Synthesis of high-performance electrochromic thin films by a low-cost method

Metal-doping is an effective method to adjust the physical and chemical properties of semiconductor metal oxides. This work adopts a simple solvothermal method to synthesize Mo-doped tungsten oxide nanoparticles. The high-performance electrochromic films can be homogenously formed on ITO glass without post-annealing. Compared with pure WO₃ films, the optimized Mo-doped WO₃ films show improved electrochromic properties with significant optical contrast (68.3% at 633 nm), the short response time (6.3 s and 3.9 s for coloring and bleaching, respectively), and excellent coloration efficiency (107.2 cm² C^?1). The improved electrochromic behavior is mainly due to the increasing diffusion rate of Li⁺ in Mo-doped WO₃ films (increased 20% than that of pure WO₃ films). The porous surface of Mo-doped WO₃ film shortens the diffusion path of Li⁺. Besides, Mo doping reduces the resistance and improves conductivity. Furthermore, 2at% Mo-doped WO₃ films indicate satisfactory energy-storage properties (the specific capacitance is 73.8 F g^?1), resulting from the enhanced electrochemical activity and fast electrical conductivity. This work presents a practical and economical way of developing high-performance active materials for bifunctional electrochromic devices.     

Fast electrochromic response and high coloration efficiency of Al-doped WO3 thin films for smart window applications

Herein, vertically aligned Al:WO₃ nanoplate arrays were directly grown on ITO glass by a facile electrodeposition method and annealed in an argon atmosphere at 450 °C for 2h. Besides, this study reports the influence of Al doping on the electrochromic properties of WO₃ film in detail. Electrochromic properties such as cyclic voltammetry, chronoamperometry and optical transmittance were analyzed by protonic insertion/extraction in the 1 M LiClO₄/propylene carbonate as an electrolyte. The noticeable reversible color changing from transparent to the blue can be realized under the potential bias of ±1.0 V. XRD studies show that the produces films have highly crystalline structure. The EDS results clearly confirm the incorporation of Al element into the WO₃ network. From the optical absorption measurement, direct band gap energies are calculated as 3.62 and 3.34 eV for the WO₃ and the Al:WO₃, respectively. Compared to the as-prepared WO₃, the Al:WO₃ film exhibits outstanding electrochromic performance, including wide optical modulation (55.9%), high coloration efficiency (148.1 cm²C^-1), quick reaction kinetics (1.23 s and 1.01 s for colored and bleaching times, respectively), good rate capability and cycle durability at a wavelength of 632.8 nm. EIS measurements based on a charge-transfer resistance reveal that the dramatic improvement in the electrochemically active surface is achieved in the Al:WO₃ film. The increase of active surface facilitates transport kinetics for electron and ion intercalation/deintercalation within the porous metal oxide to enhance coloration efficiency. Comparatively energy levels of the WO₃ and the Al:WO₃ electrochromic films are also represented. From the Mott-Schottky studies, it is estimated that the donor concentration of the films is of the order of 10²⁰ cm⁻³. Taken together, these results not only provide important insight into a promising electrode for electrochromic displays applications, but also offer an economic and effective strategy for manufacturing of other doped metal oxide films.     

Tailoring the morphology of WO3 films with substitutional cation doping: Effect on the photoelectrochemical properties

With the aim of improving the performance and extending the range of applications of mesoporous WO₃ films, which were initially developed for the photoelectrochemical oxidation of water, we investigated the effect of a number of dopants (lithium, silicon, ruthenium, molybdenum and tin) upon the transparency, crystallinity, porosity and conductivity of the modified films. Tin, molybdenum and silicon were shown to improve the electrochromic behaviour of the layers whereas ruthenium enhanced considerably the electronic conductivity of the WO₃ films. Interestingly, most of the dopants also affected the film morphology and the size of WO₃ nanocrystals. X-ray photoelectron spectra revealed absence of significant segregation of doping elements within the film. Raman analyses confirmed that the monoclinic structure of WO₃ films does not change upon substitutional cation doping; thus, the crystallinity of WO₃ films is maintained.     

