Structure changes and optical properties of Mg2Ni switchable mirrors

A multilayer film of Mg and Ni was prepared by dc/ac magnetron sputtering and annealed below 623 K in vacuum to obtain polycrystalline Mg₂Ni thin films. The phase transformation during heating process and optical switching properties of the films were investigated. The influence of the original crystalline state of Mg₂Ni films on optical switching properties such as transmission, optical band gaps and the cycle times was discussed. The indirect optical band gaps of the fully hydrogenated amorphous Mg₂Ni films were estimated by linear extrapolation.     

Electrochromic properties of porous NiO thin films prepared by a chemical bath deposition

Highly porous nickel oxide thin films were prepared on ITO glass by a simple chemical bath deposition (CBD) method in combination with a following heat-treatment process. XRD analysis revealed that the as-deposited precursor film contained β-Ni(OH)₂ and γ-NiOOH, and they changed to cubic polycrystalline NiO after annealing. The FTIR results showed presence of free hydroxyl ion and water in the NiO thin films. The electrochromic properties of NiO thin films were investigated in an aqueous alkaline electrolyte (1 M KOH) by means of transmittance, cyclic voltammetry (CV) and chronoamperometry (CA) measurements. The NiO thin film annealed at 300 °C exhibited a noticeable electrochromism and good memory effect. The coloration efficiency was calculated to be 42 cm² C⁻¹ at 550 nm, with a variation of transmittance up to 82%. The porous NiO thin films also showed good reaction kinetics with fast switching speed, and the coloration and bleaching time were 8 and 10 s, respectively.     

Solid electrolyte of tantalum oxide thin film deposited by reactive DC and RF magnetron sputtering for all-solid-state switchable mirror glass

All-solid-state switchable mirror glass was prepared by magnetron sputtering. The device exhibited the multi-layer structure of Mg₄Ni/Pd/Ta₂O₅ on WO₃/ITO/glass substrate. The Mg₄Ni, Pd, and Ta₂O₅ in the device acted as optical switches, proton injector and solid electrolyte, respectively. Reactive DC magnetron sputtering was employed as a new deposition method for Ta₂O₅ electrolyte thin film for the device. The transmittance of the device, at a wavelength of 670 nm using reactive DC-sputtered Ta₂O₅ thin film, reached 0.1% (a reflective state) to 48% (a transparent state). The transmittance change occurred in less than 40 s when 5 V was applied, and the switching speed was 60 times faster than that of the device using reactive RF-sputtered Ta₂O₅ thin film.     

Electrochemical performance of In2O3 thin film electrode in lithium cell

Indium oxide (In₂O₃) coating on Pt, as an electrode of thin film lithium battery was carried out by using cathodic electrochemical synthesis in In₂(SO₄)₃ aqueous solution and subsequently annealing at 400 °C. The coated specimens were characterized by X-ray photoelectron spectroscopy (XPS) for chemical bonding, X-ray diffraction (XRD) for crystal structure, scanning electron microscopy (SEM) for surface morphology, cyclic voltammetry (CV) for electrochemical properties, and charging/discharging test for capacity variations. The In₂O₃ coating film composed of nano-sized particles about 40 nm revealing porous structure was used as the anode of a lithium battery. During discharging, six lithium ions were firstly reacted with In₂O₃ to form Li₂O and In, and finally the Li_4.33In phase was formed between 0.7 and 0.2 V, revealing the finer particles size about 15 nm. The reverse reaction was a removal of Li⁺ from Li_4.33In phase at different oxidative potentials, and the rates of which were controlled by the thermodynamics state initially and diffusion rate finally. Therefore, the total capacity was increased with decreasing current density. However, the cell delivering a stable and reversible capacity of 195 mAh g⁻¹ between 1.2 and 0.2 V at 50 μA cm⁻² may provide a choice of negative electrode applied in thin film lithium batteries.     

Metal buffer layer inserted switchable mirrors

Thin buffer layers of hydrogen diffusive metals such as Ti, Nb, and V were inserted between a Mg₄Ni thin film and a Pd top layer, which were prepared by DC magnetron sputtering. Their optical, electrochemical properties, and switching durability were investigated using both gasochromic and electrochromic switching methods. It has been proved that Ti, Nb, and V buffer layers can protect the migration of Mg to surface of thin film during the switching processes, and also service as a protection layer against the oxidization of Mg. These metal buffer layers do not affect the hydrogenation of Mg–Ni alloy mirrors system when switching with hydrogen gas or electrochromic, rather, its dehydrogenation speed is accelerated greatly. Switching cyclic number of those metal buffer layer inserted mirrors achieved 400–500 cycles which was enhanced ca. 3 times than non-inserted one.     

