 at.% molybdenum doping produces best electrochromic response in WO₃ films, the electrochemical stability is highest when the nominal concentration of molybdenum is about 2.0 at.%. The improved electrochromic behavior of the Mo doped WO₃ films has been explained from the improved H⁺ ion diffusion coefficient in the films during coloration and decoloration process.     

Solvothermally grown WO3·H2O film and annealed WO3 film for wide-spectrum tunable electrochromic applications

Tungsten trioxide (WO₃) is a classical electrochromic (EC) material with advantages of abundant reserves, high coloration efficiency and cyclic stability. However, WO₃ films are often accompanied by a narrow spectrum of modulation due to a single-color change from transparent to blue. In this work, we report a wide-spectrum tunable WO₃·H₂O nanosheets EC film solvothermally grown on fluorine-doped tin oxide (FTO) glass. Interestingly, the crystalline WO₃·H₂O nanosheets film is transformed into amorphous WO₃ after annealing at 250 °C for 1 h. The amorphous film can be transformed into crystalline WO₃ film by increasing the annealing temperature to 450 °C. After annealing at 250 °C, the WO₃ film exhibits an optical modulation of 75.8% in a broad solar spectrum range of 380–1400 nm and blocks 88.9% of solar irradiance. Fast switching responses of 4.9 s for coloration and 6.0 s for bleaching, and a coloration efficiency of 86.4 cm² C⁻¹ are also achieved. Additionally, the WO₃ film annealed at 250 °C also demonstrates an excellent cyclic stability, where 99.6% of the initial optical modulation can be retained after 1500 cycles. This simple and mild solvothermal method used in this work provides a new idea for the preparation of wide-spectrum tunable WO₃ EC films.     

Preparation and characterization of WO3/SiO2 catalysts

Two sets of WO₃/SiO₂ catalysts were prepared from (NH_{4 6}H₂W₁₂O₄₀ (aqueous method) and W(³-C₃H₅)₄ (non-aqueous method). The molecular structures and dispersions of the surface tungsten oxide species for the WO₃/SiO₂ catalysts under ambient and in situ dehydrated conditions were investigated by Raman spectroscopy. The samples prepared from (NH₄)₆H₂W₁₂O₄₀ (aqueous method) exhibit very strong Raman features due to the presence of crystalline WO₃ and the samples prepared from W(³-C₃H₅)₄ (non-aqueous method) do not possess crystalline WO₃. These results suggest that the preparation method exerts an influence on the dispersion of the surface tungsten oxide species on SiO₂. The surface tungsten oxide species under ambient conditions possess polytungstate clusters, W₁₂O ₄₂ ^12– , on the silica support. Upon dehydration at elevated temperatures, the hydrated polytungstate clusters decompose and interact with the silica support via the formation of isolated, octahedrally coordinated tungsten oxide species.     

A tungsten-trioxide/prussian blue complementary electrochromic cell with a polymer electrolyte

Optically variable windows (smart windows), which control the transmission of light into buildings and vehicles, are of interest both for the control of solar heat load and for privacy applications. Such windows are likely to utilize electrochromic technology to achieve optical control. An electrochromic device consisting of a cathodically colouring tungsten trioxide (WO₃) film, an anodically colouring Prussian blue (PB) film, and a polymer electrolyte was made. The polymer electrolyte was prepared from polyvinyl alcohol doped with H₃PO₄ and KH₂PO₄ to accommodate the conduction of both H⁺ and K⁺ ions. The electrochromic WO₃ and PB films functioned in a complementary way such that the device was coloured or bleached by the application of –0.5 V or +0.5 V (WO₃ films vs PB film), respectively. The spectral characteristics of the coloured device confirmed the complementary colouration of WO₃ and PB in the device.     

