Sol–gel electrochromic coatings and devices: A review

A brief updated review is made on sol–gel-derived electrochromic films (some of which used as ion storage films) of different chemical systems. Performances of selected films measured in electrochemical cells or in devices are discussed and the degradation problems experienced by different authors enumerated.     

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.     

Sol–gel niobium pentoxide: A promising material for electrochromic coatings, batteries, nanocrystalline solar cells and catalysis

In the last decade the sol–gel process became a promising method to synthesize materials in form of coatings, nanoscale powders and porous systems. The technique has been mainly used at laboratory scale and has brought interesting contributions for the development of new nanomaterials. Nevertheless, several products or devices made with such a process already exist and new ones should be available in the market in the near future. This paper briefly reviews the state of the art in the development of electrochromic (EC) coatings and devices, batteries, nanocrystalline solar cells and in the field of catalysis achieved during the last decade using sol–gel derived pure and doped niobium pentoxide.     

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.     

Boron doping effects in electrochromic properties of NiO films prepared by sol–gel

In this paper, NiO films doped with B₂O₃ were first prepared by sol–gel. The effects of boron content on the structure and electrochromic properties of NiO films were studied with X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetric (CV) and UV–vis spectrophotometer, respectively. In addition, the roughness and phase of the bleached/colored were studied by atom force microscopy (AFM). B-doped prevent the crystallization of the films. The colored state transmittance could be significantly lowered when the boron added. The NiO film doped with boron exhibited a noticeable electrochromism with a variation of transmittance up to ∼60% at the wavelength range of 300–500 nm.     

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.     

Effect of humidity on structure and electrochromic properties of sol–gel-derived tungsten oxide films

The influence of varying relative humidity (RH55 and 75%) during thin film deposition from an oxalato-acetylated peroxotungstic acid sol by dip coating, on the microstructure and electrochromic properties of pristine tungsten oxide (WO₃) films obtained upon annealing is presented. The films fabricated under a relative humidity of 55% are amorphous whereas the ones cast under a substantially humid atmosphere (RH75%) are characterized by interconnected nanocrystallites with a triclinic phase and a nanoporous surface morphology as well. Upon lithium insertion, larger integrated values of transmission modulation and coloration efficiency are observed over the photopic and solar regions, for the films prepared under a RH75% as compared to that observed for the films deposited under a RH of 55%. Functional improvements are due to the larger surface area of nanocrystallites and a porous microstructure, a consequence of a higher degree of hydration and hydroxylation in the former films in contrast to the non-porous and a rather featureless structure of the latter films. Faster switching kinetics between the clear and blue states, a greater current density for lithium intercalation, a higher diffusion coefficient for lithium and a superior cycling stability, again shown by the film fabricated under a 75% RH confirm that the WO₃ film microstructure is most conducive for a more facile ion insertion–extraction process, which hints at its potential for electrochromic window applications.     

Aging effect of diethanolamine stabilized sol on different properties of TiO2 films: Electrochromic applications

Diethanolamine derived clear precursor sol has been utilized for the deposition of TiO₂ films annealed at 470 °C for 5 min. Effect of the precursor sol's aging on different properties of the films has been examined in the present study. Films obtained from aged sol have exhibited superior electrochemical (diffusion coefficient—2.46×10⁻¹⁰ cm² s⁻¹) and electrochromic characteristics due to enhanced Li ion insertion upon application of electric field. The aged sol derived films have exhibited a higher optical modulation (40% at 550 nm) between the colored and bleached states. The ion storage capacities of the films derived from freshly prepared and aged sols are 4.1 and 8.1 mC cm⁻², respectively, upon applied voltage of ±1.5 V. X-ray diffraction studies have affirmed an increase in the TiO₂ crystallite size upon the use of aged sol for the deposition of films. FTIR investigations have confirmed the conversion of Ti–O–Ti to Ti–O network in the aged sol derived films. SEM studies have evidenced porosity changes in films obtained from the sol aged for different durations. The index of refraction as measured by the ellipsometry method corroborates the SEM results and shows reduced porosity (pore size—38 nm) in films derived from the sol just reaching the state of gelation. Thickness of the aged sol derived film is measured to be the highest i.e. 350 nm. Energy bandgaps of the films for both direct and indirect transitions tend to decrease as a function of sol's aging.     

Studies on electrochromic properties of nickel oxide thin films prepared by spray pyrolysis technique

Electrochromic nickel oxide thin films were prepared by using a simple and inexpensive spray pyrolysis technique (SPT) onto fluorine-doped tin oxide (FTO) coated glass substrates from nickel chloride solution. Transparent NiO-thin films were obtained at a substrate temperature 350°C. The films were cubic NiO with preferred orientation in the (1 1 1) direction. Infrared spectroscopy results show presence of free hydroxyl ion and water in nickel oxide thin films. The electrochromic properties of the thin films were studied in an aqueous alkaline electrolyte (0.1 M KOH) using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. The films exhibit anodic electrochromism, changing colour from transparent to black. The colouration efficiency at 630 nm was calculated to be 37 cm²/C.     