All oxide solid-state lithium-ion cells

Solid-state lithium-ion cells have been prepared using thin film Li₄Ti₅O₁₂ as the anode, thin film LiCoO₂ as the cathode and Li_0.33La_0.56TiO₃ as the electrolyte. The electrolyte was prepared as a relatively thick ceramic with a thickness close to 1 mm. This type of cell develops a voltage of slightly greater than 2 V and is stable to cycling. Perhaps the most interesting aspect of this cell, is that even with a relatively thick, poor quality ceramic electrolyte, this cell has been able to develop current densities as great as 40 μA/cm².     

Electrochromism in nickel oxide and tungsten oxide thin films: Ion intercalation from different electrolytes

Electrochromic (EC) NiO_z and WO_y thin films were prepared by sputtering and were used in a feasibility study aimed at investigating mixtures of these two oxides. The object was to identify a suitable electrolyte, compatible with both NiO_z and WO_y. To that end we carried out cyclic voltammetry (CV) in potassium hydroxide (KOH), propionic acid, and lithium perchlorate in propylene carbonate (Li-PC). WO_y could be coloured in propionic acid and Li-PC, while NiO_z could be coloured only in KOH. Both films showed best stability in Li-PC, which hence is well suited for further studies of mixed NiO_z and WO_y.     

Factors affecting the electrochemical reactivity vs. lithium of carbon-free LiFePO4 thin films

The electrochemical stability of various current collector materials such as Si, Pt, 304 stainless steel, Ti, Al exposed to the most common lithium-ion electrolyte salts (LiPF₆, LiBF₄, LiAsF₆, LiTFSI, LiClO₄) have been herein investigated. For applied potentials greater than 3 V, the acidic fluorine-based electrolytes were shown to be the most corrosive. Consequently, aqueous and non-aqueous electrolytes (1 M LiNO₃/H₂O vs. 1 M LiClO₄/EC-DMC) were successfully applied to study the electrochemical properties of C-free LiFePO₄ thin films whose redox potential is near 3.5 V vs. Li⁺/Li⁰. Using aqueous electrolyte has resulted in a lowering of both cell resistance and interfacial charge transfer resistance by almost one order of magnitude, hence enabling to considerably increase the electrochemical capacity of our LiFePO₄ thin films. Besides, we unravel the importance of the mechanical strains at the substrate/LiFePO₄ thin film interface on the film textural, structural modification and electrochemical stability upon cycling.     

Preparation and characterization of semiconducting Zn1−xCdxSe thin films

The electrodeposition of Zn_1−xCd_xSe polycrystalline semiconducting thin films from aqueous acidic bath without any additives onto tin oxide-coated conducting glass and titanium substrates are described. The influence of deposition parameters on the film formation and deposition mechanism based on cyclic voltammetry is discussed. X-ray diffraction studies showed the polycrystalline wurtzite nature for all the films deposited under the proposed conditions. The optical studies revealed the band gap values in the range between 2.82 and 1.72 eV as the film composition changes from ZnSe to CdSe. It has been observed that the concentration of cadmium salt plays an essential role on the alloy formation. The surface morphological studies and composition analysis were carried out and the results are discussed.     

Characterization of honeycomb-like “β-Ni(OH)2” thin films synthesized by chemical bath deposition method and their supercapacitor application

Nanostructured nickel hydroxide thin films are synthesized via a simple chemical bath deposition (CBD) method using nickel nitrate Ni(NO₃)₂ as the starting material. The deposition process is based on the thermal decomposition of ammonia-complexed nickel ions at 333 K. The structural, surface morphological, optical, electrical and electrochemical properties of the films are examined. The nanocrystalline “β” phase of Ni(OH)₂ is confirmed by the X-ray diffraction analysis. Scanning electron microscopy reveals a macroporous and interconnected honeycomb-like morphology. Optical absorption studies show that “β-Ni(OH)₂” has a wide optical band-gap of 3.95 eV. The negative temperature coefficient of the electrical resistance of “β-Ni(OH)₂”, is attributed to the semiconducting nature of the material. The electrochemical properties of “β-Ni(OH)₂” in KOH electrolyte are examined by cyclic voltammetric (CV) measurements. The scan-rate dependent voltammograms demonstrate pseudocapacitive behaviour when “β-Ni(OH)₂” is employed as a working electrode in a three-electrode electrochemical cell containing 2 M KOH electrolyte with a platinum counter electrode and a saturated calomel reference electrodes. A specific capacitance of ∼398 × 10³ F kg⁻¹ is obtained.     

