Comparative studies of “all sol–gel” electrochromic devices with optically passive counter-electrode films, ormolyte Li ion-conductor and WO3 or Nb2O5 electrochromic films

Laminated electrochromic (EC) devices are becoming increasingly important for making “smart” windows and switchable displays. Mostly, polymeric Li⁺ ionic conductors in combination with vacuum deposited active electrochromic and counter-electrode films are used. In this paper we report on the development of all sol–gel EC devices, that is, those where all three internal layers are prepared via the sol–gel route, including the ionically conductive inorganic–organic hybrid (ormolyte). The electrochemical and optical properties of EC devices are presented and the cycling stability and reversibility of their optical modulation assessed. The results show that WO₃/ormolyte/SnO₂ : Mo, WO₃/ormolyte/SnO₂ : Sb, WO₃/ormolyte/SnO₂ : Sb : Mo, Nb₂O₅/ormolyte/SnO₂ : Sb : Mo and WO₃/ormolyte/LiCo-oxide exhibit a transmission modulation dependent on the thickness of the active electrochromic and counter-electrode films and the thickness of the ormolyte layer. Electrochemical and optical properties of individual films are described and correlated with the stability of the all sol–gel EC devices.     

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.     

Intercalation studies on electron beam evaporated MoO3 films for electrochemical devices

Now-a-days a large number of extensive research has been focused on electrochromic oxide thin films, owing to their potential applications in smart windows, low cost materials in filters, low cost electrochemical devices and also in solar cell windows. Among the varieties of electrochromic transition metal oxides, the molybdenum oxide (MoO₃) and tungsten oxide (WO₃), form a group of predominant ionic solids that exhibit electrochromic effect. The electrochromic response of these materials are aesthetically superior to many other electrochromic materials, because WO₃ and MoO₃ absorb light more intensely and uniformly. In the present case, we have discussed about the electrochromic behaviour of electron beam evaporated MoO₃ films. Moreover, the MoO₃ film can also be used as a potential electro-active material for high energy density secondary lithium ion batteries; because it exhibits two-dimensional van der Waals bonded layered structure in orthorhombic phase. The films were prepared by evaporating the palletized MoO₃ powder under the vacuum of the order of 1 × 10⁻⁵ mbar. The electrochemical behaviour of the films was studied by intercalating/deintercalating the K⁺ ions from KCl electrolyte solutions using three electrode electrochemical cell by the cyclic-voltammetry technique. The studies were carried out for different scanning rates. The films have changed their colour as dark blue in the colouration process and returns to the original colour while the bleaching process. The diffusion coefficient values (D) of the intercalated/deintercalated films were calculated by Randle's Servcik equation. The optical transparency of the coloured and bleached films was studied by the UV–Vis–NIR spectrophotometer. The change in bonding assignment of the intercalated MoO₃ films was studied by FTIR spectroscopic analysis. A feasible study on the effect of substrate temperatures and annealing temperatures on optical density (OD) and colouration efficiency of the films were discussed and explored their performance for the low cost electrochemical devices.     

The temperature behavior of smart windows under direct solar radiation

The purpose of this paper was to investigate the variation in temperature of electrochromic devices under direct solar radiation and to compare the results with double-glazed glass. The devices consisted of a V₂O₅ layer as an ion storage film and a WO₃ layer as an electrochromic layer. The V₂O₅ and WO₃ films were prepared by thermal and electron beam evaporation, respectively. The optical properties and structures of these films were investigated. Both the ion storage film and the electrochromic layer were amorphous. The optical absorption was caused by a direct-forbidden transition in V₂O₅ and by an indirect-allowed transition in WO₃. The maximum temperatures under solar radiation were measured for colored and bleached devices, double glass and air, they were found to be approximately 63, 63, 53 and 36 °C, respectively. The rates of increasing temperature to the incident power density for colored, bleached devices and double glass were 0.051, 0.049 and 0.041 °C/(W/m²), respectively.     

Electrochromic interference filters fabricated from dense and porous tungsten oxide films

Smart windows offer an opportunity to reduce energy consumption. However, the use of multiple optical elements, such as low emittance coatings and electrochromic devices, is detrimental to the luminous transmittance of these high performance windows. Although the addition of antireflective coatings has helped to reduce this problem, some elements, such as high index of refraction materials still give rise to loss of light. We show that replacing the single WO₃ active coating, the main component of an electrochromic device, by an appropriately designed electrochromic interference filter can significantly increase the transmittance. This active filter is based on a stack of dense and porous WO₃ layers. We first study the effect of porosity on the physical and electrochromic properties of WO₃ prepared by radio frequency magnetron sputtering. We demonstrate that the overlying dense coating does not inhibit the coloration of the underlying porous coating. The best performing films are combined into a 27 layer quarter-wave interference filter which is shown to cycle between bleached and colored states, while providing attractive transmission. Finally, we discuss various filter designs which can increase the transmission of an electrochromic device in its bleached state, as well as the potential use of active filters for optical security devices possessing two levels of authentication.     

