Optical properties of chemical vapor deposited thin films of molybdenum and tungsten based metal oxides

Thin films of tungsten oxide, molybdenum oxide and mixed MoO₃–WO₃ oxides were obtained by atmospheric pressure chemical vapor deposition (CVD). All the films were prepared using identical technological parameters and through investigation of the optical properties of as deposited and annealed at 400°C a comparative study is reported. Raman, IR and VIS spectrophotometry and spectral ellipsometry methods were used. The mixed MoO₃–WO₃ films have higher optical absorption with maxima at a closer position with respect to the human eye sensitivity peak at 2.5 eV. The observed electrochromic effect is better expressed in the mixed films; the electrical charge inserted is higher.     

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.     

Electrochromic behavior of Ni---W oxide electrodes

A new electrochromic material, Ni---W oxide, was fabricated by a reactive sputtering method and the effects of tungsten concentration in Ni---W oxide thin films on the electrochromic behavior were investigated. It has been found that the charge transfer resistance which has been known to be very high in NiO_x becomes significantly low with the addition of tungsten in NiO_x. It turned out that the charge transfer density during the cyclic voltammetry increased considerably with the addition of tungsten in NiO_x such that at an optimum concentration of tungsten (atomic ratio of W/Ni = 0.33), a fast optical switching with the insertion and removal of lithium in Ni---W oxide thin films could be expected. The electrochromic display device composed K_0.3WO_3.15 and Ni---W oxide was fabricated and its optical switching characterized.     

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.     

Stress in photochromic and electrochromic effects on tungsten oxide film

Optical absorbance at 632.8 nm and the stress generated in tungsten oxide film due to photochromic and electrochromic effects were measured. WO₃ thin films were deposited by reactive sputtering and the absorbance was obtained by measuring the optical transmittance of a laser beam through the film. The stress was calculated by measuring the substrate curvature and using the Stoney equation for multilayered films, since two layers are deposited onto a substrate for the electrochromism studies. The optical absorbance and the stress in the tungsten oxide film, as a function of UV irradiation time in photochromism and of inserted charge in electrochromism, are showed and discussed. In both effects the stresses generated were rendered as due to cation insertions into the film: H⁺ protons in photochromism and Li⁺ ions in electrochromism. The accuracy of the Stoney equation used for the stress calculation was also discussed.     

The electrochromic and photocatalytic properties of electron beam evaporated vanadium-doped tungsten oxide thin films

The electrochromic and photocatalytic properties of vanadium-doped tungsten trioxide thin films prepared at room temperature (300 K) by the electron beam evaporation technique are reported in this paper. The vanadium to tungsten ratio (V/W) in these films are 0.003, 0.019, 0.029 and 0.047. The optical band gap of the vanadium-doped tungsten oxide (WO₃) thin film initially increases from 3.16 to 3.28 eV for V/W ratio 0.003 then decreases to 3.15 eV for V/W ratio 0.047. These vanadium-doped films switch between neutral gray and transparent states. The coloration efficiency (CE) decreases from 82 cm² C⁻¹ (pure WO₃) to 27 cm² C⁻¹ for the film containing V/W ratio 0.047. The photocatalytic activity has enhanced with vanadium doping and maximum activity of 15% (percentage change in optical density of methylene blue due to photo degradation) has been observed for the film containing V/W ratio of 0.019. The Kelvin probe measurements show that the work function of pure WO₃ films is 4.07 eV and vanadium doping initially increases the work function to 4.19 eV for V/W ratio 0.019 and then decreases it to 3.97 eV for film with V/W ratio 0.047.     

The electrochromic properties of chemically deposited tungsten oxide films

Thin films of tungsten oxide were prepared by deposition from a solution of tungsten chloride, and, for comparison, by the acidification of a solution of sodium tungstate. The electrochromic behavior of these films was investigated by studying their current-voltage behavior, absorbance spectra, response time, and the diffusion coefficient of lithium ions in the film.     

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.     

Hydrothermal synthesis of electrode materials pyrochlore tungsten trioxide film

Hydrothermal synthesis methods have been successfully used to prepare new transition-metal oxides for cathodes in electrochemical devices such as lithium batteries and electrochromic windows. The tungsten oxides were the first studied, but the method has been extended to the oxides of molybdenum, vanadium and manganese. Sodium tungsten oxide films with the pyrochlore structure have been prepared on gold/alumina and indium-doped tin oxide substrates. These films reversibly and rapidly intercalate lithium and hydrogen ions.     

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 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.     