Fabrication and photoelectrochemical study of Ag@TiO2 nanoparticle thin film electrode

Ag@TiO₂ nanoparticle thin film was fabricated for photoelectrochemical water splitting in the visible light region. Under the irradiation of UV light, positive photocurrent was enhanced in both electrolytes of 0.1 M HNO₃ and 0.1 M NaOH owing to the excitation of photoelectrons within the TiO₂ shells. However, under the irradiation of visible light, the enhancement of positive photocurrent was observed only in 0.1 M HNO₃ because of the formation of a Schottky barrier band bending at the Ag-TiO₂ core-shell interface and the generation of photoelectrons resulted from the surface plasmon resonance of Ag cores. In 0.1 M NaOH, significant negative photocurrent was enhanced due to the influences of higher pH on the surface state and energy level of TiO₂ shells. Such a visible light-induced photoresponse enhancement and photocurrent direction switching made the Ag@TiO₂ nanoparticle thin film useful not only as a photoelectrode for water splitting but also as a photo-switch in a basic electrolyte.     

Synthesis and characterization of co-electroplated Cu2ZnSnS4 thin films as potential photovoltaic material

Cu₂ZnSnS₄ thin films have been successfully prepared by a novel synthesis process that involves a single step deposition of Cu₂ZnSnS₄ followed by a post-annealing treatment at 550 °C for 60 min in the atmosphere of N₂+H₂S (5%). The microstructure, morphology, composition and optical property of the film have been investigated in detail. It is found that the Na₂S₂O₃5H₂O concentration in the solution has a significant effect on the Cu₂ZnSnS₄ thin films. X-ray diffraction data indicates that the annealed Cu₂ZnSnS₄ thin films have a kesterite structure with preferred orientation along the (1 1 2) plane. Uniform and compact topographies are observed in some annealed films. From the energy dispersive X-ray spectroscopy analysis, it can be seen that Cu-poor and Zn-rich Cu₂ZnSnS₄ thin films have been obtained. The direct band gap energy of the film is about 1.5 eV.     

Studies on photoelectrochemical (PEC) cell formed with SILAR deposited Bi2Se3–Sb2Se3 multilayer thin films

Nanocrystalline Bi₂Se₃–Sb₂Se₃ multilayer thin films were deposited by simple and less investigated successive ionic layer adsorption and reaction (SILAR) method onto glass- and fluorine-doped tin oxide (FTO)-coated glass substrate from aqueous solution. Characterizations such as XRD, surface morphology and optical absorption have been carried out for Bi₂Se₃–Sb₂Se₃ thin films onto glass substrates. The films deposited onto FTO-coated glass substrates were used to study photoelectrochemical behaviour in 0.1 M (NaOH–Na₂S–S) electrolyte and results are reported.     

Dynamic behavior of surface film on LiCoO2 thin film electrode

Electrochemical oxidation behavior of non-aqueous electrolytes on LiCoO₂ thin film electrodes were investigated by in situ polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). LiCoO₂ thin film electrode on gold substrate was prepared by rf-sputtering method. In situ PM-FTIR spectra were obtained at various electrode potentials during cyclic voltammetry measurement between 3.5 V vs. Li/Li⁺ and 4.2 V vs. Li/Li⁺. During anodic polarization, oxidation of non-aqueous electrolyte was observed, and oxidized products remained on the electrode at the potential higher than 3.75 V vs. Li/Li⁺ as a surface film. During cathodic polarization, the stripping of the surface film was observed at the potential lower than 3.9 V vs. Li/Li⁺. Depth profile of XPS also showed that more organic surface film remained on charged LiCoO₂ than that on discharged one. AFM images of charged and discharged electrodes showed that some decomposed products deposited on charged electrode and disappeared from the surface of discharged one. These results indicate that the surface film on LiCoO₂ is not so stable.     

