Towards electrochromic stability in sol–gel-derived tungsten oxide films: cyclic voltammetric and spectrophotometric investigations

Hitherto unexplored irreversible changes during initial coloration/bleaching cycles for sol–gel-derived tungsten oxide (WO₃) films have been investigated using cyclic voltammetric and spectrophotometric techniques. Non-ideal features appearing in the initial five anodic (deintercalation) cycles in the voltammogram with simultaneous decreased optical transmission of the bleached films have been explained in terms of possible stoichiometric variations affecting the coloration efficiency (CE) of the films and the associated mechanisms. Electrochromic stability attained thereafter manifests in retraceable voltammograms and almost invariant value of the CE.     

Electrochromic thin films prepared by sol–gel process

New methods are shown for lower temperature preparation of amorphous tungsten oxide thin film and preparation of crystalline iridium oxide thin film by sol–gel process using metal chloride as the starting materials and ethanol as a solvent. These electrochromic materials were combined with gel solid electrolyte, and preparation of fully solid-state electrochromic display (ECD) was made. The transmittance of the ECD could be made to change by 35% by applying a voltage of 3 V for 0.2 sec.     

Structural and electrochromic properties of tungsten oxide prepared by surfactant-assisted process

By virtue of gemini surfactant template, nanostructured tungsten oxides thin films were prepared from the modified tungsten hexachloride sol-gel techniques. Temperature was varied as it is an important factor for crystallization, surface morphology and microstructure of tungsten oxides, from the studies of X-ray diffractions, scanning electron microscopy and transmission electron microscopy. The mesoporous sample calcined at 300 °C has tri-dimensional vermicular mesopores with nanocrystallites embedded in the pore wall, while such uniform structure would be destroyed by higher calcination temperature of about 400 °C. X-ray photoelectron spectroscopy was used for analyzing the surface-binding states and the stoichiometry for the oxides. Electrochromic characterization was implemented by simultaneous voltametric and spectrophotometric measurements of tungsten oxides/indium tin oxide (ITO) electrodes. The investigation results showed that organized pore-wall nanostructure has strong effects on the electrochemical and chromogenic properties depending on the specific surface area and the impacts from the evolved crystallization.     

Sol–gel deposited nickel oxide films for electrochromic applications

The electrochromic (EC) behavior, the microstructure, and the morphology of sol–gel deposited nickel oxide (NiO_x) coatings were investigated. The films were produced by spin and dip-coating techniques on indium tin oxide (ITO)/glass and Corning glass (2947) substrates.The coating solutions were prepared by reacting nickel(II) 2-ethylhexanoate as the precursor, and isopropanol as the solvent. NiO_x was heat treated at 350 °C for 1 h. The surface morphology, crystal structure, and EC characteristics of the coatings were investigated by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS), atomic force spectroscopy (AFM), X-ray diffractometry (XRD), and cyclic voltammetry (CV).SEM and AFM images revealed that the surface morphology and surface characteristics of the spin- and dip-coated films on both types of substrate were different. XRD spectra revealed that both films were amorphous, either on ITO or Corning glass substrates. CV showed a reversible electrochemical insertion or extraction of the K⁺ ions, cycled in 1 M KOH electrolyte, in both type of film. The crystal structure of the cycled films was found to be XRD amorphous. Spectroelectrochemistry demonstrated that dip-coated films were more stable up to 1000 coloration–bleaching cycles, whereas spin-coated films gradually degraded after 500 cycles.     

Influence of polyethylene glycol template on microstructure and electrochromic properties of tungsten oxide

Electrochemical synthesis of tungsten oxide (WO₃) thin film nanostructures by potentiostatically controlling the surface aggregates formed at the electrode–electrolyte interface, in the presence of a polymeric template (polyethylene glycol 400, PEG) from a plating sol of peroxotungstic acid (PTA) is presented. The nanoparticulate morphology of the WO₃ film changes drastically upon varying PEG content in the precursor sol; from an amorphous structure with randomly distributed pores for a film derived from a PTA sol with PEG:ethanol in a 3:7 volume ratio, to a mesoporous, nanocrystalline material with hybrid structures encompassing spherical grains and nanorod-like shapes with a triclinic modification for a film formed in a sol with PEG:ethanol in a 1:1 volume ratio. This approach highlights the role of the PEG proportion in controlling crystal growth, assembly patterns and pore structure. The film derived from the sol with PEG:ethanol in a 1:1 volume ratio exhibits superior transmission modulation and coloration efficiency as compared to the film obtained from a sol with PEG:ethanol in a 3:7 volume ratio. While the latter film deteriorates rapidly within 35 color-bleach cycles, the former film sustains more than 3500 cycles, without significant degradation. This film also exhibits fast switching between the clear and blue states; these are repercussions of the mesopore structure and the interconnected nanocrystallite phase.     