Corrosion behavior of electrodeposited Wo3 thin films

In this study, nanostructured tungsten trioxide (WO₃) thin films were deposited on Indium tin oxide (ITO)-coated glass substrate using electrochemical deposition (ECD). After deposition, the films were annealed at 450 °C for 2 h in an air atmosphere. X-ray diffraction (XRD) analysis confirmed that the prepared WO₃ thin films have crystalline phases. According to the absorption measurements, the optical bandgap of the WO₃ film was calculated as Eg 2.80 eV. Based on the scanning electron microscopy (SEM) images, the surface morphology of the thin films was influenced by deposition conditions. Raman spectroscopy analysis was also used to further examine the structure and chemical compositions of the thin films. The nature of the nanostructured WO₃ thin films was studied with Electrochemical Impedance Spectroscopy (EIS) and Tafel. Nyquist, open circuit potential and Bode analysis were used to evaluate structural changing and corrosion behavior of the prepared WO₃ thin films. With the help of these measurements and analyzes, the parameters such as solution resistance (Rs), polarization resistance (Rpo), a constant phase element (CPE) and a CPE exponent (n) were calculated as 43.43 Ω cm², 2.67 × 10⁶ Ω cm², 18.45 × 10⁻⁶ Ω⁻¹ s cm⁻², 0.958, respectively. Also, the corrosion features of the WO₃ thin films were investigated with the help of tafel measurements and the corrosion potential and current values were calculated as −0.583 V and 5.09 × 10⁻¹⁵ A, respectively. It is thought that the prepared thin film might have the potential to be used industrially with these features.     

In situ reactive synthesis and plasma-activated sintering of binderless WC ceramics

Binderless micrometre tungsten carbide ceramics (～1.1?μm) were in situ synthesised and densified by plasma-activated sintering (PAS) from mixed powders of tungsten trioxide and carbon black. The influence of sintering process and powders’ composition ratio on the phase composition, microstructure and mechanical properties of as-prepared samples was clarified in detail. The phase evolution was ascertained by X-ray diffraction to be WO₃→WO_2.72→WO₂→W₂C→WC, with the formation of CO and CO₂ gases. The sample with nearly single WC phase, dense structure and excellent mechanical properties was fabricated under the optimised process with the proper composition ratio. Owing to the micrograin size, the fracture toughness (8.88?MPa?m^1/2) was enhanced while high hardness (2159 HV10) was maintained, in the absence of any ceramic toughening phase.     

Preparation and photocurrent generation of an electrostatically self‐assembled film of hemicyanine and poly(4‐styrenesulfonic acid‐co‐maleic acid)

In this article, we report on electrostatically self‐assembled thin films prepared by the alternative immersion of quartz‐coated and indium tin oxide coated glass substrates in aqueous solutions of a copolymer of poly(4‐styrenesulfonic acid‐co‐maleic acid) (PSSMA) and a hemicyanine of (E)?1,1′‐(propane‐1,3‐diyl)bis{4‐[4‐(dimethylamino)styryl]pyridinium} bromide (H³Br₂). The films were studied by means of ultraviolet–visible absorption and X‐ray photoelectron spectroscopies, scanning electron microscopy, and photoelectrochemical measurements. When irradiated with white light, the PSSMA/H³ monolayer film gave a stable cathodic photocurrent. The effects of the applied bias voltages, layer numbers of the (PSSMA/H³)_n films (where n stands for the number of bilayer films on both sides of the substrates), light intensities, pH value, and electron acceptor on the photocurrent generation of the (PSSMA/H³)_n film were examined. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39871.     

Synthesis of highly transparent ultrananocrystalline diamond films from a low-pressure,low-temperature focused microwave plasma jet

