Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Self-supported semi-interpenetrating polymer networks for new design of electrochromic devices

This paper reports the preparation of conducting films combining linear poly(3,4-ethylenedioxythiophene) (PEDOT) and cross-linked polyethylene oxide (PEO) into semi-interpenetrating networks. Due to the synthetic pathway, PEDOT is distributed within the PEO matrix and specifically along the two outer faces of the film. Such a distribution of the conducting polymer inside the matrix leads to the design of a self-supported and symmetrical PEDOT-Polymer electrolyte-PEDOT electrochromic device which can substitute the usual multilayer configuration. Optical contrast ΔT_630 nm (%) up to 33% is reached without contrast loss after 1500 switches. The switching time is 30 s for bleaching with a good memory effect (less than 1% decrease of transmittance after 1 h) of the device.     

Solid-state electrochromic devices with Nb2O5:Mo thin film and gelatin-based electrolyte

A gelatin-based electrolyte has been developed and characterized by impedance spectroscopy, X-ray diffraction, UV-vis-NIR spectroscopy and atomic force microscopy (AFM). The heat treatment temperature was found the key factor affecting its ionic conductivity that increases from 1.5 × 10⁻⁵ S/cm to 4.9 × 10⁻⁴ S/cm by heating from room temperature up to 80 °C. The temperature dependence of the ionic conductivity exhibits an Arrhenius behavior. EC-devices with the configuration K-glass/Nb₂O₅:Mo EC-layer/gelatin-based electrolyte/(CeO₂)_x(TiO₂)_1−x ion-storage (IS) layer/K-glass, have been assembled and characterized. They show a good long time cyclic stability, but the change of the optical density measured at 550 nm after 25 000 cycles was only 0.13.     

Electrosynthesis and characterization of an electrochromic material from poly(1,4-bis(2-thienyl)-benzene) and its application in electrochromic devices

1,4-Bis(2-thienyl)-benzene monomer is successfully synthesized via coupling reaction. Poly(1,4-bis(2-thienyl)-benzene) (PBTB) is electrochemically synthesized and characterized. Resulting polymer film has distinct electrochromic properties. Its application in electrochromic devices (ECDs) is discussed. PBTB is switched between yellow in the neutral state and green in the oxidized state. Electrochromic switching of PBTB film is performed and the polymer film shows a maximum optical contrast (ΔT %) of 44.8% at 610 nm in visible region with a response time of 1.6 s. The coloration efficiency (CE) of PBTB is calculated to be 162 cm² C⁻¹. Electrochromic device (ECD) based on PBTB and poly(3,4-ethylenedioxythiophene) (PEDOT) is also constructed and characterized. Maximum contrast (ΔT %) and switching time of the device are measured as 29.5% and 0.43 s at 628 nm. The CE of the device is calculated to be 408.9 cm² C⁻¹. Clear change from green (at neutral state) to blue color (at full oxidized state) of this ECD is demonstrated with reasonable cycle life.     

Preparation of electrochromic Ni1−xO and TiO2 coatings from pigment dispersions and their application in electrochromic foil based devices

Thin (100–400 nm) electrochromic TiO₂ and Ni_1−xO coatings providing transmissive light modulation were made from an anatase pigment dispersion obtained by co-grinding nanocrystalline titanium particles (6–10 nm in size) with trisilanol heptaisobutylsilsesquioxane as dispersant, while Ni_1−xO based pigment dispersions were made by milling pre-prepared Ni_1−xO pigment with nickel oxyhydroxide (NiO_xH_y) dispersant. Dispersions were obtained by milling the pigments with zirconia beads of various sizes (0.1, 0.2 and 0.4 mm) and the particle size was determined with the dynamic light scattering technique (DLS). Pigment dispersions were deposited by spin-coating on glass and plastic (PET) film and thermally treated at 150 °C to obtain thin TiO₂ and Ni_1−xO pigment coatings. SEM and AFM were used for determination of the surface morphology, revealing their homogenous structure and low surface roughness (up to 20 nm). The optical transmittance and haze of the coatings deposited on glass and PET film were determined from the UV–vis spectra. Their electrochromic effect was analyzed by electrochemical charging/discharging the coatings in a LiClO₄/PC electrolyte. The results demonstrated a convenient, simple and robust technique for making “electrochromic paint” coatings. Pre-prepared TiO₂ and pigments were used for construction of foil-based electrochromic devices with transmissive modulation of light.     

