Electrochromic properties of nanocomposite WO3 films

A new nanocomposite WO₃ (NWO) film-based electrochromic layer was fabricated by a spray and electroplating technique in sequence. An indium–tin oxide (ITO) nanoparticle layer was employed as a permanent template to generate the particular nanostructure. The structure and morphology of the NWO film were characterized. The optical and electrochromic properties of the NWO films under lithium intercalation are described and compared to the regular WO₃ film. The NWO films showed an improved cycling life and an improved contrast with compatible bleach-coloration transition time, owing to the larger reactive surface area. The nanocomposite WO₃ film-based electrochromic device (NWO-ECD) was also successfully fabricated. Most importantly, the NWO film can be prepared on a large scale directly onto a transparent conductive substrate, which demonstrates its potential for many electrochromic applications, especially, smart windows, sunroof and displays.     

Palladium nanoparticle deposition onto the WO3 surface through hydrogen reduction of PdCl2: Characterization and gasochromic properties

Nowadays, gasochromic Pd/WO₃ coatings as optically switchable materials have become more applicable for hydrogen sensors and smart windows. In this study, WO₃ films were prepared by Pulsed Laser Deposition (PLD) and spin-coating sol-gel techniques. For deposition of Pd, first a layer of PdCl₂ was obtained via a simple drop-drying process by dropping PdCl₂ solution onto WO₃ substrates and drying them at room temperature. Then Pd nanoparticles were synthesized via hydrogen gas exposure that causes reduction of the PdCl₂ layer. According to Scanning Electron Microscope (SEM) observations before hydrogen reduction, many individual nanoparticles or fractal-like constructions of palladium were formed in the PdCl₂ layer in which the fractal branches were distorted after hydrogen treatment. Surface chemistry of the observed Pd nanoparticles was studied using X-ray Photoelectron Spectroscopy (XPS) at different stages of the reduction process. The results showed that after hydrogen treatment, the chlorine atoms were desorbed from the PdCl₂ layer and a metallic Pd layer remained on the surface of WO₃. Gasochromic properties in the presence of H₂ or O₂ gases for different PdCl₂ amounts revealed that the rate and saturated level of coloring depends on the PdCl₂ amounts as well as on the preparation method of the WO₃ substrates due to different porosities.     

Modeling the optical properties of WO3 and WO3-SiO2 thin films

The optical properties and surface morphology of sol-gel spin coated WO₃ and WO₃-SiO₂ composite films annealed at 250 and are investigated. For the purpose of extracting the optical parameters of the films, a novel form for the dielectric function is introduced, consisting of two Tauc-Lorentz oscillators and an Urbach tail component, which is suited for amorphous multi-transition materials with substantial subgap absorption. The evolution of the refractive indices, transmittances, and band gaps with doping is marked by sizable shifts at 2.0-2.5% SiO₂ doping for the films, and 4.0-4.5% doping for the films. In addition, pronounced changes in the surface roughness of the films occur at these doping values.     

Wet chemical preparation and characterization of electrochromic WO3

Thin films of electrochromic WO₃ were prepared via wet chemical deposition. Precursor solutions containing WOCl₄ in isopropanol were used and films were deposited by spin coating. Various techniques were used for characterization of the films such as Rutherford backscattering spectroscopy (RBS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), UV-VIS spectroscopy and electrochemical methods. Composition, structural characteristics and electrochromic properties were studied as function of the curing temperature, in the range 80–500°C.     

Application of WO3 thin films for enhancement of photolysis in AgCl

A double-layer AgCl–WO₃ structure was employed to produce photochemical hydrogen for doping of an AgCl film. Atomic photochemical hydrogen, detached under the action of light from hydrogen donor molecules, previously adsorbed on the WO₃ surface, migrated through the WO₃ film into the AgCl film, which provided doping of the AgCl surface and yielded hydrogen sensitization simultaneous to illumination and yielded the enhancement of photochromism in the AgCl films. The atomic hydrogen played the role of a reducing agent and triggered the formation of sensitization centers on the halide surface, which in turn facilitated the growth of silver clusters and colloids under the action of light. The double-layer AgCl–WO₃ structure realizes the idea of two-stage catalysis: first the oxide surface catalyses hydrogen production under the action of light, then the photochemical hydrogen atoms act as catalysts during the photolysis of the halide.     