This paper describes a new low-temperature process underlying the synthesis of highly transparent ultrananocrystalline diamond [UNCD] films by low-pressure and unheated microwave plasma jet-enhanced chemical vapor deposition with Ar-1%CH₄-10%H₂ gas chemistry. The unique low-pressure/low-temperature [LPLT] plasma jet-enhanced growth even with added H₂ and unheated substrates yields UNCD films similar to those prepared by plasma-enhanced growth without addition of H₂ and heating procedure. This is due to the focused plasma jet which effectively compensated for the sluggish kinetics associated with LPLT growth. The effects of pressure on UNCD film synthesis from the microwave plasma jet were systematically investigated. The results indicated that the substrate temperature, grain size, surface roughness, and sp ³ carbon content in the films decreased with decreasing pressure. The reason is due to the great reduction of H _α emission to lower the etching of sp ² carbon phase, resulting from the increase of mean free path with decreasing pressure. We have demonstrated that the transition from nanocrystalline (80 nm) to ultrananocrystalline (3 to 5 nm) diamond films grown via microwave Ar-1%CH₄-10%H₂ plasma jets could be controlled by changing the pressure from 100 to 30 Torr. The 250-nm-thick UNCD film was synthesized on glass substrates (glass transition temperature [T _g] 557°C) using the unique LPLT (30 Torr/460°C) microwave plasma jet, which produced UNCD films with a high sp ³ carbon content (95.65%) and offered high optical transmittance (approximately 86% at 700 nm).     

Novel approach to synthesize morphology variant tungsten oxide thin films for efficient chemical sensing

A new approach has been designed to synthesize and modify the morphology of high quality nanocrystalline tungsten oxide (WO₃) thin films using hot filament chemical vapor deposition (HFCVD) technique. The thin films were successfully synthesized having completely distinct morphologies using different processing conditions in very short duration of time 4–6 min. Two types of morphologies resembling a broccoli decorated with WO₃ nanograins (BWN) and another having faceted, pyramidal growth of WO₃ nanograins (PWN) were obtained. Both as-prepared films displayed excellent uniformity and exhibited the formation of standard monoclinic structure without undergoing any additional calcination/sintering. The morphology variant WO₃ thin films were applied as sensing electrodes to detect toxic chemical such as diethylamine (DEA) chemical. Due to smaller particle size, higher surface area and higher oxygen contents, the BWN thin film offered promising performance in DEA sensing with good sensitivity of ～3.5 μAμM^?1cm^?2 and fast response ～10 s.     

Effect of laser power density on the electrochromic properties of WO3 films obtained by pulsed laser deposition

Pulsed laser deposition (PLD) was used to prepare tungsten trioxide (WO₃) films on ITO substrates with a varying laser power density of 4.0–5.5 W/cm². XPS indicated that when the laser power density decreased, the peak positions of the W 4f and O 1s orbits shifted slightly to low energy due to the difference in oxygen vacancies. As the laser power density decreased, W⁶⁺ gradually replaced the lattice position of O^2?, increasing oxygen vacancies in the lattice. The transmittance modulated values (ΔT) were over 44% at 830 nm, indicating strong absorption by the WO₃ thin films in the near-infrared ray. The switching time of the WO₃ thin films between bleached states and coloured states decreased as the laser power density increased due to the amorphous structure, morphology, and lower oxygen deficiency at a high power density. The high ΔT and very fast switching time of t_b (1.09 s) and t_c (6.01 s) demonstrated the excellent electrochromic (EC) properties of the WO₃ films prepared by PLD.     

Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation

Mesoporous tungsten trioxide (WO₃) was prepared from tungstic acid (H₂WO₄) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO₃ sample (denoted as WO₃-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO₃-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores. N₂ physisorption studies show a Brunauer-Emmett-Teller (BET) surface area up to 57 m² g^-1 together with type IV isotherms and uniform distribution of a nanoscale pore size in the mesopore region. Scanning electron microscopy (SEM) images exhibit well-connected tiny spherical WO₃ particles with a diameter of ca. 5 to 20 nm composing the mesoporous network. The WO₃-DDA electrode generated photoanodic current density of 1.1 mA cm^-2 at 1.0 V versus Ag/AgCl under visible light irradiation, which is about three times higher than that of the untemplated WO₃. O₂ (1.49 μmol; Faraday efficiency, 65.2%) was evolved during the 1-h photoelectrolysis for the WO₃-DDA electrode under the conditions employed. The mesoporous electrode turned out to work more efficiently for visible-light-driven water oxidation relative to the untemplated WO₃ electrode.     