A red-to-gray poly(3-methylthiophene) electrochromic device using a zinc hexacyanoferrate/PEDOT:PSS composite counter electrode

In this paper, we describe a novel red-to-gray poly(3-methylthiophene) (PMeT) electrochromic device (ECD) with the aid of a zinc hexacyanoferrate (ZnHCF)/PEDOT:PSS counter electrode. The application of ZnHCF to an ECD is first reported. ZnHCF has long suffered from poor deposition yield problem, but we demonstrate that a robust ZnHCF film can be prepared by spin coating of a liquid suspension composed of ZnHCF nanoparticles and PEDOT:PSS ink on ITO. It was found that the ZnHCF/PEDOT:PSS composite worked much better with PMeT than pure ZnHCF or pure PEDOT:PSS from both electrochemical and optical aspects. With a LiClO₄/PC electrolyte, the PMeT ECD having ZnHCF/PEDOT:PSS as its counter electrode could be reversibly switched between its red state (>0.8 V) and its gray state (<0 V). For a 2 cm × 2 cm prototype device, the response time for coloration was less than 1 s. The maximum transmittance modulation of the device could attain 45.3% at 750 nm, which resulted in a corresponding coloration efficiency of 336.8 cm²/C. The maximum contrast ratio was 5.45 at 720 nm. In addition, the charge capacity of the ECD could retain 95% of its original value after 10,000 cycles of cyclic voltammetry aging test, although an electrodeposited PMeT film alone could be cycled several hundred times only. To sum up, this work proposes a new, cost-effective transparent counter electrode and brings a stable, high visual-contrast PMeT ECD prototype for further development of a red-color bistable display.     

工艺参数对磁控溅射WO_3薄膜电致变色性能的影响

本文采用磁控溅射法制备了用于电致变色器件的WO_3薄膜,用X射线衍射仪(XRD)、场发射扫描电镜(FE-SEM)、紫外-可见分光光度计(UV-Vis)对其物相组成、微观形貌以及电致变色性能进行了表征。结果表明:在溅射压强为2 Pa、氩氧比为60:20时所制备的WO_3薄膜厚度适中,且有利于离子的嵌入/脱出,而以此薄膜制备的电致变色器件光调制范围最大,褪色时间最短,着色效率达82.9 cm~2/C。     

Synthesis of transfer-free graphene films on dielectric substrates with controllable thickness via an in-situ co-deposition method for electrochromic devices

The solutions and polymer supported materials in graphene transfer process would introduce lots of containments, defects and wrinkles, which weakens the performance of graphene. Herein, an in-situ co-deposition method is carried out to obtain transfer-free graphene films with controllable thickness on several dielectric substrates. The amorphous carbon (carbon source) and copper (catalyst) are co-deposited on dielectric substrates. Followed by an in-situ annealing process, the amorphous carbon is transformed to few-layer graphene. High co-deposition temperature could promote the decomposition of Cu(acac)₂ precursors, leading to the controllable thickness of amorphous carbon layer in Cu@C films. Finally, 3-, 5-, 8- and 10- layers graphene films with transmittance of up to 93.5% and square resistance of 0.8 kΩ·sq^?1 are obtained and a high-performance electrochromic device is fabricated using 3 layers graphene films as electrodes. The “color” and “bleach” time of the electrochromic device is 16.6 s and 6.8 s with the transmittance of 26.8% and 79.7% separately. This method paves an alternative way for the batch production of transfer-free graphene film as electrode materials.     

