WO_3薄膜的微观结构与电致变色机制研究

采用直流反应磁控溅射方法在ITO导电玻璃上沉积了WO3薄膜,研究了靶基距对其微结构和电致变色性能的影响,利用XRD、SEM和XPS对薄膜的微结构和成分进行了表征。通过可见光透射谱对样品的电致变色性能进行了研究,并且讨论了WO3薄膜电致变色性能与其微结构、价态变化之间的关系。发现靶基距为7cm的情况下沉积得到的WO3薄膜呈非晶态,薄膜有更多的孔隙,有利于Li+的抽取,进而显示出较好的电致变色性能。反应溅射制备的WO3薄膜中W是W6+价态,颜色为透明状,当发生着色反应时,随着薄膜中Li+成分增加,薄膜颜色变为蓝色,薄膜中W原子为W6+和W5+的混合价态。认为其电致变色的行为是由于Li+和e-在薄膜中的注入和拉出引起的W6+和W5+发生转化所致。     

电色膜和电色器件的光电特性

介绍了电子束蒸发沉积WO3膜在0．5mol/LH2SO4溶液和NiOx膜在1molKOH溶液中的电色性能；介绍了沉积到玻璃片上的ITO膜作透明导电电极、光学上活性的WO3阴极变色膜作工作电极、光学上活性的NiOx阳极变色膜作反电极（贮存电荷试样的贮存器）和1molLiClO4丙酮溶液的电解质作锂离子导体组成的互补型电色器件的光电特性。     

Nanostructured mesoporous tungsten oxide films with fast kinetics for electrochromic smart windows

A potential driven self-assembly of sodium dodecyl sulfate/tungsten oxide aggregates at the electrolyte-electrode interface followed by template extraction and annealing yielded mesoporous thin films of electrochromic tungsten oxide (WO(3)). Electron microscopy images revealed that the films are characterized by a hitherto unreported hybrid structure comprising nanoparticles and nanorods with a tetragonal crystalline phase of WO(3) with the measured lattice parameters: a = 0.53?nm and c = 0.37?nm. In addition to pentagonal voids characteristic of the tetragonal WO(3) phase at the lattice scale, open channels and pores of 5-10?nm in diameter lie between the nanoparticles, which cumulatively promote rapid charge transport through the film. This resulted in colouration efficiency (η(max)～90?cm(2)?C(-1) at λ = 900?nm) and switching kinetics (colouration time = 3?s and bleaching time = 2?s for a 50% change in transmittance) higher and faster than previously reported values for mesoporous WO(3) films. Repetitive cycling between the clear and blue states has no deleterious effect on the electrochromic performance of the film, which is suggestive of its potential as a cathode in practical electrochromic windows.     

直流磁控溅射沉积WO3薄膜电致变色性能研究

以金属钨为靶材,采用直流反应磁控溅射方法,在玻璃上制备电致变色WO3薄膜.利用X射线衍射(XRD)方法对薄膜的结构进行了分析,得出了WO3薄膜的沉积工艺.制备了WO3/TTO/Glass电致变色器件,并对其性能进行了研究.结果表明在Li+注入前后,薄膜的透射率平均变化约50%,具有较好的可逆变色特性;Li+注入后,WO3薄膜中的一部分W6+变为W5+,转化比例约为25%.     

Resistive switching behavior and multiple transmittance states in solution-processed tungsten oxide

In this work, a tungsten oxide (WO(x)) film is prepared using a thiourea-assisted solution process. We demonstrate a device composed of fluorine doped tin oxide (FTO)-glass/WO(x)/electrolyte/indium-tin oxide (ITO)-glass stacking electrochromic (EC) structure and Al electrodes that are locally patterned and interposed between the WO(x) film and electrolyte, which form an Al(top electrode)/WO(x)/FTO(bottom electrode) resistance random access memory (RRAM) unit. According to transmission electron microscopy and X-ray photoelectron spectroscopy analyses, the WO(x) film contains nanosize pores and metallic-tungsten nanoclusters which are scattered within the tungsten oxide layer and concentrated along the interface between the Al electrode and WO(x) film. With application of voltage to the ITO electrode, multiple transmittance states are achieved for the EC unit due to the different quantity of intercalated Li ions in the WO(x) film. As for the Al/WO(x)/FTO RRAM unit, a bipolar nonvolatile resistive switching behavior is attained by applying voltage on the Al top electrode, showing electrical bistability with an ON/OFF current ratio up to 1 × 10(4).     

