Structure, electrochromic and optical properties of WO3 film prepared by dip coating-pyrolysis

The tungsten oxide (WO₃) film was grown by dip coating-pyrolysis method with the PEG-400 as the structure-directing agent. Microstructure of the WO₃ film was characterized by TG-DSC, XRD and SEM techniques. It was found that the film annealed at 350 °C for 2 h comprised cubic WO₃ and orthorhombic WO₃. The measurements of the cyclic voltammetry (CV) and UV-vis spectrum suggested that the WO₃ film had a good electrochromic reversibility performance. The film possessed excellent modulation to the visible light and the maximal average transmittance modulation reached 70.06%.     

Electrochemical lithium incorporation into WO3 and MoO3 thin films

The generally accepted mechanism of electrochromic phenomena into WO₃ thin films involves the simultaneous injection of cations and electrons to form a tungsten bronze M_xWO₃, e.g. H_xWO₃,Li_xWO₃. Electrochromic cells of the type ITO MO₃/LiClO₄(M) in propylene carbonate/Pt, where M = W or MO and MO₃ is an amorphous thin film have been used. Different amounts of charges have been injected through these cells by electrochemical means at room temperature. The variations of the MO₃ electrode potential with the injected charge are in good agreement with the assumption of the formation of Li_xMO₃ compounds. The free enthalpies of formation of these bronzes have been calculated. The behavior of thin film electrodes seems to be intermediate between amorphous and crystallized bulky materials. Some measurements of electrode potential have also been carried out with crystallized thin films of sputtered WO₃.     

Prototype electrochromic device and dye sensitized solar cell using spray deposited undoped and ‘Li’ doped V2O5 thin film electrodes

Lithium (Li) (0–5 wt%) doped V₂O₅ thin films were spray deposited at 450 °C onto ITO substrates. Structural analysis using X-ray diffraction and Raman spectroscopy revealed orthorhombic phase of the films. In addition to the V₂O₅ phase, presence of VO₂ peaks due to high deposition temperature is also evident from structural and optical characterization. The non-stoichiometric nature of the films due to loss of the terminal O atom was confirmed from Raman spectroscopy. The direct band gap, indirect bandgap, and phonon energies were also calculated from optical studies. Different charge states of vanadium ions present in the film were identified from X-ray photoelectron spectroscopy study. Results from cyclic voltammetry experiments reflected significant differences between the undoped and Li doped V₂O₅ samples. Transport properties by Hall-effect measured at room temperature indicated significant increase in conductivity, carrier concentration and mobility of V₂O₅ thin films on doping with Li. A Dye Sensitized Solar Cell (DSSC) was fabricated using mobility enhanced 5 wt% Li doped V₂O₅ film as photoanode and its efficiency was found to be 2.7%. A simple electrochromic cell is fabricated using undoped V₂O₅ thin film to demonstrate the colour change.     

Highly uniform electrochromic tungsten oxide thin films deposited by e-beam evaporation for energy saving systems

In the last few decades, there has been a surge of interest in using tungsten oxide thin films as an active layer of electrochromic device. These devices have several practical applications such as smart window of buildings and automobile glazing for energy saving. The main objective of this work was to construct highly homogeneous and uniform e-beam evaporated amorphous WO_3-x based films into electrochromic devices, which were fully characterized for switching speed, coloration efficiencies and cycling voltammetry responses. Fabricated devices contain indium doped transparent oxide coated glass as the transparent conductive electrode, ～200?nm thickness of WO_3-x as the cathodically coloring material and a lithium perchlorate based conducting gel electrolyte. X-ray diffraction patterns indicate that all as-deposited films are amorphous. Experimental results showed that both solid and liquid electrolyte electrochromic devices are initially very transparent that exhibit perfect optical modulation and coloration efficiency (up to 68.7?cm²/C and 52.6?cm²/C at 630?nm, respectively) due to easier intercalation of the Li⁺ within their structure. One of the more significant findings to emerge from this study is that e-beam coated electrochromic devices based on tungsten oxide thin films showed superior performance among to other coating methods. Therefore, excellent reversibility of color change behavior is attractive for pertinent use in electrochromic energy storage devices.     