Effects of SiO2 and Al2O3 nanofillers on polyethylene properties

Polymers filled with inorganic nanoparticles have become interesting materials as dielectrics because of their improved mechanical and electrical properties compared with the unfilled polymers and with polymer microcomposites. These improvements are mainly due to the large surface area of nanoparticles and new polymer–nanofiller interface characteristics. In the present work, polyethylene nanocomposites with SiO₂ and Al₂O₃ nanoparticles were prepared by melt mixing. Mechanical and electrical properties of these composites were determined and morphological aspects were revealed by scanning electron microscopy, wide‐angle X‐ray diffraction, and atomic force microscopy. The effect of nanostructure and the importance of nanofiller dispersion were analyzed in connection with mechanical and electrical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The investigation of the tribocorrosion properties of DLC coatings deposited on Ti6Al4V alloys by CFUBMS

Various machine components produced from titanium alloys used in various industries are subject to a combination of electrochemical and mechanical effects. The science of surface transformations resulting from the interaction of mechanical loading and chemical reactions that occur between elements of a tribosystem exposed to corrosive environments is described as tribocorrosion. This research focuses on the tribocorrosion behaviour of Ti6Al4V alloys after coated by using closed field unbalance magnetron sputtering (CFUBMS). The structural analyses of the coatings were performed using Raman spectroscopy and scanning electron microscopy (SEM). Tribocorrosion experiments were performed in a pin-on-disc tribotester under electrochemical polarisation in NaCl 1 wt.% solution. This study shows that the Ti-DLC coating is protecting the Ti6Al4V alloy and having good performance in corrosion and tribocorrosion conditions. The OCP values for Ti6Al4V substrate and Ti-DLC protective coatings during tribocorrosion tests were measured as −560 V and −330 V, respectively. These results showed that Ti-DLC protective coating on Ti6Al4V substrates increased the tribocorrosion resistance by acting as a barrier layer.     

Electrochromic switching and nanoscale electrical properties of a poly(5-cyano indole)-poly(3,4-ethylenedioxypyrrole) device with a free standing ionic liquid electrolyte

Poly(5-cyano indole) or PCIND and poly(3,4-ethylenedioxy pyrrole) or PEDOP films have been electro-synthesized for the first time in a hydrophobic ionic liquid: trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate. PCIND, is an anodically coloring electrochrome, and exhibited a reversible switching between a transmissive yellow and a saturated green hue, with an absorption maximum at 650 nm in the fully oxidized state. Conducting atomic force microscopy studies revealed the PCIND film to be composed of an ensemble of segregated high current islands with a nanoscale electronic conductivity of 0.1 S cm⁻¹ and a band gap of 1.41 eV. The cathodically coloring PEDOP film comprised of uniformly distributed and inter-connected high current carrying domains with a band gap of 1.82 eV and a conductivity of 5.4 S cm⁻¹. Prototype electrochromic devices were fabricated using PEDOP and PCIND as cathode and anode with a thermally stable ionic liquid based, free standing polymeric gel film with a high ionic conductivity of 1.19 × 10⁻³ S cm⁻¹ as the electrolyte. The device showed large coloration efficiencies of 480 and 796 cm² C⁻¹ at visible and NIR wavelengths of 475 and 1100 nm respectively which far exceeded the coloration efficiencies of the individual electrochromes, thereby demonstrating the synergy between the two colorants. The performance attributes of the device, which switched reversibly between red, green and blue hues, are an outcome of an interplay between the high nanolevel electron conduction capabilities (enable fast charge transport) and high ion storage capacities (increase optical contrast as more number of electrochemically addressable sites are accessed by the electrolyte ions) of the PEDOP and PCIND films. Our studies demonstrate the applicability of PCIND films as anodic electrochromes in energy efficient windows.     

