Investigation of an Electrochromic Device Based on Ammonium Metatungstate-Iron (II) Chloride Electrochromic Liquid.

Even though electrochromism has been around for more than 50 years, it still has several issues. Multi-layered films, high manufacturing costs, and a short lifetime are present in existing electrochromic devices. We demonstrate a unique high-performance device with a basic structure and no solid electrochromic sheets in this work. In this device, the electrolyte layer is also avoided. The device uses an electrochromic solution prepared from a mixture of ammonium metatungstate and iron (II) chloride solution as a functional layer with reversible redox properties. The tungstate ions on the electrode surface are reduced when the device is colored, and the Fe2+ on the electrode surface is oxidized on another electrode surface. The generated Fe3+ in the mixed functional layer oxidizes the previously reduced tungstate ions as the device fades. We determined the ΔT (transmittance modulation) and response time among ammonium metatungstate ratios, iron (II) chloride ratios, and driven current density using DOE (design of experiment) trials. Using 0.175 mol/L ammonium metatungstate and 0.30 mol/L iron (II) chloride, a device with outstanding ΔT (more than 57% at 700 nm), a short response time (less than 10 s), and high coloring efficiency (160.04 cm2/C at 700 nm) is demonstrated.

A Strategy toward Realizing Narrow Line with High Electrical Conductivity by Electrohydrodynamic Printing.

Over the past few decades, electrohydrodynamic (EHD) printing has proved to be an environmentally friendly, cost-effective and powerful tool in manufacturing electronic devices with a wire width of less than 50 µm. In particular, EHD printing is highly valued for the printing of ultrafine wire-width silver electrodes, which is important in manufacturing large-area, high-resolution micron-scale or even nanoscale structures. In this paper, we compare two methods of surface modification of glass substrate: UV treatment and oxygen plasma treatment. We found that oxygen plasma was better than UV treatment in terms of wettability and uniformity. Secondly, we optimized the annealing temperature parameter, and found that the conductivity of the electrode was the highest at 200 °C due to the smoothing silver electrode and the oxidation-free internal microstructure. Thirdly, we used EHD printing to fabricate silver electrodes on the glass substrate. Due to the decrease of conductivity as a result of the skin effect and the decrease of silver content, we found that driving voltage dropped, line width decreased, and the conductivity of silver line decreased. After the optimization of the EHD printing process, Ag electrode line width and conductivity reached 19.42 ± 0.24 µm and 6.01 × 106 S/m, demonstrating the potential of electro-hydraulic printing in the manufacturing of flexible, wearable, high-density, low-power-consumption electronics.

Alloy-Electrode-Assisted High-Performance Enhancement-Type Neodymium-Doped Indium-Zinc-Oxide Thin-Film Transistors on Polyimide Flexible Substrate.

Flexible thin-film transistors with high current-driven capability are of great significance for the next-generation new display technology. The effect of a Cu-Cr-Zr (CCZ) copper alloy source/drain (S/D) electrode on flexible amorphous neodymium-doped indium-zinc-oxide thin-film transistors (NdIZO-TFTs) was investigated. Compared with pure copper (Cu) and aluminum (Al) S/D electrodes, the CCZ S/D electrode changes the TFT working mode from depletion mode to enhancement mode, which is ascribed to the alloy-assisted interface layer besides work function matching. X-ray photoelectron spectroscopy (XPS) depth profile analysis was conducted to examine the chemical states of the contact interface, and the result suggested that chromium (Cr) oxide and zirconium (Zr) oxide aggregate at the interface between the S/D electrode and the active layer, acting as a potential barrier against residual free electron carriers. The optimal NdIZO-TFT exhibited a desired performance with a saturation mobility (µ sat) of 40.3 cm2·V-1·s-1, an I on/I off ratio of 1.24 × 108, a subthreshold swing (SS) value of 0.12 V·decade-1, and a threshold voltage (V th) of 0.83 V. This work is anticipated to provide a novel approach to the realization of high-performance flexible NdIZO-TFTs working in enhancement mode.

Physical Simulation Model of WO3 Electrochromic Films Based on Continuous Electron-Transfer Kinetics and Experimental Verification.

Tungsten oxide (WO3) electrochromic devices have attracted a lot of interest in the energy conservation field and have shown a preliminary application potential in the market. However, it is difficult to quantitatively direct experiments with the existing electrochromic theoretical models, which can restrict the further development of electrochromism. Here, an electrochromic physical simulation model of WO3 films was built to solve the above problem. Experimentally, the actual electrochromic kinetics of WO3 in the LiClO4/propylene carbonate electrolyte was determined as a continuous electron-transfer process by cyclic voltammetry measurement and X-ray photoelectron spectroscopy analysis. Theoretically, the continuous electron-transfer process, Li+-ion diffusion process, and the transmittance change process were described by a modified Butler-Volmer equation, Fick's law, and charge versus coloration efficiency/bleaching efficiency coupling equation, respectively. The comparisons between theoretical and experimental data were conducted to verify this model. The shape of the simulated current curves was basically consistent with that of experiments. Besides, the difference of transmittance between the simulation and experiments was less than 8%. The difference between theory and experiment was attributed to the influence of the electric double layer and the actual reaction interface. The success of the simulation was attributed to the accurate description of the electrochromic process by continuous electron-transfer kinetics. This model can be applied in the research of electrochromic mechanisms, experimental result prediction, and novel device development due to its clear physical nature.