Structural and optical properties of WO<Subscript>3</Subscript> electrochromic layers prepared by the sol-gel method

Thin layers of tungsten trioxide have been prepared from an aqueous solution of peroxotungstic acid (PTA) using the sol-gel method. Compositional, structural and optical characteristics of WO₃ coated on indium tin oxide (ITO) conductive glass substrates were studied using X-ray diffractometery (XRD), cyclic voltammetery (CV), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Monoclinic and triclinic crystalline structures for thin film and powdered WO₃ were confirmed by XRD analysis. SEM micrograph of annealed samples revealed micro cracks due to a decrease in density and a contraction of layers. EDX analysis showed that 1∶2 ratio of oxygen and tungsten atoms in the prepared films is obtained at heat treatment temperatures higher than 200 °C. Furthermore, the annealed samples showed very good electrochromic behavior in cyclic voltammetery studies. Refractive index “n” and extinction coefficient “k” values were found to be reduced by increasing the wavelength and decreasing the temperature.     

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.     

Electrochromic and photoluminescence properties of cobalt oxide thin films prepared by spray pyrolysis

Cobalt oxide thin films were prepared by a facile spray pyrolysis technique, using a perfume atomizer with an aqueous solution of hydrated cobalt chloride salt with a molar concentration of 0.025?M as a source of cobalt. The films were deposited onto glass substrates at temperature of 350?°C. The structural, morphological, and electrochromic properties of the obtained films were studied. It was found from X-ray diffraction analysis that the films were polycrystalline in nature with spinel-type cubic structure and preferred orientation along [111] direction. The Scanning Electron Microscopy images revealed a porous structure with the average grain size around 200?nm. The cyclic voltammetry measurements revealed that Cobalt oxide thin film is an anodically coloring electrochromic material with a transmittance variation in the visible range of 31%, and a fast response time (about 2?seconds) and a good cycling stability. These electrochromic performances make cobalt oxide thin film an attractive material for using as an anodic electrochromic material in smart windows devices. The photoluminescence spectra exhibited a strong emission in the visible region confirming the good crystallinity properties of Co₃O₄ thin films.     

Electrochromic properties of nano-composite nickel oxide film

In this study, we develop a nano-composite nickel oxide (NNO) film on the indium tin oxide (ITO)-coated glass substrate for electrochromic applications. The NNO film is composed of the core-shell structure of NiO/conducting ITO nano-particles. High porosity in the NNO film offers large active surface area for redox reaction. Electrochromic electrodes fabricated with the NNO films produce high transmittance variation (66.2% at a wavelength of 550 nm), fast switching speed (coloring: 3.5 s; bleaching: 4 s) and good durability, which are much better than those of ones made with the traditional nickel oxide films. The structure, morphology, and electrochromic properties are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and UV-vis spectroscopy.     

Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H₂O₂), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H₂O₂ detection. The linear response range of the biosensor to H₂O₂ concentration was from 5 × 10⁻⁷ mol L⁻¹ to 1.5 × 10⁻³ mol L⁻¹ with a detection limit of 3.75 × 10⁻⁸ mol L⁻¹ (based on S/N = 3).     

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO₃ (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO₃. These amorphous thin films of about 4 μm in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO₃ microcrystals in the amorphous phase.     

Electrodeposition and growth mechanism of SnSe thin films

Tin selenide (SnSe) thin films were electrochemically deposited onto Au(1 1 1) substrates from an aqueous solution containing SnCl₂, Na₂SeO₃, and EDTA at room temperature (25 °C). The electrochemical behaviors and the codeposition potentials of Sn and Se were explored by cyclic voltammetry. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and UV-vis absorption spectroscopy were employed to characterize the thin films. When the electrodeposition potential increased, the Se content in the films decreased. It was found that the stoichiometric SnSe thin films could be obtained at −0.50 V. The as-deposited films were crystallized in the preferential orientation along the (1 1 1) plane. The morphologies of SnSe films could be changed from spherical grains to platelet-like particles as the deposition potential increases. The SEM investigations show that the film growth proceeds via nucleation, growth of film layer and formation of needle-like particles on the overlayer of the film. The optical absorption study showed the film has direct transition with band gap energy of 1.3 eV.     