电子束蒸发制备氧化钨、氧化镍薄膜的电致变色性能

电致变色(EC)材料在外加电压作用下能可逆地改变其光学性能.其中氧化钨与氧化镍是典型的电致变色用材料.本文用电子束蒸发的方法在ITO玻璃基片上制备了此两种薄膜,研究了热处理工艺对薄膜结构与电致变色性能的影响.电致变色性能由电化学方法测试.封装的半固态智能窗器件具有很好的电致变色性能.     

Electrochromic properties of tungsten-titanium oxide films

The last decade has seen great in electrochromic (EC) technology for smart windows and displays. In this study, WTiOx films formed from TiO2 and WO3 were deposited onto ITO glass with a sheet resistance of 10 Omega cm and on silicon substrates, by pulsed magnetron sputtering using a W and Ti alloy target. The films were deposited at plasma powers 100, 200, 300, 400 and 500 W using a gaseous Ar (150 sccm)/O2 (50 sccm) mixture; the working pressure was fixed at 5E-2 torr. The film thickness increased with the plasma power. However, increasing the plasma power yielded a more crystalline structure with poorer electrochromic properties. The influence of Ti doping and plasma power on the structural, optical and electrochromic properties of the WTiOx thin films was studied. WTiOx films grown at various plasma powers of under 400 W were amorphous. Deposition of films at 400 W yielded the optimal electrochromic properties, with high optical modulation, high coloration efficiency and the lowest color memory effect at wavelengths 400, 550 and 800 nm. An XPS study indicated that Ti can stabilize the valence state of W6+. The improvements caused by the doping with Ti were tested: an optical density (OD) of close to 0.85 and a maximum delta T (%) at 400 nm of 25.8%, at 550 nm of 52.5% and at 800 nm (in the near-IR region) of 62.4%.     

Nanostructured nickel oxide films prepared by chemical vapor deposition and their electrochromic properties

The influence of the deposition conditions on the structural features and electrochromic properties of nickel oxide (NiO) films prepared by chemical vapor deposition has been investigated. NiO films have been prepared on fluorine doped tin oxide (FTO) coated glass substrates from nickel-acetylacetonate precursor and their electrochromic properties have been studied by cyclic voltammetry in a 0.1 M KOH solution at room temperature. Films exhibiting only the NiO phase were obtained at deposition temperatures higher than 450 degrees C in a wide range of reactor pressures (0.13 to 66.6 kPa). Particularly, NiO films prepared at 500-550 degrees C from 0.13 to 53.3 kPa are transparent in nature and exhibit a crystallite size varying from 10 to 60 nm. An appreciable anodic electrochromic change from transparent to black coloured resulted from a very porous surface morphology and film thickness of about 3.5 microm. The electrochromic change was maintained over 3000 switching cycles. Nanostructured 3.5 microm-thick NiO films showed a maximum difference in optical transmittance of about 40% in the near-infrared region. These results make the nanostructured NiO films comparables with those prepared by other deposition techniques.     

多晶氧化钨薄膜的制备及其红外反射调制性能研究

通过工艺参数的优化,采用直流反应溅射工艺成功地制备了具有良好的电化学循环稳定性的多晶氧化钨薄膜.Raman散射光谱研究表明:随着锂离子和电子的共同注入,多晶薄膜中的W⁶⁺逐渐被还原为W⁵⁺.红外反射测试表明:电子注入薄膜后,成为自由载流子,使得氧化钨薄膜表现出一定的金属特性,具有一定的红外反射调制能力.采用该工艺制备的WO₃/ITO/Glass结构的发射率可在0.261～0.589的范围内可逆调节.     

Preparation and characterization of spray deposited n-type WO3 thin films for electrochromic devices

The n-type tungsten oxide (WO₃) polycrystalline thin films have been prepared at an optimized substrate temperature of 250 °C by spray pyrolysis technique. Precursor solution of ammonium tungstate ((NH₄)₂WO₄) was sprayed onto the well cleaned, pre-heated fluorine doped tin oxide coated (FTO) and glass substrates with a spray rate of 15 ml/min. The structural, surface morphological and optical properties of the as-deposited WO₃ thin films were studied. Mott-Schottky (M-S) studies of WO₃/FTO electrodes were conducted in Na₂SO₄ solution to identify their nature and extract semiconductor parameters. The electrochromic properties of the as-deposited and lithiated WO₃/FTO thin films were analyzed by employing them as working electrodes in three electrode electrochemical cell using an electrolyte containing LiClO₄ in propylene carbonate (PC) solution.     