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.     

WO3−x nanowires based electrochromic devices

A simple method was developed to fabricate tungsten oxide (WO_3−x) nanowires based electrochromic devices. The WO_3−x nanowires are grown directly from tungsten oxide powders in a tube furnace. The WO_3−x nanowires have diameters ranging from 30 to 70 nm and lengths up to several micrometers. The WO_3−x nanowires based device has short bleach-coloration transition time and can be grown on a large scale directly onto an ITO-coated glass that makes it potential in many electrochromic applications. The structure, morphology, and composition of the WO_3−x nanowires were characterized using the scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometer. The optical and electrochromic performance of the nanowires layer under lithium intercalation was studied in detail by UV–VIS–NIR spectroscope and cyclic voltameter.     

Kinetics and thermodynamic behavior of WO3 and WO3:P thin films

 There is a considerable interest in the research and development of materials and devices, that can be used for optical switching of large-scale glazings. Several potential switching technologies are available for glazings, including those based on electrochromic, thermochromic and photochromic phenomena. One of the most promising technologies for optical switching devices is electrochromism (EC). In order to improve the electrochromic properties of tungsten oxide, we have investigated the effect of phosphorous insertion on the electrochromic behavior of oxide films prepared by the sol–gel process.The kinetics and thermodynamics of electrochemical intercalation of lithium into Li_xWO₃ and Li_xWO₃:P films prepared by the sol–gel process were investigated. The standard Gibbs energy for lithium intercalation was calculated. The chemical diffusion coefficients, D, of lithium intercalation into oxide, were measured by galvanostatic intermittent titration technique (GITT), as functions of the depth of lithium intercalation.     

Optical properties of electrochromic all-solid-state devices

We have investigated the optical properties of an all-thin-film electrochromic device, with a thin film of ZrO₂ acting as an ion conductor. The device also employed electrochromic layers of amorphous or crystalline WO₃ and NiV_xO_yH_z. Transmission (T) and reflection (R) spectra were recorded in the wavelength range 300–2500 nm at different intercalation levels, both for single films and complete devices. The results show that T decreases significantly upon intercalation in the WO₃ thin films as well as in the devices. The reflectance only shows minor changes.     

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.     

Study on the WO3 dry lithiation for all-solid-state electrochromic devices

In this report, a simple WO₃ dry lithiation is proposed for fabrication of all-solid-state electrochromic devices and characterized completely by X-ray photoelectron spectroscopy and electrochemical method. Lithiation is carried out by electron-beam evaporation of metal lithium, and the lithiated films have different components and electrochromic properties with different lithiation degrees. It is found that if Li/W ratio is less than 0.25, tungsten bronze Li_xW0₃ is formed and the lithiated by wet method. Finally, a lithium-based all-solid-state electrochromic device with proper lithiation degree is fabricated using this dry method.     

V0.50Ti0.50Ox thin films as counterelectrodes for electrochromic devices

Thin films of V_0.50Ti_0.50O_x have been deposited by RF sputtering from metallic targets. Their use as potential counterelectrodes in electrochromic devices has been investigated. It is found that although they are slightly yellow looking in transmission, the films can reversibly store relatively large amounts of charge, whilst showing a reasonably low electrochromic colouration efficiency. The electrochemistry of V_0.50Ti_0.50O_x is found to be simple, in fact rather similar to that of WO₃, making it an almost ideal material to use in such a variable transmission device.     

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.     

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.     

Electrochromic and photoelectrochemical behavior of electrodeposited tungsten trioxide films

Electrodeposited WO₃ films exhibit reversible photochromic and electrochromic behavior (blue coloration with absorption in the near-IR region). The W-4f core level of WO₃ film at different levels of coloration has been investigated using XPS. The W-4f peaks become broader after coloration. Photoelectrochemical measurements have shown a low photoelectric conversion, efficiency of WO₃ film.     

The kinetic behaviour of ion transport in WO3 based films produced by sputter and sol–gel deposition:: Part I. The simulation model

This paper develops a new simulation model for charge injection and extraction in electrochromic WO₃ films under conditions of constant current during the charge injection process. The model is applied to the constant current coloration and bleaching of electrochromic films, and values for the diffusion coefficient and other model parameters have been obtained by fitting the model to experimental data. Application of the model to coloration and bleaching of electrochromic devices is discussed, in particular the use of the model in the design of electrochromic switching schemes.     

