Effect of molybdenum doping on the electrochromic properties of tungsten oxide thin films by RF magnetron sputtering

Thin films of pure and molybdenum (Mo)-doped tungsten trioxide (WO₃) were deposited on indium tin oxide (ITO)-coated glass and Corning glass substrates by RF magnetron sputtering technique. The effect of Mo doping on the structural, morphological, optical and electrochromic properties of WO₃ films was studied systematically. The energy dispersive X-ray analysis (EDAX) revealed that the films consist of molybdenum concentrations from 0 to 2 at.%. X-ray diffraction (XRD) studies indicated that with the increase of Mo concentration the structural phase transformation takes place from polycrystalline to amorphous phase. The crystallite size of the films decreased from 24 to 12 nm with increase of doping concentration of Mo in WO₃. Scanning electron microscope (SEM) analysis revealed that Mo dopant led to significant changes in the surface morphology of the films. The electrochemical and electrochromic performance of the pure and Mo-doped WO₃ were studied. The WO₃ films formed with 1.3 at.% Mo dopant concentration exhibited high optical modulation of 44.3 % and coloration efficiency of 42.5 cm²/C.     

Lithium electrochromic properties of atmospheric pressure plasma jet-synthesized tungsten/molybdenum-mixed oxide films for flexible electrochromic device

An investigation is conducted into the enhanced lithium electrochromic performance of flexible tungsten/molybdenum-mixed oxide (WMo _x O _y C _z ) films deposited onto 40 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates, using a low temperature (~23 °C) atmospheric pressure plasma-enhanced chemical vapor deposition with an atmospheric pressure plasma jet at various substrate distances. The rapid synthesis of flexible WMo _x O _y C _z films is performed by injecting the mixed hexacarbonyl and precursors W(CO)₆ and Mo(CO)₆ into an air plasma jet and exposing the substrate in the plasmas for short exposure durations (19–34 s) at various substrate distances. The flexible WMo _x O _y C _z films possess the remarkable Li⁺ ion electrochromic performance, even though after being bent 360° around a 2.5-cm diameter rod for 1,000 cycles and tested for 200 cycles of reversible Li⁺ ion intercalation and deintercalation in a 1-M LiClO₄-propylene carbonate electrolyte, respectively, by a potential sweep switching at the scan rates of ±50 mV/s from the potential of ?1 to 1 V and a potential step switching at the potentials of ?1 and 1 V. Significant optical modulation and optical density change of up to 71.2 % and 0.73 at a wavelength of 622 nm are respectively achieved.     

Crystallization and thermochromism of annealed heterostructures containing titanium and tungsten oxide films

Crystalline phases in heterostructures containing titanium and tungsten oxide films are studied after step annealing in vacuum at temperatures between 500 and 750°C. The films are deposited on a silica glass substrate by dc reactive magnetron sputtering. It is found that crystalline phases in single layers and bilayer structures form in a different way. In the latter, crystallization is influenced by the order of layer arrangement on the substrate. Thermochromism in structures annealed in vacuum is due to the oxygen-deficient phase WO_{3 ? x} belonging to the hexagonal syngony. This phase intensely grows as the temperature rises from 650 to 750°C.     

Correlation between lithium storage and diffusion properties and electrochromic characteristics of WO3 thin films

As essential electrochromic(EC) materials are related to energy savings in fenestration technology,tungsten oxide(WO3) films have been intensively studied recently.In order to achieve better understanding of the mechanism of EC properties,and thus facilitate optimization of device performance,clarification of the correlation between cation storage and transfer properties and the coloration performance is needed.In this study,transparent polycrystalline and amorphous WO3 thin films were deposited on SnO2:F-coated glass substrates by the pulsed laser deposition technique.Investigation into optical transmittance in a wavelength range of 400-800 nm measured at a current density of 130 μA·cm-2 with the applied potential ranging from 3.2 to 2.2 V indicates that polycrystalline films have a larger optical modulation of ～ 30% at 600 nm and a larger coloration switch time of 95 s in the whole wavelength range compared with amorphous films(～ 24% and 50 s).Meanwhile,under the same conditions,polycrystalline films show a larger lithium storage capacity corresponding to a Li/W ratio of 0.5,a smaller lithium diffusion coefficient(2×10-12cm2·s-1 for Li/W=0.24) compared with the amorphous ones,which have a Li/W ratio of 0.29 and a coefficient of ～2.5×10-11cm2·s-1 as Li/W=0.24.These results demonstrate that the large optical modulation relates to the large lithium storage capacity,and the fast coloration transition is associated with fast lithium diffusion.     