Effect of laser power density on the electrochromic properties of WO3 films obtained by pulsed laser deposition

Pulsed laser deposition (PLD) was used to prepare tungsten trioxide (WO₃) films on ITO substrates with a varying laser power density of 4.0–5.5 W/cm². XPS indicated that when the laser power density decreased, the peak positions of the W 4f and O 1s orbits shifted slightly to low energy due to the difference in oxygen vacancies. As the laser power density decreased, W⁶⁺ gradually replaced the lattice position of O^2?, increasing oxygen vacancies in the lattice. The transmittance modulated values (ΔT) were over 44% at 830 nm, indicating strong absorption by the WO₃ thin films in the near-infrared ray. The switching time of the WO₃ thin films between bleached states and coloured states decreased as the laser power density increased due to the amorphous structure, morphology, and lower oxygen deficiency at a high power density. The high ΔT and very fast switching time of t_b (1.09 s) and t_c (6.01 s) demonstrated the excellent electrochromic (EC) properties of the WO₃ films prepared by PLD.     

Design and fabrication of MoSe2/WO3 thin films for the construction of electrochromic devices on indium tin oxide based glass and flexible substrates

Electrochromic devices (ECDs) have the ability to block the heat generated by sunlight, making them ideal for use in smart windows. Herein, we report the fabrication of ECDs using MoSe₂/WO₃ (MSW) as the electrochromic material, for smart windows applications. A solvothermal method was used for the synthesis of MoSe₂, while WO₃ was synthesized using a sol-gel approach. Subsequently, MoSe₂/WO₃ (MSW) hybrids with different wt% of MoSe₂ (0.05 wt%, 0.2 wt%, 0.5 wt%) were synthesized using an ultra-sonication approach. The physicochemical features of these MSW hybrids herein termed as MSW 0.05, MSW 0.2 and MSW 0.5, were investigated using X-ray diffraction (XRD), X-ray photon electron spectroscopic (XPS), scanning electron microscope (SEM), and EDS techniques and compared with pristine MoSe₂ and WO₃. The ECDs synthesized using MSW 0.05 showed increased coloration efficiency (62 cm^2 C-1) with an applied potential range of 0 to −1.5 V. Subsequently, the ECDs based on indium tin oxide (ITO) and MSW 0.05 demonstrated excellent electrochromic performance and stability for 10,000 cycles. The enhanced electrochromic performance of the MSW-based ECDs may be attributed to the conductive nature as well as the synergistic effects between MoSe₂ and WO₃ when compared to the WO₃-based ECDs. The synthesized MSW also showed promise as an electrochromic material in flexible ECDs for smart windows applications.     

Effect of microstructure on the adhesion strength of TiBx coating on Ti6Al4V substrate

TiB_x coatings were deposited on Ti6Al4V and Si (100) wafer substrates by D.C. magnetron sputtering with various target-to-substrate distances (T.S. distances) from 50 mm to 200 mm. The influence of T.S. distance on the microstructure, hardness and adhesion strength of TiB_x coatings and Ti6Al4V substrate system was investigated. Results showed that the microstructure of TiB_x coatings transformed from dense to fibre columnar grain with the increase in T.S. distance, whilst the hardness decreased from 20.9 GPa to 9.4 GPa. The Rockwell-C indentation adhesion strength grade was also improved from HF6 to HF1. An adhesion evaluation factor G, which is related to the mechanical properties and the microstructure of TiB_x coating, is proposed based on the test results. The adhesion strength increased with G, which corresponded well with the results of indentation test. The high-speed rubbing test with a sliding speed of 300 m/s was performed to check the Al-adhesion resistance of the TiB_x coating against Al–hBN seal coating.     

Room temperature sputtering deposition of high-haze Ga-doped ZnO transparent conductive thin films on self-textured bio-based poly(ethylene 2, 5-furandicarboxylate) substrates

In this work, bio-based poly(ethylene 2,5-furandicarboxylate) (PEF) films were prepared by drop-casting method and used as substrates for depositing Ga-doped ZnO (GZO) transparent conductive thin films. Results showed that the 300-nm GZO thin films deposited on PEF substrates exhibited haze values above 65% at 550 nm without post-treatment. The high haze value was because of the large surface roughness of PEF films. The total optical transmittance and electrical properties of GZO thin films on PEF were comparable to those of GZO thin films on PET. The present study provides a simple way for the sputtering deposition of high-haze transparent conductive thin films on flexible substrates.     