Spin coated versus dip coated electrochromic tungsten oxide films: Structure, morphology, optical and electrochemical properties

A sol-gel derived acetylated peroxotungstic acid sol encompassing 4 wt.% of oxalic acid dihydrate (OAD) has been employed for the deposition of tungsten oxide (WO₃) films by spin coating and dip coating techniques, in view of smart window applications. The morphological and structural evolution of the as-deposited spin and dip coated films as a function of annealing temperature (250 and 500 °C) has been examined and compared by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A conspicuous feature of the dip coated film (annealed at 250 °C) is that its electrochromic and electrochemical properties ameliorate with cycling without degradation in contrast to the spin coated film for which these properties deteriorate under repetitive cycling. A comparative study of spin and dip coated nanostructured thin films (annealed at 250 °C) revealed a superior performance for the cycled dip coated film in terms of higher transmission modulation and coloration efficiency in solar and photopic regions, faster switching speed, higher electrochemical activity as well as charge storage capacity. While the dip coated film could endure 2500 color-bleach cycles, the spin coated film could sustain only a 1000 cycles. The better cycling stability of the dip coated film which is a repercussion of a balance between optimal water content, porosity and grain size hints at its potential for electrochromic window applications.     

Solvothermally grown WO3·H2O film and annealed WO3 film for wide-spectrum tunable electrochromic applications

Tungsten trioxide (WO₃) is a classical electrochromic (EC) material with advantages of abundant reserves, high coloration efficiency and cyclic stability. However, WO₃ films are often accompanied by a narrow spectrum of modulation due to a single-color change from transparent to blue. In this work, we report a wide-spectrum tunable WO₃·H₂O nanosheets EC film solvothermally grown on fluorine-doped tin oxide (FTO) glass. Interestingly, the crystalline WO₃·H₂O nanosheets film is transformed into amorphous WO₃ after annealing at 250 °C for 1 h. The amorphous film can be transformed into crystalline WO₃ film by increasing the annealing temperature to 450 °C. After annealing at 250 °C, the WO₃ film exhibits an optical modulation of 75.8% in a broad solar spectrum range of 380–1400 nm and blocks 88.9% of solar irradiance. Fast switching responses of 4.9 s for coloration and 6.0 s for bleaching, and a coloration efficiency of 86.4 cm² C⁻¹ are also achieved. Additionally, the WO₃ film annealed at 250 °C also demonstrates an excellent cyclic stability, where 99.6% of the initial optical modulation can be retained after 1500 cycles. This simple and mild solvothermal method used in this work provides a new idea for the preparation of wide-spectrum tunable WO₃ EC films.     

On the coupled ferroelectric‐electrochromic effect of ε‐WO3

A reversible electrochromic effect has been observed for the first time in flame spray pyrolysis (FSP) processed ε‐WO₃ thin films without the use of an ion storage layer and an electrolytic layer. The dark coloration that appears upon the application of a voltage in films deposited on top of interdigitated gold electrodes is localized to the low voltage (?) electrode arm and it switches to the opposite arm upon a reversal of the polarity. Raman spectroscopy indicated that the coloration was not due to intercalation. It is argued here that the coloration is driven by the asymmetric ferroelectric properties of the ε‐WO₃ crystals and that this electrochromic reversibility is intrinsically coupled with the polarization switching of the device.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

基于WO3-MoO3和TiO2/CdS复合电极的光电致变色器件

电致变色广泛应用于智能窗领域,但电致变色材料仍需外部电源驱动,将太阳能电池与电致变色材料结合起来的光电致变色器件可实现无需外部供电的智能变色调控。性能优异的变色阴极和光阳极是当下光电致变色器件的研究热点。通过水热法制备WO₃-MoO₃薄膜,研究其电致变色性能;通过水热法结合连续离子层沉积法制备TiO₂/CdS复合薄膜,研究其光电转换性能。最后将WO₃-MoO₃薄膜和TiO₂/CdS复合薄膜分别作为光电致变色器件的变色阴极、光阳极构建WO₃/MoO₃-TiO₂/CdS光电致变色器件。WO₃/MoO₃-TiO₂/CdS光电致变色器件具有较大的光学调制范围(630nm处为41.99%)、更高的着色效率(35.787%),将其作为智能窗应用在现代建筑、通行工具等领域具有重要应用价值。     