Optimizing indium tin oxide thin films with bipolar d.c.-pulsed magnetron sputtering for electrochromic device applications

In this paper, indium tin oxide (ITO) films were prepared by bipolar d.c.-pulsed magnetron sputtering in a mixture of argon and oxygen onto unheated glass substrates. A target of ITO with 10 weight percent (wt %) tin was used. The influences of ratios of t^– _on/t⁺ _on (negative pulse-on time/positive pulse-on time) on the optical, electrical, and structural properties of ITO films have been investigated. The correlations between the deposition parameters and the film properties were discussed. An optimal condition based on reactive bipolar d.c.-pulsed sputtering for obtaining high transmittance, low resistivity, and low surface roughness of ITO films with high deposition rate is suggested. Then, ITO films grown at room temperature by bipolar d.c.-pulsed sputtering were used to form electrochromic devices of WO₃. Better electrochromic performances were found in comparison to those measured with commercially available ITO films on glass substrates.     

Nanostructured WO₃/BiVO₄ heterojunction films for efficient photoelectrochemical water splitting

We report on a novel heterojunction WO(3)/BiVO(4) photoanode for photoelectrochemical water splitting. The heterojunction films are prepared by solvothermal deposition of a WO(3) nanorod-array film onto fluorine-doped tin oxide (FTO) coated glass, with subsequent deposition of a low bandgap, 2.4 eV, visible light responding BiVO(4) layer by spin-coating. The heterojunction structure offers enhanced photoconversion efficiency and increased photocorrosion stability. Compared to planar WO(3)/BiVO(4) heterojunction films, the nanorod-array films show significantly improved photoelectrochemical properties due, we believe, to the high surface area and improved separation of the photogenerated charge at the WO(3)/BiVO(4) interface. Synthesis details are discussed, with film morphologies and structures characterized by field emission scanning electron microscopy and X-ray diffraction.     

基于氧化钨和氧化镍的电致变色器件研究进展

电致变色器件(Electrochromic Devices,ECDs)是一种颜色变化受电压调控的智能装置,具有工作温度范围宽、光学对比度高、可逆双稳态性能好、驱动电压低和能耗低等优点,在智能动态调光窗、全彩色电子显示屏、防眩光护目镜、自适应双隐身伪装以及可视化储能等领域展现出了巨大的应用潜力.阴极着色材料氧化钨(WO3...     

以聚合物凝胶为电解质的多层全固态电变色器件的研究

本文在掺ＬｉＣｌＯ４与碳酸丙烯酯的聚乙二醇固体电解质离子电导特性与ＷＯ３、ＮｉＯ薄膜离子插入性能研究了基础上，设计并制备了互补型ＷＯ３／ＮｉＯ全固态电变色器件。同时研究了该器件变色过程的循环伏安特性与不同状态的可见、近红外透过特性。结果表明，互补型的ＷＯ３／ＰＥＧ－ＬｉＣｌＯ４－ＰＣ／ＮｉＯ器件在可见与近红外均具有良好的电变色特性，其漂白态在波长６００ｎｍ的透过率为７０％，着色态为２０％。     

微波辐射溶胶-凝胶法制备TiO2薄膜及其降解铬黑T的活性

通过微波辐射溶胶一凝胶法（sol-gel）法在导电玻璃（ITO）基体上制备TiO2纳米薄膜光催化剂，考察不同加热方式、微波时间、酸处理、薄膜层数等对TiO2纳米粒子及薄膜的影响。以可见光谱（UV-VIS）、X射线衍射（XRD）对TiO2薄膜进行了表征，并通过薄膜光催化降解铬黑T溶液的性能进行了研究。实验表明，ITO玻璃表面的TiO2纳米薄膜经HNO3和微波处理后，因协同效应使薄膜的光催化活性大大增强。     

Dip-coated hydrotungstite thin films as humidity sensors

Thin films of a hydrated phase of tungsten oxide, viz. hydrotungstite, have been prepared on glass substrates by dipcoating method using ammonium tungstate precursor solution. X-ray diffraction shows the films to have a strongb — axis orientation. The resistance of the films is observed to be sensitive to the humidity content of the ambient, indicating possible applications of these films for humidity sensing. A homemade apparatus designed to measure the d.c. electrical resistance in response to exposure to controlled pulses of a sensing gas has been employed to evaluate the sensitivity of the hydrotungstite films towards humidity.     