Electrochromic properties of one-dimensional tungsten oxide nanobundles

In this study, one-dimensional (1D) tungsten oxide nanobundles (TNB) were synthesized via a simple solvothermal method. The phase of 1D tungsten oxide was W₁₈O₄₉, and the diameter and length of the building units (nanowires) were about 7 and 800 nm, respectively. TNB films were fabricated by the Langmuir–Blodgett (LB) method. The locally arranged domains of the long nanobundles form the LB films, but it is difficult for them to align perfectly owing to the inter-nanobundle interaction and dispersion problems. The electrochromic (EC) property of the TNB LB films was characterized by electrochemical potential cycling tests and in situ transmittance measurement. The deposition condition of the LB films influenced their EC property. The heat treatment and surface pressure of the TNB LB films plays an important role in the response time and transmittance of the TNBs.     

Characterization of ion diffusion and transient electrochromic performance in PECVD grown tungsten oxide thin films

Electrochromic tungsten oxide thin films were synthesized by plasma-enhanced chemical vapor deposition (PECVD). Film density and electrochromic performance were controlled by the degree of ion bombardment. A moderate degree of ion bombardment was optimal, and the refractive index was shown to be a sensitive indicator of electrochromic performance. Chronoamperometry in concert with optical transmission was used to determine diffusion and absorption coefficients using both H⁺ and Li⁺ containing electrolytes. The absorption coefficients were similar for both ions, scaling with the degree of intercalation to 50,000 cm⁻¹ in the opaque state. The diffusion coefficients for optimized films were found to be relatively insensitive to the degree of ion intercalation, with values of 10⁻⁹ and 10⁻¹⁰ cm²/s for H⁺ and Li⁺, respectively. These values are about an order of magnitude greater than values reported for vacuum-deposited films, which was attributed to low relative density in the PECVD films. The diffusion and absorption coefficients were incorporated into a model that successfully reproduced transient optical performance.     

Optical properties of sol–gel dip-coated Ta2O5 films for electrochromic applications

Amorphous Ta₂O₅ films were prepared by sol–gel dip process on different substrates. The dip-coating technique was used to prepare amorphous Ta₂O₅ films by hydrolysis and condensation of tantalum ethoxide, Ta(OC₂H₅)₅, precursor. Stable coating solutions were prepared using acetic acid as a chelating ligand and catalyzer. Single layer and multi-layered Ta₂O₅ films were fabricated at a dipping rate of 107 mm/min. The microstructure, stoichiometry and optical properties of these films were investigated as a function of the film thickness. Room temperature CV measurements clearly revealed a protonic conductor behavior for Ta₂O₅ films. Optical properties such as refractive index, extinction coefficient and optical band gap value of the Ta₂O₅ films were calculated from optical transmittance measurements. It was found that the refractive index and extinction coefficient values were affected by the thickness of the coatings. The refractive index at a wavelength of 550 nm increased from 1.70 to 1.72 with increasing film thickness. The optical band gap value (3.75±0.12 eV) of the coating was unaffected by the film thickness. These results indicate that sol–gel-deposited Ta₂O₅ films have a promising application as proton conductors in electrochromic devices.     

Investigation of sol–gel derived thin films of titanium dioxide doped with vanadium oxide

Thin films of titanium dioxide and titanium–vanadium oxide were obtained by a sol–gel method. The coatings are uniform, smooth with very good optical properties. The solutions of both kinds are stable for more than a year. Structure and vibrational properties were studied with the help of X-ray diffraction (XRD) analysis and infrared spectroscopy (IR). The refractive indices and film thicknesses were measured by an ellipsometer at a wavelength of 638.2 nm, as a function of annealing temperature. The optical properties were investigated by ultraviolet–visible (UV–VIS) spectroscopy.     

Optical properties of mixed V/Ce oxide films prepared via inorganic sol–gel route

New mixed V/Ce films at 55, 38, and 32 at% of V were prepared via inorganic sol–gel route by dip-coating technique. The absorption edge of prepared films shifts towards higher wavelengths at higher concentration of added vanadium pentoxide. The indirect-allowed band gap (E_G) also changes in dependence of added vanadium oxide from 2.8 up to 2.3 eV.     