Optical property and cycling durability of polytetrafluoroethylene top-covered and metal buffer layer inserted Mg-Ni switchable mirror

Pd-capped Mg-rich Mg-Ni alloy thin film shows excellent reversible switching properties in optical transmittance by the exposure to hydrogen containing gas. However, it shows fast degradation due to the oxidization of magnesium and the switching durability is not good enough for practical applications. To resolve this problem we tried to improve its switching durability of Mg-Ni based switchable mirror by the combined use of metal buffer layer insertion between Pd and Mg-Ni layer and polytetrafluoroethylene (PTFE) protective coating. PTFE thin film has been prepared on the surface of Mg-Ni thin films by RF magnetron sputtering in the Ar and CF₄ mixed gas discharge plasma at room temperature and a power of 30 W. The sample of Pd/Ti/Mg₄Ni thin film with the protective coating of 900-nm-thick PTFE layer can be switched over 1600 switching cycles, which suppress the degradation by 15% of its initial transmission modulation level.     

Rapid hydrogen charging on metal hydride negative electrode of Fuel Cell/Battery (FCB) systems

The characteristics of rapid gaseous H₂ charging/electrochemical discharging of the metal hydride negative electrode were investigated for the application in Fuel Cell/Battery (FCB) systems. They were evaluated with the H₂ gas absorption, followed by the subsequent electrochemical discharging in the electrolyte solution (6M KOH). Then, the cyclability of charge–discharge was also examined. It was observed that more than 70% of the theoretical capacity was charged within 10 min with 0.3 MPa and 0.5 MPa of the initial H₂ pressures. The electrochemical discharge curve showed that more than 86% of the absorbed H₂ was discharged. Furthermore, the cycled charge–discharge process indicated that the H₂ gas charge and electrochemical discharge process is an effective way to rapidly charge and activate the metal hydride without degeneration.     

Effects of different electrolytes containing Na2WO4 on the electrochemical performance of nickel hydroxide electrodes for nickel–metal hydride batteries

To improve the high-temperature performance of the nickel hydroxide electrodes in nickel–metal hydride batteries, sodium tungstate (Na₂WO₄) used as an electrolyte additive has been added into two types of binary electrolytes (KOH–LiOH and NaOH–LiOH) in this study. The effects of electrolyte composition on the electrochemical performance of nickel electrodes have been systematically investigated via a combination of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM), energy-dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and charge/discharge tests. It is found that by adding (1.0 wt.%) Na₂WO₄, the performance of nickel electrodes is significantly improved in both NaOH and KOH electrolytes at 70 °C. The improved performance can be attributed to the deposition of WO₃·2H₂O solid film on the surface of nickel electrode, which is beneficial to the increase in oxygen evolution overpotential, the slow-down of oxygen evolution rate and the decrease in charge-transfer resistance.     

p-Type CuSbS2 thin films by thermal diffusion of copper into Sb2S3

We report the preparation of copper antimony sulfide (CuSbS₂) thin films by heating Sb₂S₃/Cu multilayer in vacuum. Sb₂S₃ thin film was prepared from a chemical bath containing SbCl₃ and Na₂S₂O₃ salts at room temperature (27 °C) on well cleaned glass substrates. A copper thin film was deposited on Sb₂S₃ film by thermal evaporation and Sb₂S₃/Cu layers were subjected to annealing at different conditions. Structure, morphology, optical and electrical properties of the thin films formed by varying Cu layer thickness and heating conditions were analyzed using different characterization techniques. XRD analysis showed that the thin films formed at 300 and 380 °C consist of CuSbS₂ with chalcostibite structure. These thin films showed p-type conductivity and the conductivity value increased with increase in copper content. The optical band gap of CuSbS₂ was evaluated as nearly 1.5 eV.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Step potential analysis of cobalt oxide-based electrochromic devices

The characterization of electrochemical behavior of electrochromic intercalation device based on cobalt oxide thin film was carried out using the step potential excitation method. A method based on generating plots of current density as a function of passed charge has been applied for characterization of electrochromic cobalt oxide thin films using an aqueous KOH electrolyte. The device resistance and the intercalation capacity of the material are calculated. Dynamic built-in potential estimated from step potential experiment and plots of the built-in potential as function of the passed charge, V_bi(ΔQ), are generated for intercalation process. The intercalation efficiency curve is obtained to confirm the nature of energy distribution of intercalation sites in electrochromic cobalt oxide.