Polarity sensitive electro-optical response in liquid crystal devices due to ionic diffusion in WO3 thin films

The present work is aimed to a deeper understanding of the polarity sensitive electro-optical response observed in a liquid crystal cell with asymmetric insertion of a thin film of tungsten trioxide, deposited by r.f. sputtering on a transparent ITO substrate. After preliminary structural characterization of the films, the electro-optical response of the liquid crystal cells containing a WO₃ layer has been analyzed. The voltage thresholds of the Frédericksz transition are increased or decreased for the anodic or the cathodic charge of the tungsten trioxide film, respectively. In such a way a polarity-sensitive electro-optical response is generated, with the same frequency of the applied field. Impedance and cyclic voltammetry measurements have been performed on liquid crystal cells having WO₃ films inserted as electrode, for as-deposited films as well as for annealed films at increasing temperatures. A strong decrease of the ionic current is observed in the cell where the film underwent the highest temperature treatment, above 300 °C. All the measurements suggest that a charge redistribution occurs for the hydrogen ions, always present in the films, during the intercalation-deintercalation processes induced by the applied voltage, and it is responsible for the changes of the effective electric field acting on the liquid crystal layer. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Electro-optic spectroscopy of electrochromic processes in tungsten trioxide

The nature of the electrochromic processes in solid-state electrochromic devices (ECD) ITO/a-WO₃/a-SiO₂/Au is investigated by analysing their electro-optical behavior during the current pulses and the linear sweeping of the bias voltage. It is shown that the character of the current-coltage curve of the ECD is determined by passivation, by hydrogen/oxygen evolution on the counter electrode (Au) and by redox reactions on the electrochronic electrode (amorphous WO₃ film: a-WO₃). The light transmittance versus voltage and the high-frequency differential impedance of the active component versus voltage curves are dependent mainly on electrochromic reactions.     

Superior performance characteristics for the poly(2,5-dimethoxyaniline)–poly(styrene sulfonic acid)-based electrochromic device

We have fabricated an electrochromic (EC) device with poly(2,5-dimethoxyaniline), PDMA, entrapped in poly(styrene sulfonic acid) (PSS) as an electrochromic layer. The device showed improved performances like stability, optical contrast, etc., over the device with a PDMA layer doped by H₂SO₄. In the process of fabrication of the EC device with a sandwich configuration, indium tin oxide (ITO)/PDMA–PSS||poly(ethyleneimine) (PEI)/orthophosphoric acid (H₃PO₄)/WO₃/ITO, electrochemical polymerization of 2,5-dimethoxyaniline (DMA) was performed with PSS as electrolyte and ITO coated glass as working electrode. The performance characteristics of EC device, like optical contrast, stability, switching time, etc., were followed by cyclic voltammetry, double potential step chronoamperometry and in-situ spectroelectrochemistry. The device was operated in between − 1 V and + 1 V, and absorption characteristics were followed by in-situ UV–visible spectroscopy. A visible contrast in color upon switching the potential from − 1 V to + 1 V was noticed for the device. The device was pale yellow at − 1 V and dark green at + 1 V. Incorporation of PSS into PDMA resulted enhancement in the performance of the complementary electrochromic device. The optical contrast of the device was improved by incorporating PSS into PDMA matrix. The device retained nearly 50% of their optical contrast after 10,000 double steps informing the superior performance of PDMA–PSS in the EC device.     

Nanoporous nickel oxide thin films and its improved electrochromic performance: Effect of thickness

Electrochromic properties of chemically bath deposited nanoporous NiO thin films were investigated as a function of film thickness using Ni sulphate precursor, aqueous ammonia and potassium persulphate as complexing and oxidizing agents respectively. The films were characterized for their structural, morphological, optical and electrochromic properties using X-ray diffraction, scanning electron microscopy, FT-IR spectroscopy, cyclic voltammetry, chronoamperometry and optical transmittance studies. X-ray diffraction patterns show that the films are polycrystalline, consisting of NiO cubic phase. Infrared spectroscopy results show the presence of free hydroxyl ion and water in NiO thin films. SEM micrographs revealed nanoporous nature composed of interconnected nanoporous network, forming well defined 3D nano envelopes. The optical band gap energy was found to be decreased from 3.22 to 2.80 eV with increasing film thickness. The electrochromic properties of all the films were investigated in aqueous (KOH) and non aqueous (LiClO₄-PC) electrolyte by means of cyclic voltammetry (CV), chronocoulometry (CC) and optical studies. The transmittance modulations or optical density differences during the coloring/bleaching process were found to be increased with the film thickness. This increment in optical differences led to an increase in coloration efficiency (CE) to about 95 cm²/C, which is two times more than that observed in KOH and response time of 2.9 s for bleaching (reduction) and 3.5 s for coloration (oxidation) observed for the film deposited at 60 min with excellent electrochemical stability up to 3000 c/b cycles in LiClO₄-PC electrolyte.     