Electrochromic WO3 thin films active in the IR region

Herein, we investigate the electrochromic performances in the infrared (IR) region, in particular in the midwavelength (MW, 3–5 μm) and long wavelength (LW, 8–12 μm) bands, of WO₃ thin films grown by RF-sputtering and pulsed laser deposition. For an optimized voltage window, 200 nm room temperature thin films are the most efficient in the MW band, with the highest contrast in reflection, namely 35%, whereas thicker films, typically 500 nm, are required in the LW band. At 400 °C films show contrasts in reflection lower than 10%, surprisingly associated with a reasonable insertion amount of 0.20. Indeed, no straight correlation between the electrochemical and the optical properties in the IR region was established.     

Study on photocurrent of bilayers photoanodes using different combination of WO3 and Fe2O3

Bilayer photoanodes were prepared onto glass substrates (FTO) in order to improve generated photocurrents using UV-vis light by water splitting process. A comparative study of photocatalytic was performed over the films surface using Fe₂O_3, WO₃ and mixture of bicomponents (Fe₂O₃:WO₃). Different types of films were prepared using Fe₂O_3, WO₃ and bicomponents (mixture) on FTO substrates. The films were grown by sol gel method with the PEG-300 as the structure-directing agent. The photo-generated of the samples were determined by measuring the currents and voltages under illumination of UV-vis light. The morphology, structure and related composition distribution of the films have been characterized by SEM, XRD and EDX respectively. Photocurrent measurements indicated surface roughness as the effective parameter in this study. The deposited surfaces by bicomponents or mixture are flat without any feature on the surface while the deposited surfaces by WO₃ appears rough surface as small round (egg-shaped particles) and cauliflower-like. The surface deposited by Fe₂O₃ show rough no as well as WO₃ surface. The deposited surfaces by WO₃ reveal the higher value of photocurrent measurement due to surface roughness. Indeed, the roughness can be effective in increasing contact surface area between film and electrolyte and diffuse reflection (light scattering effect). The solution (Fe₂O₃:WO₃) shows the low photocurrent value in compare to WO₃ and Fe₂O₃ hat it may be due to decomposition the compound at 450 ± 1 °C to iron-tungstate Fe₂(WO₄)₃.     

Analysis of the influence of the gas pressure during the deposition of electrochromic WO3 films by reactive r.f. sputtering of W and WO3 target

Tungsten trioxide is the most accepted material for electrochromic devices. In the work thin films of WO₃ were deposited by reactive r.f. sputtering of both metallic (W) and ceramic (WO₃) targets to study the correlation between the electrochromic properties and the structures of the films. Samples were grown at different pressures of Ar+O₂ in order that the energy regimes of the sputtered particles on the condensing surface could be set either below or above the thermalisation diffusion limit. Lithium ions were intercalated in the films in an aprotic electrolyte and the colouring/bleaching behaviour as a function of the intercalated amount of lithium was detected in the 1st and 10th cycle. From these measurements, the electrochromic properties of the films were worked out. The optical and morphological characteristics were analysed respectively, by spectrophotometric and X-TEM measurements. The amount of water present in the films, detected by IR spectroscopy, turned out to be well correlated to the film morphology and also to the porosity.     

Yb-doped WO3 photocatalysts for water oxidation with visible light

Yb-doped WO₃ photocatalysts were prepared by co-sputtering WO₃ and Yb, followed by annealing in air for water oxidation with visible light. All the obtained photocatalysts were monoclinic with sputtering power of Yb up to 10 W and displayed no optical absorption red shift. In photoelectrochemical (PEC) studies, the photocurrent densities were improved with up to 0.34 at.% Yb in WO_3, with the highest photocurrent of 1.3 mA/cm² (1.2 V vs. Ag/AgCl) achieved with <0.1 at.% Yb. Electrochemical impedance spectroscopy (EIS) measurements showed that optimized Yb doping reduced charge transfer resistance and increased donor density of WO₃ photocatalyst. The improvement in photocurrent density was attributed to enhanced conductive carrier path, increased oxygen vacancies and 4f¹³ orbital configuration due to Yb³⁺ substitution of W⁶⁺.     