Optically passive counter electrodes for electrochromic devices: transition metal–cerium oxide thin films

Films of W–Ce oxide and Ti–Ce oxide were made by reactive DC magnetron sputtering. Li⁺ intercalation/deintercalation showed that the electrochromic coloration efficiency depended on the Ce/W and Ce/Ti ratio, and at proper values of these ratios the films remained transparent irrespective of their ion content. Ti–Ce oxide combines this property with good electrochemical cycling durability, and this material can serve as a counter electrode in transparent 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.     

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.     

Sol–gel derived CuCoMnOx spinel coatings for solar absorbers: Structural and optical properties

A novel black coloured coating with the composition CuCoMnO_x was prepared using sol–gel synthesis. The coatings were deposited using the dip-coating technique from alcoholic sols based on Mn-acetate and Co- and Cu-chloride precursors. Thermogravimetric analysis showed that xerogels become crystalline at 316°C while X-ray diffraction analysis revealed that the coatings and powders correspond predominantly to CuCoMnO_x spinels. Rutherford back scattering (RBS) and transmission electron microscopic (TEM) studies combined with energy dispersive X-ray spectroscopy (EDXS) measurements confirmed that Cu, Mn and Co are present in the films in stoichiometric ratios close to that in the initial sols. IR spectroscopy has been employed to study the formation of sols by following the changes in the vibrational bands of the acetate groups during both thermal hydrolysis and the ageing of sols to xerogels. It was found that ageing of xerogels was accompanied by the formation of −COO⁻ bridging units, which at 250°C are no longer visible in the IR spectra but substituted by the vibrational modes characteristic for CuCoMnO_x. The solar absorptance (a_s) and thermal emittance (e_T) of the coatings when deposited on an Al-substrate are a_s=0.9 and e_T=0.05, which rank deposited black sol–gel CuCoMnO_x spinels among the promising candidates for spectrally selective absorber coatings for solar collectors and solar facades.     

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.     

Chemically deposited electrochromic cuprous oxide films for solar light modulation

Thin cuprous oxide electrochromic films on the transparent conductive electrodes were prepared by chemical electroless method. The films cycled in K⁺-based electrolyte revealed typical red-ox peaks with higher intensity compared to those in the Li⁺ and the Na⁺-based electrolytes. The durability of the cuprous oxide due to cycling into LiClO₄ was about 60 cycles. The thermal treatment of the films invoked decrease in red-ox peak intensity, and thus deterioration in the electrochromic properties. The response time of the coloration and bleaching to an abrupt voltage change from −4.5 to +4.5 V and reverse was found to be in the range of about 10 s. The maximum light intensity modulation ability of the films, as the AM1.5 spectrum is taken for an input, was calculated to be about 65%.     

Sol–gel derived nanocrystalline CeO2–TiO2 coatings for electrochromic windows

Mixed CeO₂–TiO₂ coatings synthesized by sol–gel spin coating process using mixed organic–inorganic Ti(OC₃H₇)₄ and CeCl₃·7H₂O precursors with different Ce/Ti mole ratios were investigated by a wide range of characterization techniques. The attempts were directed towards achieving coatings with high transparency in the visible region and good electrochemical properties. Elucidation of the structural and optical features of the films yielded information on the aspects relevant to their usage in transmissive electrochromic devices. The films have been found to exhibit properties for counter electrode in electrochromic smart windows in which they are able to retain their transparency under charge insertion, high enough for practical uses. The high optical modulation and fastest switching for WO₃ film in the device configuration with the Ce/Ti (1:1) film is interpreted in terms of conducive microstructural changes induced by addition of TiO₂ in an amount equivalent to CeO₂.     

Fabrication of tin oxide film by sol–gel method for photovoltaic solar cell system

Transparent conducting tin(IV) oxide thin films have been developed with a sol–gel method, which is a low-cost process for the electrode materials of solar cell substrate. The precursor solution was made of tin isopropoxide dissolved in isopropyl alcohol. The hydrolysis rate was controlled by the addition of triethanolamine. Dipping and spin-coating technique were applied to coat tin oxide on borosilicate glass. The resistivity of the thin film was lower than 0.01 Ω-cm and the transmittance was higher than 90% in a visible range.     

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.     

Electrochromism of sol–gel derived niobium oxide films

Niobium oxide films are promising cathodic electrochromics that in many aspects can compete with the more frequently studied WO₃ films. The films reported herein were prepared using the sol–gel route from a NbCl₅ precursor. The electrochromic properties were pronounced for crystalline films heat-treated at 500°C and exhibited transmittance changes between coloured and bleached states of 60% in the ultraviolet (UV) and 80% in the visible (VIS) and near-infrared (NIR) regions. Improved bleaching and more reversible electrochromism of thick niobium oxide films (thickness (d)>250 nm) were obtained by lithiation.Electrochromic (EC) devices were also prepared by assembling niobium oxide and lithiated niobium oxide films of different thicknesses with a hybrid inorganic/organic Li⁺ ionic conductor (organically modified electrolyte-ormolyte) and a molybdenum and antimony doped tin oxide (SnO₂ : Sb(7%) : Mo(10%) counter electrode films. The EC devices exhibited adequate colouring/bleaching kinetics (<2 min) and colouring/bleaching changes up to 40–50%.     

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.