The effect of water on the electrochromic properties of WO3 films prepared by vacuum and chemical methods

We present a comparative study on the effect of absorbed water on the properties of tungsten oxide films prepared by two different methods (e-gun evaporation, and an aqueous sol–gel technique). Scanning electron microscopy, Fourier transform infrared spectroscopy and electrochemical techniques have been used to assess the film properties. It has been found that the preparation method of the films greatly affects their water content and thus, electron gun evaporated films have less water incorporated into their structure than their sol–gel counterparts. The former are closely packed and transparent with most of their water content adsorbed on their surface, while the latter have a porous structure, being opaque, highly hydroxylated and hydrated to a lesser extent.Both types of films exhibit reversible electrochromism, with the evaporated films being stable up to 5000 coloration-bleaching cycles and the sol–gel ones gradually degrading after 1000 cycles. Irreversible Li⁺ trapping related to the presence of water and hydroxyl radicals has been envisaged as the cause of the inferior cycling stability of the sol–gel films.     

Effect of stabilizer on structural, optical and electrochemical properties of sol–gel derived spin coated TiO2 films

Thin films of TiO₂ were prepared using two different sol–gel routes. The two routes employed diethanolamine (DEA) and acetylacetone as stabilizing agents with titanium isopropoxide (Ti(OPrⁱ)₄) in ethanol as the deposition solution. The densification at 500 °C achieved the nanophase TiO₂ films, which were investigated by performing structural, optical and electrochemical studies. Ion storage capacity and transmission measurements showed superior response of the films derived from DEA. Between the films obtained from the two routes, the appearance of the rutile phase at lower temperature for the film synthesized using DEA was predicted on the basis of the thermal analysis of the corresponding xerogel. The nanocrystalline nature of the films was evident from the X-ray diffraction, atomic force microscopy, and scanning electron microscopy. The films deposited from both the stabilizers exhibited electrochromism in 1 M LiClO₄-propylene carbonate electrolyte on cathodic polarization.     

Synthesis and characterization of aluminum-doped CdO thin films by sol–gel process

Aluminum-doped cadmium oxide (CdO:Al) thin films are deposited on glass substrates by the sol–gel dip-coating method, taking cadmium acetate dihydrate as the precursor material. Aluminum nitrate has been taken as a source of Al-dopant. XRD pattern reveals the good crystallinity of CdO thin films. SEM micrograph showed the presence of faceted crystallites. Optical study shows 40–85% transparency with a bandgap value lying in the range 2.76–2.52 eV, depending upon the Al content in the films. Optimum percentage of Al was 5.22 for a maximum room temperature conductivity of 2.81×10³ (Ω cm)⁻¹. Hall measurement confirmed that the material is of n-type, with mobility and carrier concentrations lying in the range 413–14.7 cm²/V s, and 3.4×10¹⁹–8.11×10²⁰ cm⁻³, when percentage of Al varies in the range 1.32–7.24.     

Electrical characterization and Poole–Frenkel effect in sol–gel derived ZnO:Al thin films

Electrical properties of ZnO:Al thin films, prepared by sol–gel dip-coating technique were studied in the range of 0.32% to 1.62% Al concentrations in the films. Room temperature electrical conductivity was found in the range of 0.08 to 1.39 S/cm for different aluminium concentrations in the films. I–E characteristics of the films at a constant temperature showed non-linearity, while non-linearity becomes more and more pronounced with increase in temperature and this could be explained by Poole–Frenkel model of thermionic emission. Presence of adsorbed oxygen and excess Al atoms at grain boundaries is assumed to be the cause of this effect. These atoms produce defect levels, which trapped electrons and created a potential barrier across the grain boundaries. In the presence of an external field, the barrier height was attenuated, resulting in the thermionic emission of electrons from the trapped level to the conduction band. The trapped potentials (φ_t) were calculated for different doping concentrations in the films. The thermoelectric power (TEP) measurement confirmed the n-type nature of the films and the room temperature Seebeck coefficient was found to be −91.65 μV/K.     