Opportunities and challenges in science and technology of WO3 for electrochromic and related applications

Since the discovery of the electrochromic (EC) effect in transition metal oxides in the mid-1960s, intense research and development work spanning four decades has led to many exciting developments in the science and technology of this class of materials. Tungsten oxide (WO₃) has emerged as one of the key materials, not only for EC devices, but also for many other related applications. After many years of technology development efforts, WO₃-based EC “smart windows” have finally emerged as a viable commercial product. In spite of enormous progress being made on the structural, electrical, and optical properties of amorphous and crystalline WO₃, a detailed understanding of the EC effect in this material still remains somewhat qualitative. Although theoretical models based on intervalence charge transfer and polaron formation have been widely accepted, these models are still unable to explain some of the experimental results on the coloration phenomena. The coloration in WO₃ is a structure-sensitive phenomenon, and excess electrons can be either localized or delocalized. The presence of structural defects such as oxygen vacancies, impurities, and degree of disorder plays a crucial role in determining the coloration efficiency. Although significant progress has been made in recent years on the calculation of electronic structure and defect properties of both amorphous and crystalline WO₃, the structural complexity of the material presents many challenges and opportunities for theoretical computation. The unique ability to induce bistable optical and electrical properties in WO₃ by a variety of excitation sources has led to many devices of significant technological interest. Some of the applications currently being pursued include the photoelectrochemical cell for solar energy conversion and storage; photoelectrochemical splitting of water to generate hydrogen; chemical and biological sensors based on the gasochromic effect; photo- and electrocatalysts for a variety of chemical reactions; demonstration of high-temperature (91 K) superconductivity in WO₃ doped with H, Na, and K; synthesis of a new class of hybrid organic/inorganic (WO₃) materials; and application in ultra-high-resolution electron beam lithography. The emergence of nanostructured WO₃ in recent years will undoubtedly provide new opportunities and significant impact to many of these technologies. This paper presents a brief overview of some of the key research issues the author believes will impact the science and technology of this exciting material.     

Photoelectrochemical and structural characterization of carbon-doped WO3 films prepared via spray pyrolysis

Carbon-doped tungsten trioxide (WO₃) films were produced using a spray-pyrolysis methodology, with glucose used as the carbon dopant source. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV–vis, scanning electron microscopy, and solid-state nuclear magnetic resonance. The photoelectrochemical activity was evaluated under near UV–visible light and visible light only irradiation conditions. The presence of carbonate-type species in the C-doped sample was confirmed by XPS and SSNMR. The C-doped WO₃ electrodes exhibited photocurrent densities up to 1.6 mA/cm² in 1 M HCl electrolyte and as high as 2.6 mA/cm² with the addition of methanol as a sacrificial agent. A high contribution (∼50%) of the photocurrent density was observed from visible light. C-doped WO₃ produced approximately 50% enhanced photocurrent densities compared with the undoped WO₃ electrode synthesized using the same procedures. The photoelectrochemical performance was optimized with respect to several synthetic parameters, including dopant concentration, calcination temperature and film thickness. These results indicate the potential for further development of WO₃ photocatalysts by simple wet chemical methods, and provide useful information towards understanding the structure and enhanced photoelectrochemical properties of these materials.     

The character of WO3 film prepared with RF sputtering

The effects of preparation conditions on WO₃ films using RF reactive sputtering were investigated in order to prepare a high efficiency semiconductor electrode. The properties of the electrodes were measured in the solution of H₂SO₄. We found the optimum condition for the photocurrent in our system. The photocurrent is independent of O₂ concentration in the range of 20–50%. We suppose that a photocurrent of WO₃ depends on an orientation and a grain size. The result of XRD spectra corresponded well with SEM image. From the SEM images and the absorption spectra it was considered that the thicker the WO₃ films were the rougher the surface became.     

Residual charges and infrared absorption in electrochromic WO3 films prepared by hydrogen-introduced sputtering

Electrochromic WO₃ films were prepared by rf−sputtering in atmosphere consisting of Ar/H₂/O₂ mixed gas. The as-sputtered films require several times of injection/extraction of ions (the aging) for obtaining reversible coloration/bleaching. After the aging, there are ions (protons) remaining in the films, namely residual charges. From the results of IR absorption of the as-sputtered and aged films, the residual charges contribute to create OH and HOH bonds. Hydrogen introduced in the films during sputtering is transformed only into OH bonds combining with unstable oxygen in the films. The introduced hydrogen is considered to suppress the growth of grain in WO₃ films from AFM observation.     