Fabrication and capacitive characteristics of conjugated polymer composite p-polyaniline/n-WO3 heterojunction

A nanocrystalline and porous p-polyaniline/n-WO₃ dissimilar heterojunction at ambient temperature is reported. The high-quality and well-reproducible conjugated polymer composite films have been fabricated by oxidative polymerization of anilinium ion on predeposited WO₃ thin film by chemical bath deposition followed by thermal annealing at 573 K for 1 h. Atomic force microscopy (AFM) analyses reveal a homogenous but irregular cluster of faceted spherically shaped grains with pores. The scanning electron microscopy confirms the porous network of grains, which is in good agreement with the AFM result. The optical absorption analysis of polyaniline/WO₃ hybrid films showed that direct optical transition exist in the photon energy range 3.50–4.00 eV with bandgap of 3.70 eV. The refractive index developed peak at 445 nm in the dispersion region while the high-frequency dielectric constant, ? _∞, and the carrier concentration to effective mass ratio, N/m^*, was found to be 1.58 and 1.10 × 10³⁹ cm^?3, respectively. The temperature dependence of electrical resistivity of the deposited films follows the semiconductor behavior while the C–V characteristics (Mott–Schottky plots) show that the flat band potential was ?791 and 830 meV/SCE for WO₃ and polyaniline.     

Hydrothermal synthesis of hierarchical WO3 nanostructures for dye-sensitized solar cells

Hierarchical architectures consisting of one-dimensional (1D) nanostructures are of great interest for potential use in energy and environmental applications in recent years. In this work, hierarchical tungsten oxide (WO₃) has been synthesized via a facile hydrothermal route from ammonium metatungstate hydrate and implemented as photoelectrode for dye-sensitized solar cells. The urchin-like WO₃ micro-patterns are constructed by self-organized nanoscale length 1D building blocks, which are single crystalline in nature, grown along (001) direction and confirm an orthorhombic crystal phase. The obtained powders were investigated by XRD, SEM, TEM and UV–Vis Spectroscopy. The photovoltaic performance of dye-sensitized solar cells based on WO₃ photoanodes was investigated. With increasing the calcination temperature of the prepared nanopowders, the light-electricity conversion efficiency (η) was increased. The results were attributed to increase the crystallinity of the particles and ease of electron movement. The DSSC based on hierarchical WO₃ showed a short-circuit current, an open-circuit voltage, a fill factor, and a conversion efficiency of 4.241 mA/cm², 0.656 V, 66.74, and 1.85 %, respectively.     

Efficient electrochromic device based on sol–gel prepared WO<Subscript>3</Subscript> films

Tungsten oxide (WO₃) films were prepared on indium–tin oxide (ITO) glass by sol–gel method. The influence of annealing temperature on the structural, morphological, optical, electrochemical, and electrochromic properties has been investigated. The film annealed at 250 °C with an amorphous structure exhibits a noticeable electrochromic performance, such as the highest optical modulation of 58.5 % at 550 nm, high electrochemical stability, and excellent reversibility (Q _b/Q _c?=?96.3 %). An electrochromic (EC) device based on WO₃/NiO complementary structure shows improved performance. It exhibits high optical transmittance modulation of 62 % at 550 nm, excellent cycling stability, and relatively fast electrochromic response time (10 s for coloration and 19 s for bleaching).     

Electrical conductivity and local structure of lithium iron tungsten vanadate glass