Electrodeposited Prussian blue films: Annealing effect

The correlation between the temperature-dependent electrochromic (EC) activity and other properties of galvanostatically deposited Prussian Blue (PB) films is presented here. Films subjected to annealing treatment in air at temperatures up to 500 °C were characterized by a variety of techniques which include TGA, XRD, FTIR, UV-vis spectrophotometry, SEM, XPS, cyclic voltammetry etc. The as-deposited X-ray amorphous hydrated PB films were blue in color and had Fe in both Fe^II and Fe^III valence states and were electrochromically active. Consequent to changes in the valence state, degree of hydration and coordination environment of the iron ions upon annealing, EC activity and morphology of the films exhibited dramatic changes. Annealing at moderate temperatures retained the blue color of the films and decreased the EC activity consistent with dehydration and decreased the Fe^II content. Lack of EC activity at higher temperatures was consistent with dehydration and quenching of Fe^II states accompanied with change of color from blue to rust (Fe^III) typical of Fe₂O₃. Independent of the annealing temperature, the films retained their amorphicity, however, prolonged annealing at 500 °C yielded hexagonal Fe₂O₃.     

Multi-electrochromism behavior and electrochromic mechanism of electrodeposited molybdenum doped vanadium pentoxide films

Molybdenum doped vanadium pentoxide (Mo doped V₂O₅) films are prepared by cathodic electrodeposition on indium tin oxide substrate from Mo doped V₂O₅ sol. As an anodic and cathodic coloration electrochromic material, the electrodeposited Mo doped V₂O₅ film presents a better cycling stability, reversibility and multi-electrochromic behavior (orange-yellow-green-blue) with an optical modulation of 60-90% in the spectral region 550-900 nm, which can be expected as a result of enhanced electron intervalence transfer between Mo⁶⁺ and V⁵⁺, V⁴⁺ states, in addition to V⁵⁺ and V⁴⁺ transition. The electrochromic mechanism of Mo doped V₂O₅ films is investigated with atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The surface roughness of the film increase at the different coloration states due to the increasing crystallinity degree. The change of the interlayer spacing for the host V₂O₅ and the change of the C and Li element states verify the insertion of organic solvent into the interlayer of the host V₂O₅ and some of the Li⁺ ions into the sites in the V-O layers. The electrochromic kinetics process indicates that the electrochromism of Mo doped V₂O₅ films can be considered as a reversible reduction/oxidation process accompanying the insertion/extraction of Li⁺ ions and electrons.     

Effects of Sb-doped SnO2–WO3 nanocomposite on electrochromic performance

With the increase in global challenges related to energy depletion, there is significant emphasis on studies involving next-generation optoelectronic applications such as smart windows and electronic displays. In particular, electrochromic devices (ECDs) have been identified as strategic innovations for energy-saving “smart windows” to address these challenges. Despite this increased level of attentions, ECDs have not yet attained broad commercial acceptance because of their limited electrochromic (EC) properties including coloration efficiency (CE,< 30.0 cm²/C) and switching speeds (> 10.0 s). To address these limitations, critical effort is required to enhance the EC properties by tuning the film structure and electronic structure of ECDs. In this study, we demonstrated the effect of nanocomposite structure of conductive metal oxides and WO₃ EC films. Antimony-doped tin oxide nanoparticles (ATO NPs) were utilized because of their superior electrical conductivity and large band gap. To achieve the optimum addition amount of ATO NPs in EC films, we adjusted the amount as 0, 0.6, 1.2, 2.4 wt%. WO₃ EC films with the optimum addition amount (1.2 wt%) of ATO NPs exhibited improved EC performance including both the switching speeds (5.4 s for the coloration speed and 2.4 s for the bleaching speed) and CE value (48.2 cm²/C). The enhancement of EC performance was attributed to the well-dispersed ATO NPs in the WO₃ films that can effectively improve electrical conductivity via the formation of by forming preferred electron pathway. In addition, the large band gap of ATO NPs broadens the transmittance modulation of the EC layer which contributed to the increment of the CE value. Therefore, our results suggest a strategy to obtain the enhanced WO₃ films with superior EC performances using conductive metal oxides nanocomposite structure.     