Electrical conductivity as a function of temperature in amorphous lithium tungsten oxide

Tungsten oxide is a widely used electrochromic material for smart windows. In order to study the charge carriers involved in the electrochromic process, it is important to characterize the electrical transport in tungsten oxide. Substoichiometric amorphous tungsten oxide films were prepared by DC-magnetron sputtering. The films were electrochemically intercalated with lithium. The Li/W intercalation ratios for the tungsten oxide films were in the range 0.15–0.53. Temperature dependent resistivity measurements were performed in the temperature range 77–300 K for samples at different lithium intercalation levels. It was found that the data are consistent with the variable range hopping model.     

Electrochromic glasses prepared by the sol–gel method

Electrochromic glass films of tungsten oxide have been prepared by the sol–gel method. Counter electrode of titanium and cerium oxide were obtained by the same method. The spectral time response as well as the charge capacity were measured as a function of the conductivity of the conductive support glasses. Optimum conditions for the electrochromic device operation were established.     

Promotion of electrochromism in spray-deposited molybdenum oxide-doped iridium oxide thin films

Electrochromic molybdenum oxide-doped iridium oxide thin films were prepared by using a pneumatic spray pyrolysis technique onto fluorine-doped tin oxide (FTO) coated conducting glass substrates. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride in different volume proportions and the resultant solution was used as a precursor for spraying. An aqueous electrolyte (0.5 N H₂SO₄) was used to study electrochromic properties of thin films using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. During the potential scan the iridium oxide electrode switches between coloured and bleached state due to Ir⁺⁴–Ir⁺³ intervalency charge transfers. The optical density difference (ΔOD)_λ=630 nm and colouration efficiency was maximum for 2% molybdenum oxide-doped sample. Moreover, loss in charge density during extended cycling is less than undoped and other doped (>2%) samples.     

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%.     

Optical indices of lithiated electrochromic oxides

Optical indices have been determined for thin films of several electrochromic oxide materials. One of the most important materials in electrochromic devices, WO₃, was thoroughly characterized for a range of electrochromic states by sequential injection of Li ions. Another promising material, Li_0.5Ni_0.5O, was also studied in detail. Less detailed results are presented for three other common lithium-intercalating electrochromic electrode materials: V₂O₅, LiCoO₂, and CeO₂–TiO₂. The films were grown by sputtering, pulsed laser deposition (PLD) and sol–gel techniques. Measurements were made using a combination of variable-angle spectroscopic ellipsometry and spectroradiometry. The optical constants were then extracted using physical and spectral models appropriate to each material. Optical indices of the underlying transparent conductors, determined in separate studies, were fixed in the models of this work. The optical models frequently agree well with independent physical measurements of film structure, particularly surface roughness by atomic force microscopy. Inhomogeneity due to surface roughness, gradient composition, and phase separation are common in both the transparent conductors and electrochromics, resulting sometimes in particularly complex models for these materials. Complete sets of data are presented over the entire solar spectrum for a range of colored states. These data are suitable for prediction of additional optical properties such as oblique transmittance and design of complete electrochromic devices.     

Recent advances in electrochromics for smart windows applications

Electrochromic smart windows are able to vary their throughput of radiant energy by low-voltage electrical pulses. This function is caused by reversible shuttling of electrons and charge balancing ions between an electrochromic thin film and a transparent counter electrode. The ion transport takes place via a solid electrolyte. Charge transport is evoked by a voltage applied between transparent electrical conductors surrounding the electrochromic film/electrolyte/counter electrode stack. This review summarizes recent progress concerning: (i) calculated optical properties of crystalline WO₃, (ii) electrochromic properties of heavily disordered W oxide and oxyfluoride films produced by reactive magnetron bias sputtering, (iii) novel transparent reactively sputter-deposited Zr–Ce oxide counter electrodes and (iv) a new proton-conducting antimonic-acid-based polymer electrolyte. Special in depth presentations are given on elastic light scattering from W-oxide-based films and of electronic band structure effects affecting opto–chronopotentiometry data in Zr–Ce oxide. The review also contains some new device data for an electrochromic smart window capable of very high optical transmittance.     

A complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane and tungsten oxide

In this paper we report a high-contrast complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane (POSS-PANI) and tungsten oxide (WO₃). The electrochromic properties, cyclic voltammetry behavior and coloration efficiency of the device are studied. Due to the loosely packed structure of POSS-PANI, it possesses more accessible doping sites and hence gives rise to a significantly higher electrochromic contrast than polyaniline (PANI). Furthermore, the replacement of PANI with POSS-PANI as the complementary layer for WO₃ leads to an enhanced complementary effect, for which the underneath mechanism is also discussed.     

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.     

电子束蒸发氧化钨薄膜电致变色性能的研究

报道了电子束蒸发制备的氧化钨薄膜的电臻变色特性和开关寿命，给出了电极电压和电解浓浓度对氧化钨薄膜电致变色性能的影响。