A relationship between physical properties and local structure of 20Li₂O·10Fe₂O₃·xWO₃·(70–x)V₂O₅ glass, abbreviated as xLFWV glass (x?=?0???25 in mol%), was investigated by ⁵⁷Fe-Mössbauer spectroscopy, Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol% HCl and DC two- or four-probe method. ⁵⁷Fe-Mössbauer spectra of xLFWV glass showed an increase of quadrupole splitting (Δ) from 0.67 to 0.73_±0.02 mm s^???1 and a constant isomer shift (δ) of 0.39_±0.01 mm s^???1 with an increase of ‘x’ from 0 to 25. This suggests that Fe^IIIO₄ tetrahedra gradually increase their local distortion along with a substitution of WO₃ for V₂O₅. DTA of xLFWV glass showed an increase in glass transition temperature (T _g) from 252 to 298 $_{\pm 5}^{\circ}$ C with an increase of ‘x’. Composition dependency of T _g and Δ indicates that Fe^III atoms occupy substitutional sites of WO₆ octahedra as network former (NWF), since a large slope of 680 K (mm s^???1)^???1 was obtained in T _g ? Δ plot. Comparable electrical conductivities (σ) of 2.5 × 10^???6, 1.9 × 10^???6, 8.4 × 10^???7 and 2.9 × 10^???6 S cm^???1 obtained for xLFWV glasses with ‘x’ of 0, 10, 20 and 25, respectively increased to 2.4 × 10^???2, 2.4 × 10^???3, 3.5 × 10^???4 and 8.8 × 10^???5 S cm^???1 after annealing at 400 °C for 100 min. Smaller Δ values of 0.58 and 0.67_±0.02 mm s^???1 obtained in annealed xLFWV glasses with ‘x’ of 0 and 10, respectively indicate that structural relaxation occurs in VO₄ units of vanadate glass units, as had been observed in other vanadate glasses.     

Electrochromic performance of the mixed V2O5–WO3 thin films synthesized by pulsed spray pyrolysis technique

Vanadium pentoxide (V₂O₅) mixed tungsten trioxide (WO₃) thin films have been synthesized by a novel pulsed spray pyrolysis technique (PSPT) on glass and fluorine doped tin oxide (FTO) coated glass substrates at 400 °C. Aqueous solutions of equimolar vanadium chloride and ammonium tungstate were mixed in volume proportions (5%, 10% and 15%) for the deposition of V₂O₅–WO₃ thin films. The structural, morphological, optical and electrochemical properties of V₂O₅–WO₃ thin films were investigated by FT-IR, XRD, SEM, cyclic voltammetry, chronoamperometry and chronocoulometry techniques. The results showed that the electrochemical properties of V₂O₅ were altered by mixing WO₃. All the films exhibited cathodic electrochromism in lithium containing electrolyte (0.5 M LiClO₄ + propylene carbonate (PC)). Maximum coloration efficiency (CE) of about 49 cm² C⁻¹ was observed for the V₂O₅ film mixed with 15% WO₃. The electrochemical stability of the sample was examined and it was found to be stable up to 1000 cycles.     

Spectroscopic Investigation of Tungsten Ions in Lead Scandium Phosphate Glass System

Lead scandium phosphate glasses (PbO-Sc₂O₃-P₂O₅) containing different concentrations of tungsten oxide (WO₃) ranging from 0 to 5 mol% were prepared. A number of studies, viz. differential thermal analysis (DTA), infrared spectra, optical absorption, and electron spin resonance (ESR) spectra, have been carried out. The results of DTA indicated the highest glass forming ability for the glass containing 5 mol% of WO₃. The results of spectroscopic studies have been analyzed in light of different oxidation states of tungsten ions.     

Application of Black Pearl carbon-supported WO3 nanostructures as hybrid carriers for electrocatalytic RuSex nanoparticles

RuSe_x electrocatalytic nanoparticles were deposited onto hybrid carriers composed of Black Pearl carbon-supported tungsten oxide; and the resulting system's electrochemical activity was investigated during oxygen reduction reaction. The tungsten oxide-utilizing and RuSe_x nanoparticle-containing materials were characterized using transmission electron microscopy, X-ray diffraction and electrochemical diagnostic techniques such as cyclic voltammetry and rotating ring-disk voltammetry. Application of Black Pearl carbon carriers modified with ultra-thin films of WO₃ as matrices (supports) for RuSe_x catalytic centers results during electroreduction of oxygen in 0.5 mol dm⁻³ H₂SO₄ (under rotating disk voltammetric conditions) in the potential shift of ca. 70 mV towards more positive values relative to the behavior of the analogous WO₃-free system. Also the percent formation (at ring in the rotating ring-disk voltammetry) of the undesirable hydrogen peroxide has been decreased approximately twice by utilizing WO₃-modified carbon carriers. The results are consistent with the bifunctional mechanism in which oxygen reduction is initiated at RuSe_x centers and the hydrogen peroxide intermediate is reductively decomposed at reactive WO₃-modified Black Pearl supports. The electrocatalytic activity of the system utilizing WO₃-modified Black Pearl supports has been basically unchanged upon addition of acetic acid, formic acid or methyl formate to the sulfuric acid supporting electrolyte.     