Nanosized multilayer films with concurrent photochromism and electrochromism based on Dawson-type polyoxometalate

An inorganic-organic composite multilayer film constructed of poly(vinyl alcohol) (PVA) with Dawson-type phosphotungstate anion [P₂W₁₈O₆₂]⁶⁻ (P₂W₁₈) and poly(allylamine hydrochloride) (PAH) were fabricated on quartz, ITO, silicon and CaF₂ substrates by a layer-by-layer self-assembly method. The film was provided with concurrent photochromism and electrochromism. IR spectra showed that the structure of the PVA was fully maintained in the multilayer film. And their photochromic and electrochromic properties were investigated by UV-vis spectra, cyclic voltammetry (CV), chronoamperometry (CA) measurement and X-ray photoelectron spectra (XPS). Atomic force microscopy (AFM) was used to investigate the surface topography. This study provides a new route to explore the possibility of application to polyoxometalate-based hybrid inorganic-organic materials.     

Highly porous nickel oxide thin films prepared by a hydrothermal synthesis method for electrochromic application

We report NiO nanowall thin films prepared by a facile hydrothermal synthesis method and their electrochromic application. The as-prepared porous nanowall NiO thin films show a highly porous structure built up by many interconnected nanoflakes with a thickness of about 30 nm. The electrochromic performances of the NiO films are characterized by means of UV–vis spectroscopy and cyclic voltammetry (CV) measurements. The effect of the annealing temperature on electrochromic properties is discussed. The NiO nanowall film annealed at 300 °C exhibits much better electrochromic performance than those counterparts annealed at higher temperature. The film annealed at 300 °C exhibits a noticeable electrochromism with reversible color changes from transparent to brown dark and presents a transmittance variation with 77% at 550 nm. The NiO nanowall film also shows good reaction kinetics with fast switching speed, and the coloration and bleaching times are 3 s and 4 s, respectively. The improved electrochromic performances are due to the porous morphological characteristics with fast ion and electron transfer resulting in fast reaction kinetics and high color contrast.     

Effect of oxygen partial pressure and VO<Subscript>2</Subscript> content on hexagonal WO<Subscript>3</Subscript> thin films synthesized by pulsed laser deposition technique

We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO₃ thin films. XRD results show the hexagonal phase of deposited WO₃ thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO₃ thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO₂ content on structural, electrochemical, and optical properties of (WO₃)_1−x (VO₂) _x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO₂–WO₃ thin film electrode with higher VO₂ content (x ≥ 0.2). Increase of VO₂ content in (WO₃)_1−x (VO₂) _x films leads to red shift in optical band gap.     

Electrochemical synthesis and characterization of a new conducting polymer: Polyrhodanine

An antimicrobial drug, rhodanine (Rh), was electrochemically polymerized on a Pt electrode using cyclic voltammetry (CV). The high quality and homogeneous polyrhodanine (pRh) films with a dark-purple color were obtained. The chemical structure characterization was investigated by Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy techniques. Further, thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques used to investigate thermal properties of the film. It is found that thermal stability of pRh films is relatively high. It is also observed that tetrahydrofurane (THF) and N-methyl-2-pyrrolidone (NMP) are good solvents for the polymer.     

Electrochromism in WO3 thin films. II. LiClO4-dioxolane-water electrolytes

The performances of electrochromic cells with evaporated amorphous WO₃ thin film as electrochromic material in (2.5 M) LiClO₄-dioxolane-water electrolytes are presented. A comparison with the results previously obtained in propylene carbonate instead of dioxolane solvent is carried out. The influence of the following parameters has been studied: the thickness of the film, the water content in the electrolyte, the potential applied to the electrochromic electrode during coloration and bleaching processes.