Size-controlled synthesis and gas sensing application of tungsten oxide nanostructures produced by arc discharge

Several different synthetic methods have been developed to fabricate tungsten oxide (WO(3)) nanostructures, but most of them require exotic reagents or are unsuitable for mass production. In this paper, we present a systematic investigation demonstrating that arc discharge is a fast and inexpensive synthesis method which can be used to produce high quality tungsten oxide nanostructures for NO(2) gas sensing measurements. The as-synthesized WO(3) nanostructures are characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), finger-print Raman spectroscopy and proton induced x-ray emission (PIXE). The analysis shows that spheroidal-shaped monoclinic WO(3) crystal nanostructures were produced with an average diameter of 30?nm (range 10-100?nm) at an arc discharge current of 110?A and 300?Torr oxygen partial pressure. It is found that the morphology is controlled by the arc discharge parameters of current and oxygen partial pressure, e.g.?a high arc discharge current combined with a low oxygen partial pressure results in small WO(3) nanostructures with improved conductivity. Sensors produced from the WO(3) nanostructures show a strong response to NO(2) gas at 325?°C. The ability to tune the morphology of the WO(3) nanostructures makes this method ideal for the fabrication of gas sensing materials.     

Sol-Gel法制备氧化镍电致变色薄膜研究

以镍的醇盐为前驱体并加入催化剂和各种添加剂制成涂膜溶液,采用浸涂-提拉法(dip-coating)制备NiOx电致变色膜。讨论了先体胶液的性质、热处理制度及变色参数对薄膜表面微观结构和变色性能的影响。     

Microstructures of ITO films deposited by d.c. magnetron sputtering with H2O introduction

ITO films were deposited by d.c. magnetron sputtering with/without H₂O introduction. The structural and optoelectrical properties of the films were analyzed in detail. The films deposited with H₂O introduction exhibited an entirely amorphous structure, whereas the as-deposited films deposited without H₂O introduction exhibited a polycrystalline In₂O₃ structure. The amorphous ITO films deposited under the high H₂O partial pressure were confirmed to contain a much higher concentration of hydrogen inside the films by secondary ion mass spectroscopy, which remained after post-annealing at 350 °C. The crystallization temperature of the films subjected to post-annealing was increased to higher than 220 °C. These stable amorphous ITO films had a wet-etching rate in oxalic acid solution two orders of magnitude higher than that of the films deposited without H₂O introduction.     

Thin film passive solar windows produced by reactive evaporation of In-Sn

The semiconductor indium tin oxide (ITO) when present as a thin film has been shown to be transparent to visible radiation while opaque to IR radiation. Sputtering, chemical vapor deposition and other coating methodologies have been used to prepare ITO thin films. Reactive evaporation is an alternative coating technique, which has as its major advantage technical simplicity. Our prepation of ITO thin films (30–90 nm) for passive solar windows included the reactive evaporation of In-Sn alloys (In-5wt.%Sn, In-10wt.%Sn and In-20wt.%Sn) onto commercial soda-lime glass held between 25 and 300 °C. The reactive evaporation atmosphere consisted of oxygen at partial pressures from 1 × 10^-4 to 1 × 10^-3 Torr in residual nitrogen. In selected instances ultrathin palladium nucleating layers were evaporated onto the glass substrates prior to the deposition of the ITO. This was done in order to minimize initial alloy-glass agglomeration effects, thus decreasing the final overall ITO film thickness while increasing the visible transmission properties. The film's visible and IR spectral transmission properties were examined using ratio recording spectrophotometry. The agglomeration, nucleation and growth phenomena of the films were extensively investigated by transmission electron microscopy. The agglomeration was found to be a function of the film thickness, with increasing agglomeration for thinner films. Surface analysis by scanning Auger microscopy (SAM), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy and energy-dispersive analysis of X-rays was also extensively carried out to determine our particular film properties. SAM indicated that only indium, tin and oxygen were present. No tungsten from the evaporation filament or elements from the glass were found. ESCA indicated that ITO was indeed present on the surface. Such work definitely indicated that ITO can be prepared by reactive physical vapor deposition and that the resultant films have the properties commonly found in sputtered ITO films.