Size-controllable synthesis of functional heterostructured TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> core–shell nanoparticles

Mono and bicomponent TiO₂ and WO₃ nanoparticles were synthesized inside Vycor^® glass pores, by cycles of impregnation of the glass with the respective oxide precursor followed by its thermal decomposition. The impregnation-decomposition cycle (IDC) methodology promoted a linear mass increase of the glass matrix, and allowed tuning the nanoparticle size. X-ray diffraction and Raman spectroscopy data allowed identifying the formation of TiO₂ as anatase phase, while WO₃ is a mixture of the γ-WO₃ (monoclinic) and δ-WO₃ (triclinic) phases. High resolution transmission electron microscopy images revealed that for 3, 5, and 7 IDC, the TiO₂ nanoparticles obtained presented average diameters of 3.4, 4.3, and 5.1 nm, and the WO₃ nanoparticles have 2.9, 4.6, and 5.7 nm sizes. These TiO₂ and WO₃ monocomponent nanoparticles were submitted to IDC with the other oxide precursor, resulting in bicomponent nanoparticles. The broadening and shift of the Raman bands related to titanium and tungsten oxides suggest the formation of hetero-structure core–shell nanoparticles with tunable core sizes and shell thicknesses.     

Porous WO<Subscript>3</Subscript>/reduced graphene oxide composite film with enhanced electrochromic properties

The porous WO₃/reduced graphene oxide (rGO) composite films are prepared on indium–tin oxide (ITO) glass by sol-gel method. The mixture sol combines peroxotungstic acid solution with rGO dispersion reduced by ethylene glycol (EG). The excessive EG and other organic additives are subsequently removed by annealing, which leads to the formation of porous structure. Compared with pure WO₃ film, WO₃/rGO composite film shows improved electrochromic performance because of enhanced double insertion/extraction of ions and electrons. It realizes a large optical modulation (64.2 % at 633 nm), fast switching speed (9.5 s for coloration and 4.5 s for bleaching), good cycling stability as well as reversibility.     

Photovoltaic structures using AgSb(S x Se1−x )2 thin films as absorber

Photovoltaic structures were prepared using AgSb(S _x Se_1?x )₂ as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S _x Se_1?x )₂] were prepared by heating multilayers of sequentially deposited Sb₂S₃/Ag dipped in Na₂SeSO₃ solution, glass/Sb₂S₃/Ag/Se. For this, Sb₂S₃ thin films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃. Then, Ag thin films were thermally evaporated on glass/Sb₂S₃, followed by selenization by dipping in an acidic solution of Na₂SeSO₃. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S _x Se_1?x )₂ thin films as the primary phase and AgSb(S,Se)₂ and Sb₂S₃ as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV–vis–IR transmittance and reflection spectral analysis. AgSb(S _x Se_1?x )₂ formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S _x Se_1?x )₂/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J–V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J–V characteristics resulted in the best solar cell parameters of V _oc = 520 mV, J _sc = 9.70 mA cm^?2, FF = 0.50 and η = 2.7 %.     

Radio-frequency assisted pulsed laser deposition of nanostructured WOx films

The synthesis of tungsten oxide films with large surface area is promising for gas sensing applications. Thin WO_x films were obtained by radio-frequency assisted pulsed laser deposition (RF-PLD). A tungsten target was ablated at 700 and 900 Pa in reactive oxygen, or in a 50% mixed oxygen-helium atmosphere at the same total pressure values. Corning glass was used as substrate, at temperatures including 673, 773 and 873 K. Other deposition parameters such as laser fluence (4.5 J cm⁻²), laser wavelength (355 nm), radiofrequency power (150 W), target to substrate distance (4 cm), laser spot area (0.7 mm²), and number of laser shots (12,000) were kept fixed. The sensitivity on the deposition conditions of morphology, nanostructure, bond coordination, and roughness of the obtained films were analyzed by scanning and transmission electron microscopy, micro-Raman spectroscopy, and atomic force microscopy.     