A novel approach for solution combustion synthesis of tungsten oxide nanoparticles for photocatalytic and electrochromic applications

Tungsten oxide (WO₃) and tungsten oxide hydrate (WO₃.H₂O) nanoparticles were synthesized via a novel solution combustion synthesis (SCS) method. Various organic fuels (i.e. oxalic acid, glycine, and citric acid) and heat sources were used to obtain different morphologies of nanoparticles. Combustion thermodynamic relations were explained based on propellant chemistry. Adiabatic temperature (T_ad) and specific impulse (I_sp) were also obtained. The synthesized nanoparticles were investigated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and UV–Visible spectrophotometer. XRD patterns indicated that the structures were transformed from orthorhombic and amorphous structures to monoclinic and tetragonal ones, respectively, upon combustion on the hot plate. Fourier-transform infrared (FTIR) spectra provided evidence of WO₆ octahedral. SEM images showed different microstructures from sponge or rock-like to fine spherical particles with up to 100 nm size. The obtained band gap of all samples was higher than 2.6 eV which is the band gap of bulk tungsten oxide. The synthesized WO₃ nanoparticles showed over 50% photocatalytic efficiency for the degradation of azo dye. The results exhibited that the nanoparticles can be used to make the electroactive layer for electrochromic applications.     

Improving the adhesive,mechanical, tribological properties and corrosion resistance of reactive sputtered tantalum oxide coating on Ti6Al4V alloy via introducing multiple interlayers

Tantalum oxide film has become an investigation focus for surface modification materials in the biomedical field owing to its outstanding biocompatibility, anti-corrosion, and anti-wear performances. However, tantalum oxide films exhibit poor adhesion because of the mismatch between the properties of the film and the substrate. In this study, a novel multilayer tantalum oxide coating of Ta_mO_n/Ta_mO_n-TiO₂/TiO₂/Ti (code M-Ta_mO_n) was deposited on Ti6Al4V by magnetron sputtering with Ta_mO_n single-layer coating as control. The purpose of this work is to evaluate the influence of the introduced Ta_mO_n-TiO₂/TiO₂/Ti multi-interlayer on the microstructure, adhesive, mechanical, and anti-corrosion properties of reactive sputtered tantalum oxide coatings. The outcomes show that the Ta_mO_n-TiO₂/TiO₂/Ti intermediate layer improves the bonding strength between the Ta_mO_n layer and Ti6Al4V matrix from 17.83 N to over 50 N and enables the Ta_mO_n coating to have an increased H/E and H³/E² ratio, decreased friction coefficient and wear rate, raised potential, and reduced corrosion current density. The improved properties of the multilayer system are attributed to the positive effects of the inserted multiple interlayers in reducing the residual stress in the coating, coupling the mechanical performance between the layer and the substrate, blocking the continuous growth of penetrating defects in a film with columnar structure. These experimental results provide a workable route for improving the properties of the tantalum oxide coating on Ti6Al4V alloy for medical applications.     

Effect of post annealing treatment on electrochromic properties of spray deposited niobium oxide thin films

Niobium oxide thin films were deposited on the glass and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive spray pyrolysis technique. During deposition of the films various process parameters like nozzle to substrate distance, spray rate, concentration of sprayed solution were optimized to obtain well adherent and transparent films. The films prepared were further annealed and effect of post annealing on the structural, morphological, optical and electrochromic properties was studied. Structural and morphological characterizations of the films were carried out using scanning electron microscopy, atomic force microscopy and X-ray diffraction techniques. Electrochemical properties of the niobium oxide thin films were studied by using cyclic-voltammetry, chronoamperometry and chronocoulometry.