Effect of different precursor sols on the properties of CeO2-TiO2 films for electrochromic window applications

The properties of spin coated CeO₂-TiO₂ films derived from three different sols containing equimolar quantities of cerium and titanium, fired at 500 °C have been investigated. The films have been deposited using cerium chloride and two different alkoxides and the influence of acetic acid added as a catalyst and modifier of microstructure of the coatings has also been studied. Optical, structural, thermal, and electrochemical properties have been studied and compared. Although gelation time of sols is dependent on the precursor material, enhanced transparency is exhibited by the films prepared with all the sols that have reached the state of gelation. The crystallization behavior and the porosity of the films are highly influenced by the precursor material. Acetic acid derived films with the highest porosity exhibit the highest diffusion coefficient for Li ions. Amorphicity prevailing in films derived from Ti propoxide based precursor sol as against the nanocrystalline films derived from the other sols endow higher ion insertion capacity to former films and highest coloration efficiency is attained when these films are incorporated into an electrochromic device. The highest reversibility for the charging and discharging processes and excellent electrochemical properties observed for the film derived from titanium propoxide prove its practical utility in electrochemical applications. Besides, the highest optical modulation for the electrochromic device comprising WO₃ (electrochromic electrode) and titanium propoxide derived counter electrode is a manifestation of the suitability of the latter electrode in electrochromic window applications.     

Electrochromism and reversible changes in the position of fundamental absorption edge in cathodically deposited amorphous WO3

Amorphous WO₃ (a-WO₃) films have been produced by electrodeposition from a sodium tungstate-based aqueous electrolyte. Their coloration under the action of cathode current in 1N H₂SO₄ is accompanied by a reversible shift of ∼0.42 eV in the fundamental absorption edge of the oxide towards higher quantum energies. The shift of the edge is proportional to the change in the potential of the WO₃ electrode being colored and is caused by the sequential filling, by injected electrons, of levels in the energy spectrum of electronic states formed by the unoccupied d-orbitals of W⁶⁺ centers. The optical characteristics of the W⁵⁺ centers which are formed in this case (color centers of electrochromic material) depend on whether a particular tungsten atom has a double bond to the oxygen atom (WO type bond). At the initial stage of coloration, injected electrons are captured mainly by the W⁶⁺ centers that have no such bonds. Then, W⁶⁺ centers with WO bonds, which have a higher position of the unoccupied d-orbitals on the energy scale, are also filled; this is accompanied by the appearance of an extra absorption band with maximum at ∼2 eV in the optical spectrum of films.     

WOx:Mo薄膜的结构及电致变色性能研究

采用反应磁控溅射工艺,以纯钨和纯钼为靶材在ITO玻璃上制备Mo掺杂WOx电致变色薄膜,用薄膜的透射光谱和XRD衍射方法对掺杂后薄膜的电致变色性能和结构进行了分析,研究了Mo掺杂对WOx薄膜电致变色性能和微观结构的影响机理。实验结果表明：在一定掺杂范围内,Mo掺杂对薄膜电致变色性能有较大提高;掺杂越均匀,对薄膜电致变色性能的改善越显著。影响薄膜电致变色性能的相应掺杂量由溅射时间表示,相对掺量存在最佳值,即7．7％附近,薄膜的变色性能可得到最大的提高,按实验结果趋势分析掺杂量存在有效范围,超出有效掺杂范围,掺杂便会失效。XRD分析表明,掺杂Mo之后的WOx薄膜仍为非晶态,且非晶态有增强的趋势。     

Effect of Ar/O2 ratio on double-sided electrochromic glass performance

This paper reports the qualities of WO₃ film and NiO film added to a counter electrode and their use in a double-sided electrochromic glass device. A mixture of argon and oxygen gasses with ratios of Ar/O₂ of 1.5, 2, 3, and 5 were used for the deposition of the working electrode of WO₃ film for EC glass. The structure of double-side EC glass consists of glass/ITO/NiO/electrolyte/WO₃/ITO/glass/ITO/WO₃/electrolyte/NiO/ITO/glass layers. The working electrode of WO₃ film controls the color presented, the applied voltage controls the color depth, and the counter electrode controls the transparency in the bleached state. The double-sided EC glass with double WO₃ films and double NiO films have faster coloration/bleaching rates than do single-sided EC glass. A mixture of Ar/O₂ ratio of 3.0 has the best coloration/bleaching property of the ratios tested. Compared to the single-sided EC glass, the double-sided EC glass has lower transmittance of about 72% and 6% than the 78% and 12% during coloration and bleaching states in the visible light region with +1.5 V and ?3.5 V applied.     