Structural, optical and morphological studies on laser ablated nanostructured WO3 thin films

Thin films of tungsten trioxide (WO₃) are prepared by reactive pulsed laser deposition (PLD) technique on glass substrates at three different substrate temperatures (T_s). The structural, morphological and optical properties of the deposited films are systematically studied using X-ray diffraction (XRD), grazing incidence X-ray diffraction (GIXRD), micro-Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-VIS spectrophotometry techniques. X-ray diffraction analysis reveals that crystalline WO₃ films can grow effectively even at 300 K at an oxygen pressure of 0.12 mbar. All the films deposited at various T_s exhibit mixed oxide phase consisting of orthorhombic and triclinic phase of tungsten oxide with a preferred orientation along (0 0 1) lattice plane reflection. Micro-Raman results are consistent with X-ray diffraction findings. The SEM analysis shows that deposited films are porous and crystalline grains are of nano-metric dimension. The effect of T_s on mean surface roughness studied by AFM analysis reveals that mean surface roughness decreases with increase in T_s. The optical response of WO₃ layers measured using UV-VIS spectrophotometry is used to extract the optical constants such as refractive index (n), extinction coefficient (k) and optical band gap (E_g), following the method of Swanepoel.     

Influence of space charges on the dielectric behaviour of (Li2B4O7)1−x(WO3)x-glasses

The dielectric behaviour of (Li₂B₄O₇)_1−x(WO₃)_x glass samples is to a large extent governed by space charges. A detailed analysis of the effective dielectric constant ϵ_eff and the loss tangent tan δ reveals the intrinsic dielectric properties of the materials. At large WO₃-contents (0.44<x<0.55) we find a characteristic temperature in ϵ(T) which coincides with a phase transition temperature in crystalline WO₃, suggesting a reconstruction of the local environment of many tungsten atoms near to their WO₃-crystalline state.     

Effect of citric acid on photoelectrochemical properties of tungsten trioxide films prepared by the polymeric precursor method

Effect of citric acid (CA) on microstructure and photoelectrochemical properties of WO₃ films prepared by the polymeric precursor method was investigated. The obtained materials were characterized by means of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). The results showed that samples prepared with adding different amounts of citric acid had a pure phase of cubic. The addition of citric acid could significantly increase the particle size and change the surface of WO₃ films. The photoelectrochemical measurements were performed using a standard three-electrode system cell. The films prepared from mass ratios of CA/PEG (R = 0, 0.2, 0.4, 0.6 and 1) showed 1.0, 1.4, 1.7, 2.1 and 0.9 mA cm⁻² at 1.2 V under illumination with a 500 W xenon lamp (I₀ = 100 mW/cm²), respectively.     

Surface composition modification of tungsten higher oxide under He<Superscript>+</Superscript> ion bombardment

The surface reduction of higher oxide WO₃ under irradiation by He⁺ ions with the energies 1 and 3 keV in a high vacuum is investigated by X-ray photoelectron spectroscopy. It is found that lower WO₂ and intermediate WO _x (2 < x < 3) oxides form first in WO₃ surface layers under He⁺ ion bombardment, and with an increase in the irradiation dose metallic tungsten forms. It is shown that the degree of irradiated oxide surface metallization increases with an increase in the energy of the bombarding He⁺ ions. A comparison of WO₃ oxide surface composition modification under He⁺ and Ar⁺ ion irradiation is presented.     

Rapid anisotropic diffusion of lithium in electrochromic thin films based on the hexagonal tungsten bronze structure

The chemical diffusion coefficient of lithium in oxidized potassium hexatungstate and reduced hexagonal potassium tungsten bronze films was measured by the galvanostatic transient method. Two-dimensional anisotropic diffusion was found in the hexagonal hexatungstates, while no appreciable anisotropy was observed in samples with the potassium hexagonal tungsten bronze structure. The chemical diffusion coefficients along the c-axis in thin films of the tungstates K_0.33WO_3.165 and K_0.3WO_3.15 (about 6000 Å thick) are about 10^?10 cm²/s, while those along the a-axis are about 10^?7 cm²/s. This latter value is about the same to those measured in a potassium hexagonal tungsten bronze single crystal of composition K_0.28WO₃ which was grown electrochemically. It is most likely that the presence of the additional oxygen atoms in the tunnels within the hexatungstate structure is responsible for the large decrease in the rate of motion of lithium along the c-axis that leads to the anisotropy in the macroscopic diffusion coefficient in this crystal structure.