Improved electrochromic films of NiOx and WOxPy obtained by spray pyrolysis

Electrochromic films of NiO_x and WO_xP_y were produced by the spray pyrolysis technique. The nickel-oxide-based coatings were obtained from both an alcoholic solution of nickel nitrate and aqueous solution of the mixture nickel nitrate/cobalt nitrate. Coatings obtained from alcoholic solutions showed a noticeable contrast of optical transmittance from fully bleached to colored state. X-ray diffraction analysis showed a slight crystallization in NiO_x after electrochemical treatment: one diffraction peak for as-deposited films turned to three diffraction peaks for electrochemical treated samples. Coatings obtained from aqueous solution of mixture nickel nitrate/cobalt nitrate showed an optimized electrochromic behavior at a Ni:Co proportion of 90:10. At this condition an optical contrast of 50% is found. X-ray diffraction showed that these samples comprised a phase mixture of Co₃O₄ and NiO.WO_xP_y samples were obtained from polytungsten gel in which H₃PO₄ was added. We found that for 8.3 at% of P:W, the electrochromism was optimized. Pyrolytic coatings of WO_xP_y show superior behavior than those of WO_x obtained by spray pyrolysis, both in optical contrast and durability.     

Stability of gasochromic WO3 films

Gasochromic films consist of an electrochromic layer such as WO₃ and a very thin catalyst coating, like Pt. Hydrogen is dissociated on the catalyst into H atoms, which color the electrochromic film. A complete bleaching can be achieved in oxygen, whereas flushing with argon or evacuating the sample leads to a comparatively slow and incomplete bleaching. We discuss two kinds of aging processes, i.e. catalysed poisoning by reactants in air and a change in the water content of the WO₃. Poisoning by air increases the time needed for coloring in H₂ and bleaching in O₂ or in Ar. From results with variable WO₃ film thicknesses, we conclude that poisoning results from adsorption of a blocking species on the interior surfaces of the WO₃ pores and not on the catalyst. The adsorption process is accelerated by the catalyst. After drying the device at 100°C in vacuum, there was a severe decrease in the coloring and bleaching rates due to a reduction of the diffusion in the WO₃. Furthermore, the coloration at steady state was more intense. The variation of the water content of the WO₃ was attempted by exposing it to dry or humid atmospheres and was investigated by IR spectroscopy. No changes in water content could be detected, and no significant change in the coloration velocity could be found. To demonstrate the long-term stability of the film, a 1.1 m×0.6 m large window was switched 20,000 times at 20°C over 2 yr without any significant change in performance.     

Stress changes in electrochromic thin film electrodes:: Laser beam deflection method (LBDM) as a tool for the analysis of intercalation processes

The mechanical effects of the intercalation processes in electrochromic WO₃ thin films are reported here and discussed. In particular the electrochemical insertion of H, Li and Na ions in WO₃ was studied by means of laser beam deflection method (LBDM). Linear changes of WO₃ stress were observed for small amounts of the inserted charge and linearity was always associated with a reversible mechanical behavior of thin films. An explanation in terms of homogeneity of the insertion is given. An analogous trend was also verified in the absorbance vs. charge curves. As a consequence the constancy of the electrochromic efficiency values for the three different ions was found. In this way it was possible to determine a full reversible behavior for M_xWO₃ in the composition range 0x0.2. The onset of new phases formation when x exceeded previous upper limit, was observed during Li and Na intercalation. Such transitions brought about the loss of optical and mechanical reversibility. During prolonged hydrogen insertion a reversible slope inversion occurred in stress curve so that it was necessary to take into account different possible mechanisms of the WO₃ electrochromic reaction.     

Structural and electrochemical studies of WO3 films deposited by pulsed spray pyrolysis

Transparent conductive and WO₃ electrochromic thin films were deposited by spray pyrolysis technique. The films were deposited using solutions of WCl₆ in dimethylformamide on SnO₂:F (FTO) substrates with different sheet resistances. Noticeable effects of substrate on structural, morphological and optical properties of the WO₃ films and on its electrochromic behavior are presented and discussed. Hexagonal and monoclinic WO₃ structures were obtained on amorphous glass substrates; also the monoclinic structure on polycrystalline FTO substrates was obtained. Cyclic structural changes during the colored and blanched states were found from XRD and electron diffraction result analysis: The hydrogen tungsten bronze in the tetragonal phase after the hydrogen extraction change to the original WO₃ monoclinic phase.