Thickness-dependent electrochromic properties of solution thermolyzed tungsten oxide thin films

Tungsten oxide (WO₃) thin films are prepared by using a simple and inexpensive solution thermolysis technique. Thin film samples of different thickness are obtained by varying quantity of ammonium tungstate solution sprayed onto the preheated conducting glass substrate. A simple three-electrode cell has been formed to study the electrochemical and electrochromic properties. The electrochemical parameters of the cell such as anodic peak current, anodic peak potential, threshold voltage, amount of H⁺ ions intercalated into and deintercalated out of the WO₃ samples are calculated. The effect of film thickness on these parameters are studied. The extent of electrochromism and reversibility of the colouration/bleaching processes of various WO₃ samples are described. The colouration efficiencies at 633 nm are calculated. The maximum colouration efficiency obtained for thicker film, is 56 cm²/C. The samples were found to be stable in 0.05N H₂SO₄ electrolyte up to 1×10³ colour/bleach cycles.     

Electrically activated thin film optical coatings as functional layers in electrochromic devices

This study presents results on technology and characterization of molybdenum oxide, tungsten oxide and mixed oxide films based on Mo and W. These films were deposited by low-temperature carbonyl CVD process at atmospheric pressure and by simplified sol–gel method using spinning and spraying approaches. The obtained films were structurally and optically investigated. The films show good optical quality with optical transmittance of about 70% in the visible spectral range. Cyclic voltammograms as well as the transmittance modulation at different wavelengths in the visible spectral range were measured to characterize the electrochromic behaviour of the films. The colour efficiencies of the optimized films are in the order of 110–115 cm²/C, in case of spray deposited WO₃-sol–gel films—130 cm²/C.     

Optical and electrochemical characteristics of sol–gel deposited iron oxide films

Homogenous, crack free iron oxide films are prepared by the sol–gel spin coating technique from a solution of iron iso-propoxide and isopropanol. The films were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible (UV–Vis) spectroscopy and cyclic voltammetry (CV). XRD of the films showed that they had an amorphous structure. The optical constants refractive index (n) and extinction coefficient (k) were measured by scanning spectrometer in the wavelength range of 390–990 nm. The n and k values were found n =2.3±0.01 and k =0.2±0.002 at 650 nm. The electrochemical behavior investigated in 0.5 M LiClO₄ propylene carbonate (PC) electrolyte-CV examinations showed good rechargeability of the Li⁺/e⁻ insertion extraction process beyond 300 cycles. Spectroelectrochemistry showed that these films exhibit weak cathodic coloration in the spectral range of 350–800 nm.     

Comparison of electrochromic amorphous and crystalline tungsten oxide films

A detailed systematic study of the tungsten oxide thin films has been carried out using WO₃ films after they were annealed at progressively increasing temperatures ranging from 350°C to 450°C in oxygen environments. The structural properties of the films were characterized using X-ray diffraction and Raman spectroscopy. The amorphous WO₃ films remain as an amorphous phase up to 385°C and begin to crystallize at 390°C and then are completely crystallized at 450°C. Absorption peaks of the films are found to shift to a higher energy side with increasing annealing temperature up to 385°C and then shift abruptly to a lower energy as the films begin to crystallize at 390°C. Deconvolution of the absorption spectra shows that there are two different polaron transitions in the amorphous WO₃ films.     

Comparative studies of “all sol–gel” electrochromic windows employing various counter-electrodes

Electrochromic (EC) “smart” windows for buildings represent an effective way to modulate the intensity of incoming solar radiation. While it is accepted that WO₃ films represent the best option for the working electrode, the choice of the best counter-electrode is still debatable. Optical properties of counter-electrodes such as Ce, Fe, V and Sn oxides are presented. Electrochromic windows were made with a sol–gel WO₃ active colouring film (150°C), Ce, Fe, V oxide counter-electrodes and a sol–gel organic–inorganic hybrid (Li⁺ormolyte) ion conductor. The electrochromic responses of these devices predicted from the charge capacities, photopic transmittances and coloration efficiencies of individual films are compared with measured values.     

Synthesis of cobalt–silicon oxide thin films

Silicon–cobalt oxide thin films were prepared by the dipping sol–gel process. Samples with different number of dipping–annealing cycles were prepared. Some data regarding the precursor sol are given from small angle X-ray scattering characterization. Composition, structure, surface morphology and optical properties are obtained from X-ray diffraction, reflectance, transmittance, FTIR, scanning electron microscopy and EDX spectroscopy measurements. The silicon–cobalt oxide thin films prepared in this work are mostly amorphous. They have a high absorption coefficient in the visible and infrared regions. A refractive index from 2.15 to 1.79 (at 1200 nm wavelength), and a band gap between 3.73 and 3.68 eV with increasing film thickness were measured in the films. Sol–gel prepared Si–Co oxide thin films could be well suited for use in photothermal solar collectors.