Graphene nanosheets-tungsten oxides composite for supercapacitor electrode

Graphene nanosheets-tungsten oxides (tungsten oxide/tungsten oxide hydrate mixture) (GNS-W) composite was successfully synthesized using a facile approach. WO₃/WO₃·H₂O mixtures were deposited on the graphene nanosheets (GNS) to form the GNS-W composite. The GNS-W composite was characterized by X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-prepared GNS-W composite was directly fabricated into a supercapacitor electrode for potential energy storage application, and electrochemically tested by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The GNS-W composite electrode exhibits a better electrochemical performance than that of the WO₃/WO₃·H₂O mixtures electrode. A high specific capacitance of about 143.6 F g⁻¹ at a current density of 0.1 A g⁻¹ for the GNS-W composite delivers significant improvement than that for the WO₃/WO₃·H₂O mixtures and GNS electrodes. The impedance studies also suggest that the GNS-W composite electrode shows the lower resistance and high conductivity due to the good interaction between the graphene nanosheets and the WO₃/WO₃·H₂O mixtures. The good electrochemical performance for the GNS-W composite may be attributed to the interaction between the WO₃/WO₃·H₂O mixtures and the edges of graphene nanosheets, which increases the ion diffusion rate as well as the conductivity.     

Precursor effects on ZrW2O8 formation kinetics

The synthesis of ZrW₂O₈ from different kinds of mixtures containing ZrO₂–WO₃, ZrO(NO₃)₂·2H₂O–WO₃, ZrCl₂O·8H₂O–WO₃, and ZrO₂–(NH₄)₁₀W₁₂O₄₁·5H₂O was investigated, and the kinetics was analyzed using JMA equation. It was found that ZrO(NO₃)₂·2H₂O, ZrCl₂O·8H₂O H₂O and (NH₄)₁₀W₁₂O₄₁·5H₂O that were used as inorganic precursors formed ZrO₂ and WO₃ after firing above 500 °C. The content of ZrW₂O₈ obtained by firing the mixtures is influenced by the kinds of precursors as well as mixing methods. The formation rate of ZrW₂O₈ depends on homogeneity related to mixing methods as well as the particle size of starting powders. Phase-pure ZrW₂O₈ is obtained from the ZrCl₂O·8H₂O–WO₃ mixtures at 1200 °C for 4 h, which is much shorter time than in the case of conventional ZrO₂–WO₃ mixtures. In the reaction kinetics of ZrO₂–WO₃ system, the Avrami exponent (n) is ∼0.5 above 1175 °C, indicating that the reaction is controlled by the diffusion-controlled reaction.     

Sunlight assisted photoelectrocatalytic degradation of benzoic acid using stratified WO3/TiO2 thin films

The stratified WO₃/TiO₂ thin films have been deposited onto glass and FTO coated glass substrates using simple chemical a spray pyrolysis method. The structural, morphological, compositional and photoelectrocatalytic properties of the stratified WO₃/TiO₂ thin films are studied. The photoelectrochemical (PEC) study shows that, both short circuit current (I_sc) and open circuit voltage (V_oc) are (I_sc =1.192 mA and V_oc =0.925 V) relatively high at 50 ml spraying quantity of TiO₂ solution on pre-deposited WO₃. XRD analysis confirms that films are polycrystalline with monoclinic and tetragonal crystal structures for WO₃ and TiO₂ respectively. Specific surface area of 72.14 m² g⁻¹ is measured by Brunauer-Emmett-Teller (BET) technique. Photoelectrocatalytic degradation of benzoic acid (BA) dye in aqueous solutions is studied. The end result shows that the degradation percentage of benzoic acid (BA) using stratified WO₃/TiO₂ photoelectrode has reached 66% under sunlight illumination after 320 min. The amount of degradation is confirmed by COD analysis.