Electrochromic WO3−x films with reduced lattice deformation stress and fast response time

Electrochromic properties of electrochemically deposited and etched (EDE) WO_3−x films have been investigated using voltammetry and nanogravimetry to elucidate the amount of residual stress associated with lattice polarization and deformation in WO_3−x nanoparticles. The cathodic WO_3−x deposition from pertungstic acid solution and unusual properties of the cathodic electroetching of the oxide in tetraethyl ammonium chloride solution are reported and elucidated on the basis of Electrochemical Quartz Crystal Nanogravimetry (EQCN) measurements. The stress enhanced resonant frequency shift was observed upon WO_3−x film coloration. However, the stress enhancement appeared to be much lower (up to 4-6 times) than that measured for films synthesized by other methods. The stress reduction in WO_3−x films under study has been attributed to the stress relaxing propensity of EDE film to suppress the compressive stress wave. A considerable isotopic effect has been observed in nanogravimetry of the H⁺ and D⁺ ion intercalation into WO_3−x films. We have found that the isotopic effect is primarily due to the true mass loading difference between hydrogen and deuterium ions, for the same concentration of color centers (2.65 × 10²¹ cm⁻³), since EQCN frequency shifts associated with stress in the film for H⁺ and D⁺ are very close to each other.     

Heat treatment of amorphous electrochromic WO3 thin films deposited onto indium-tin oxide substrates

Electrochromic tungsten oxide thin films, obtained by vacuum evaporation, were studied before and after heat treatment between 25 and 250°C for 2 h in air. Electrochromic properties were investigated in acid electrolyte by simultaneous measurements of the electrical and optical parameters. A.c. complex impedance techniques and voltammetry were used to characterize the films from an electrical point of view. We observed an enhancement of the electrochromic response times during both coloration and bleaching after heat treatment carried out between 150 and 220°C. This phenomenon was associated with a decrease of the ohmic drop in the electrode and a continuous variation of the impedance diagrams of these electrochromic electrodes. Moreover, we observed that the diffusion coefficient of H⁺ ions into WO₃, obtained on colored thin films, increased as the electrochromic kinetics increased.     

Interfacial Fe(III)-hydroxide formation during Fe-Pt alloy deposition

Fe-Pt films with an Fe/Pt ratio close to one can be electrodeposited from an FeSO₄-H₂PtCl₆-Na₂SO₄electrolyte. At the deposition potential, the hydrogen evolution and the reduction of the Pt complex are diffusion limited, and Fe overpotential deposition has not yet set in. The sources of the Fe incorporation are iron hydroxide formation together with Fe underpotential deposition due to Fe-Pt alloy formation. Mössbauer measurements show that the iron in the iron hydroxide is predominantly Fe(III). For stoichiometry reasons, a Pt-rich Fe-Pt phase must be present in addition to the Fe(III)-hydroxide. The Fe³⁺ that takes part in the hydroxide formation is produced in the electrolyte by the oxidation of Fe²⁺ by the complexed Pt ion. This exchange reaction results in a significantly higher Fe³⁺ content in the FeSO₄-H₂PtCl₆-Na₂SO₄ electrolyte in comparison to the same electrolyte without H₂PtCl₆. Fe(III)-hydroxide formation can be depressed by adding citric acid, that acts as buffering and complexing agent. This leads to a lower iron content of the deposits. The Fe/Pt ratio close to one that is needed for hard magnetic properties can, however, only be achieved with a significant incorporation of iron hydroxide.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Performance of a single-phase hybrid and nanocomposite polyelectrolyte in classical electrochromic devices

In this paper, we discuss the high stability of a single-phase hybrid polyelectrolyte (SPHP) and nanocomposite hybrid polyelectrolyte (NHP) in a large electrochromic (EC) device (5 cm × 10 cm) mounted with different electrodes. The electrochromic device (K-glass/FTO/WO₃/SPHP/CeO₂-TiO₂/FTO/K-glass—ECI, K-glass/FTO/WO₃/NHP/CeO₂-TiO₂/FTO/K-glass—ECII,) exhibited excellent color and bleach reversibility, high coloration efficiency (CE) (>35 cm²/C) from the first cycle up to more than 60,000 CA cycles, and a maximum constant rate of deintercalation/intercalation (O_out/Q_in = 1). Also, the life time of the EC device with Nb₂O₅:Mo (K-glass/FTO/Nb₂O₅:O/SPHP/CeO₂-TiO₂/FTO/K-glass—ECIII) was prolonged to up to more than 10,000 cycles with a fairly stable coloration efficiency (around 19 cm²/C) and O_out/Q_in = 1. The SPHP and NHP were tested in a large EC device with different configurations to evaluate its successful performance. In conclusion, its remarkable behavior and high stability render this material an excellent candidate for application in EC devices.