IR electrochromic WO3 thin films: From optimization to devices

This paper reports enhanced electrochromic properties in the infrared region, so-called IR, and in particular, in the middle wavelength (MW: 3–5 μm) and long wavelength (LW: 8–12 μm), of radio frequency sputtered (RFS) WO₃ thin films, thanks to a careful optimization of the deposition conditions, namely the duration of deposition (<240 min), the substrate nature (FTO or Au), and the chamber pressure (15 and 45 mT). Significant modulations in reflectance (as high as 73% in the MW) and in the apparent temperature (up to 35 °C) between the inserted state and the deinserted one, for WO₃ thin films cycled in H₃PO₄ liquid electrolyte, are reported. Such performances correspond to a variation in emissivity of at least 40% as required for military applications. Finally, coupling both modelling and experimental approaches, first trends on the incorporation of the WO₃ single layer in full electrochromic devices (ECDs) are discussed considering mainly an all-solid-state device configuration.     

Photoresponse and H2 production of topographically controlled PEG assisted Sol–gel WO3 nanocrystalline thin films

WO₃ thin films were fabricated by sol–gel method using polyethylene glycol (PEG) as dispersing agent. Physical and photoelectrochemical properties of the synthesized nanocrystalline films were studied by varying weight ratio of PEG to tungsten precursor (x). Based on AFM observations and statistical modeling of the WO₃ surface, the thickness of the films increased by increasing the amount of x with a nearly linear fashion while the surface roughness reached to a saturated value. However, the film synthesized with x = 4 showed a chaotic surface behavior. Optical analysis revealed that by increasing the x, transmittance of the films decreased while their band gap energies remained unchanged. According to XRD results, variation of x did not change structure of the nanocrystalline film while XPS analysis indicated a better stoichiometry for the films with higher x values. A less charge transport life time was obtained for films with higher x values, but an enhanced photoresponse of the films and also hydrogen production via water splitting reaction were observed by increasing the amount of x. On the other hand, the charge transfer resistance of the samples reduced from 6.5 kΩ to 1.2 kΩ by addition of PEG to the sol from x = 0 to x = 2.     

Layered WO3/TiO2 nanostructures with enhanced photocurrent densities

Layered WO₃/TiO₂ nanostructures, fabricated by magnetron sputtering, demonstrate significantly enhanced photocurrent densities compared to individual TiO₂ and WO₃ layers. First, a large quantity of compositions having different microstructures and thicknesses were fabricated by a combinatorial approach: diverse WO₃ microstructures were obtained by adjusting sputtering pressures and depositing the films in form of wedges; later layers of TiO₂ nanocolumns were fabricated thereon by the oblique angle deposition. The obtained photocurrent densities of individual WO₃ and TiO₂ films show thickness and microstructure dependence. Among individual WO₃ layers, porous films exhibit increased photocurrent densities as compared to the dense layer. TiO₂ nanocolumns show length-dependent characteristics, where the photocurrent increases with increasing film thickness. However, by combining a WO₃-wedge type layer with a layer of TiO₂ nanocolumns, PEC properties strikingly improve, by about two orders of magnitude as compared to individual WO₃ layers. The highest photocurrent that is measured in the combinatorial library of porous WO₃/TiO₂ films is as high as 0.11 mA/cm². Efficient charge-separation and charge carrier transfer processes increase the photoconversion efficiency for such films.     

Investigation of WO3/ZnO thin-film heterojunction-based Schottky diodes for H2 gas sensing

A comparative study of Schottky diode hydrogen gas sensors based on Pd/WO₃/Si and Pd/WO₃/ZnO/Si structure is presented in this work. Atomic force microscopy and X-ray photoelectron spectroscopy reveal that the WO₃ sensing layer grown on ZnO has a rougher surface and better stoichiometric composition than the one grown on the Si substrate. Analysis of the I–V characteristics and dynamic response of the two sensors when exposed to different hydrogen concentrations and various temperatures indicate that with the addition of the ZnO layer, the diode can exhibit a larger voltage shift of 4.0 V, 10 times higher sensitivity, and shorter response and recovery times (105 s and 25 s, respectively) towards 10,000-ppm H₂/air at 423 K. Study on the energy band diagram of the diode suggests that the barrier height is modulated by the WO₃/ZnO heterojunction, which could be verified by the symmetrical sensing properties of the Pd/WO₃/ZnO/Si gas sensor with respect to applied voltage.     