Temperature-Controlled Crystal Size of Wide Band Gap Nickel Oxide and Its Application in Electrochromism.

Nickel oxide (NiO) is a wide band gap semiconductor material that is used as an electrochromic layer or an ion storage layer in electrochromic devices. In this work, the effect of annealing temperature on sol-gel NiO films was investigated. Fourier transform infrared spectroscopy (FTIR) showed that the formation of NiO via decomposition of the precursor nickel acetate occurred at about 300 °C. Meanwhile, an increase in roughness was observed by Atomic force microscope (AFM), and precipitation of a large number of crystallites was observed at 500 °C. X-ray Diffraction (XRD) showed that the NiO film obtained at such a temperature showed a degree of crystallinity. The film crystallinity and crystallite size also increased with increasing annealing temperature. An ultraviolet spectrophotometer was used to investigate the optical band gap of the colored NiO films, and it was found that the band gap increased from 3.65 eV to 3.74 eV with the increase in annealing temperature. An electrochromic test further showed that optical modulation density and coloring efficiency decreased with the increase in crystallite size. The electrochromic reaction of the nickel oxide film is more likely to occur at the crystal interface and is closely related to the change of the optical band gap. An NiO film with smaller crystallite size is more conducive to ion implantation and the films treated at 300 °C exhibit optimum electrochromic behavior.

Effect of the Ammonium Tungsten Precursor Solution with the Modification of Glycerol on Wide Band Gap WO3 Thin Film and Its Electrochromic Properties.

Tungsten trioxide (WO3) is a wide band gap semiconductor material, which is commonly not only used, but also investigated as a significant electrochromic layer in electrochromic devices. WO3 films have been prepared by inorganic and sol-gel free ammonium tungstate ((NH4)2WO4), with the modification of glycerol using the spin coating technique. The surface tension, the contact angle and the dynamic viscosity of the precursor solutions demonstrated that the sample solution with a 25% volume fraction of glycerol was optimal, which was equipped to facilitate the growth of WO3 films. The thermal gravimetric and differential scanning calorimetry (TG-DSC) analysis represented that the optimal sample solution transformed into the WO3 range from 220 °C to 300 °C, and the transformation of the phase structure of WO3 was taken above 300 °C. Fourier transform infrared spectroscopy (FT-IR) spectra analysis indicated that the composition within the film was WO3 above the 300 °C annealing temperature, and the component content of WO3 was increased with the increase in the annealing temperature. The X-ray diffraction (XRD) pattern revealed that WO3 films were available for the formation of the cubic and monoclinic crystal structure at 400 °C, and were preferential for growing monoclinic WO3 when annealed at 500 °C. Atomic force microscope (AFM) images showed that WO3 films prepared using ammonium tungstate with modification of the glycerol possessed less rough surface roughness in comparison with the sol-gel-prepared films. An ultraviolet spectrophotometer (UV) demonstrated that the sample solution which had been annealed at 400 °C obtained a high electrochromic modulation ability roughly 40% at 700 nm wavelength, as well as the optical band gap (Eg) of the WO3 films ranged from 3.48 eV to 3.37 eV with the annealing temperature increasing.

Effects of Annealing Temperature on Optical Band Gap of Sol-gel Tungsten Trioxide Films.

Tungsten trioxide (WO3) is a wide band gap semiconductor material that is used as an important electrochromic layer in electrochromic devices. In this work, the effects of the annealing temperature on the optical band gap of sol-gel WO3 films were investigated. X-ray Diffraction (XRD) showed that WO3 films were amorphous after being annealed at 100 °C, 200 °C and 300 °C, respectively, but became crystallized at 400 °C and 500 °C. An atomic force microscope (AFM) showed that the crystalline WO3 films were rougher than the amorphous WO3 films (annealed at 200 °C and 300 °C). An ultraviolet spectrophotometer showed that the optical band gap of the WO3 films decreased from 3.62 eV to 3.30 eV with the increase in the annealing temperature. When the Li⁺ was injected into WO3 film in the electrochromic reaction, the optical band gap of the WO3 films decreased. The correlation between the optical band gap and the electrical properties of the WO3 films was found in the electrochromic test by analyzing the change in the response time and the current density. The decrease in the optical band gap demonstrates that the conductivity increases with the corresponding increase in the annealing temperature.