In situ Raman spectroscopy of the electrochemical reduction of WO3 thin films in various electrolytes

With in situ micro-Raman measurements during the electrochemical reduction of WO₃ thin films, the influence of the intercalated cation (H⁺/Li⁺) and an addition of water to the aprotic lithium electrolyte was investigated. The Raman spectra of lithium bronzes Li_xWO₃ show two main results: (i) the intercalation of hydrogen can be clearly distinguished in situ from the intercalation of lithium with this technique and (ii) even with an addition of 500 ppm of water to the lithium electrolyte no hydrogen intercalation was observed.     

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

Thin films of tungsten oxide (WO₃) were deposited onto glass, ITO coated glass and silicon substrates by pulsed DC magnetron sputtering (in active arc suppression mode) of tungsten metal with pure oxygen as sputter gas. The films were deposited at various oxygen pressures in the range 1.5×10⁻²−5.2×10⁻² mbar. The influence of oxygen sputters gas pressure on the structural, optical and electrochromic properties of the WO₃ thin films has been investigated. All the films grown at various oxygen pressures were found to be amorphous and near stoichiometric. A high refractive index of 2.1 (at λ=550 nm) was obtained for the film deposited at a sputtering pressure of 5.2×10⁻² mbar and it decreases at lower oxygen sputter pressure. The maximum optical band gap of 3.14 eV was obtained for the film deposited at 3.1×10⁻² mbar, and it decreases with increasing sputter pressure. The decrease in band gap and increase in refractive index for the films deposited at 5.2×10⁻² mbar is attributed to the densification of films due to ‘negative ion effects’ in sputter deposition of highly oxygenated targets. The electrochromic studies were performed by protonic intercalation/de-intercalation in the films using 0.5 M HCl dissolved in distilled water as electrolyte. The films deposited at high oxygen pressure are found to exhibit better electrochromic properties with high optical modulation (75%), high coloration efficiency (CE) (141.0 cm²/C) and less switching time at λ=550 nm; the enhanced electrochromism in these films is attributed to their low film density, smaller particle size and larger thickness. However, the faster color/bleach dynamics is these films is ascribed to the large insertion/removal of protons, as evident from the contact potential measurements (CPD) using Kelvin probe. The work function of the films deposited at 1.5 and 5.2×10⁻² mbar are 4.41 and 4.30 eV, respectively.     

The photoinduced evolution of O2 and H2 from a WO3 aqueous suspension in the presence of Ce/Ce

This is a report on the production of O₂ and H₂ from photocatalytic and photochemical processes in the WO₃–H₂O–Ce⁴⁺_aq–hν system. The photoproduction of O₂ and H₂ was studied over the range of WO₃ concentrations from 2 to 8 g dm⁻³, and conduction band electron scavenger concentrations 1–20 mM Ce_aq⁴⁺. Medium and high concentrations of the electron scavenger gave mainly O₂ as the main product. Dilute solutions of [Ce_aq⁴⁺]< 2 mM initially produced dioxygen, and then hydrogen after an induction period of 3–4 h. Yields of 140–250 μmol O₂  h⁻¹ and 1–7 μmol H₂ h⁻¹ were obtained and were found to depend on the physical properties and content of WO₃, the concentration of the electron scavenger, illumination period and wavelength, and the radiation geometry. The photoactivity of the suspension was correlated to the level of crystallinity of WO₃ powders. The studied system utilizes WO₃ to accomplish the initial light absorption, charge separation, and production of O₂ and H⁺ from the interaction of water molecules with photogenerated WO₃ valence band holes, in the presence of Ce⁴⁺_aq species as a scavenger of conduction band electrons. This is followed by the evolution of H₂ from a homogeneous photochemical reduction of H⁺ and/or H₂O by photoexcited Ce³⁺_aq, formed from the earlier reduction of Ce⁴⁺_aq. The obtained results show that, with an appropriate design, tungsten trioxide is a promising material that can be used as a photoactive component in energy conversion systems or in environmental photocatalysis, using artificial or solar light.