Corrosion protection properties of vanadium films formed on zinc surfaces

Vanadium films were prepared on zinc surfaces by using a solution containing vanadate. Corrosion protection properties of vanadium-treated （V-treated）, chromium-treated （Cr-treated）, and untreated zinc surfaces in contact with a 3.5 wt.% NaC1 solution were studied using potentiodynamic polarization, electrochemical impedance spectroscopy （EIS）, and neutral salt spray （NSS） tests. According to these results, the V-treated layer significantly improved the corrosion resistance of zinc surfaces. In comparison with the Cr-treated layer, the V-treated layer exhibited a better corrosion resistance. The composition of the V-treated layer was studied using X-ray photoelectron spectroscopy （XPS）. XPS measurements indicated that the vanadium layer formed on zinc surfaces and the vanadium-rich coating was a hydrated oxide with a composition of V2O5, VO2, and its hydrates such as V2O5.nH2O and VO（OH）2.

Microstructure and corrosion resistance of vanadium films deposited at different target-substrate distance by HPPMS

High power pulsed magnetron sputtering（HPPMS）, a novel physical vapor deposition technology, was applied to prepare vanadium films on aluminum alloy substrate in this paper. The influence of target–substrate distance（Dt–s）（ranging from 8 to 20 cm） on phase structure, surface morphology, deposition rate, and corrosion resistance of vanadium films was investigated. The results show that the vanadium films are textured with a preferential orientation in the（111） direction except for that fabricated at 20 cm. With Dt–sincreasing, the intensity of（111） diffraction peak of the films decreases and there exists a proper distance leading to the minimum surface roughness of 0.65 nm. The deposition rate decreases with Dt–sincreasing. All the V-coated aluminum samples possess better corrosion resistance than the control sample. The sample fabricated at Dt–sof 12 cm demonstrates the best corrosion resistance with the corrosion potential increasing by 0.19 V and the corrosion current decreasing by an order of magnitude compared with that of the substrate. The samples gain further improvement in corrosion resistance after annealing, and if compared with that of annealed aluminum alloy, then the corrosion potential of the sample fabricated at 20 cm increases by 0.415 V and the corrosion current decreases by two orders of magnitude after annealed at 200 °C. If the annealing temperature further rises to 300 °C, then the corrosion resistance of samples increases less obviously than that of the control sample.

Surface oxidation of vanadium dioxide films prepared by radio frequency magnetron sputtering

This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were characterized with several different techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and Raman, when they were fresh from sputter chamber and aged after years, respectively, in order to determine their structure and composition. It finds that a small amount of sodium occurred on the surface of vanadium dioxide films, which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature. It also finds that aging for years significantly affected the nonstoichiometry of vanadium dioxide films, thus inducing much change in Raman modes.

Effect of source temperature on phase and metal–insulator transition temperature of vanadium oxide films grown by atomic layer deposition

Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of vanadium oxide films and valence state was investigated. The crystallinity, surface morphology, film thickness, and photoelectric properties of the films were characterized by x-ray diffraction, atomic force microscope, scanning electron microscope, I–V characteristics curves, and UV–visible spectrophotometer. By varying the source temperature, the content of V6O11, VO2, and V6O13 in the vanadium oxide film increased, that is, as the temperature increased, the average oxidation state generally decreased to a lower value, which is attributed to the rising of the vapor pressure and the change of the ionization degree for organometallics. Meanwhile, the root-mean-square roughness decreased and the metal–insulator transition temperature reduced. Our study is great significance for the fabrication of vanadium oxide films by atomic layer deposition.

Probing thermal properties of vanadium dioxide thin films by time-domain thermoreflectance without metal film

Vanadium dioxide(VO_(2))is a strongly correlated material,and it has become known due to its sharp metal-insulator transition(MIT)near room temperature.Understanding the thermal properties and their change across MIT of VO_(2)thin film is important for the applications of this material in various devices.Here,the changes in thermal conductivity of epitaxial and polycrystalline VO_(2)thin film across MIT are probed by the time-domain thermoreflectance(TDTR)method.The measurements are performed in a direct way devoid of deposition of any metal thermoreflectance layer on the VO_(2)film to attenuate the impact from extra thermal interfaces.It is demonstrated that the method is feasible for the VO_(2)films with thickness values larger than 100 nm and beyond the phase transition region.The observed reasonable thermal conductivity change rates across MIT of VO_(2)thin films with different crystal qualities are found to be correlated with the electrical conductivity change rate,which is different from the reported behavior of single crystal VO_(2)nanowires.The recovery of the relationship between thermal conductivity and electrical conductivity in VO_(2)film may be attributed to the increasing elastic electron scattering weight,caused by the defects in the film.This work demonstrates the possibility and limitation of investigating the thermal properties of VO_(2)thin films by the TDTR method without depositing any metal thermoreflectance layer.

Electrochemical properties of vanadium pentoxide xerogel films

Vanadium pentoxide xerogel（VXG） films were prepared by rapid quenching, then corn type 2016 size lithium rechargeable batteries were assembled and tested with the VXG film electrodes and lithium anodes. Electrochemical impedance spectroscopy（EIS） analysis result reveals the expected response for intercalation, except that there is almost no Warburg （diffusion） component. Analyses results of cyclic voltammetry（CV）, constant discharge （CD） and discharge-charge（DC） indicate that the sample achieves a high initial discharge specific capacity of approximate 400 mA·h/g and a corresponding efficiency of 97 % in the voltage diapason of 1.5 - 4.0 V with a draining current of 60 mA/g. Its preservation ratio of capacity still keeps as high as 85 % even after 100 cycles. The good electrochemical performance indicates that VXG film material is a promising cathode for lithium rechargeable batteries.

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO2 thin films as efficient electron transport layer

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO2 as the electron transport layer in the inverted configuration of organic photovoltaic cells based on poly（3-hexylthiophene） P3HT：[6-6] phenyl-（6） butyric acid methyl ester（PCBM）. 1% vanadium-doped TiO2nanoparticles were synthesized via the solvothermal method. Crystalline structure, morphology, and optical properties of pure and vanadium-doped TiO2 thin films were studied by different techniques such as x-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and UV–visible transmission spectrum. The doctor blade method which is compatible with roll-2-roll printing was used for deposition of pure and vanadium-doped TiO2 thin films with thicknesses of 30 nm and 60 nm. The final results revealed that the best thickness of TiO2 thin films for our fabricated cells was 30 nm. The cell with vanadium-doped TiO2 thin film showed slightly higher power conversion efficiency and great Jsc of 10.7 mA/cm^2 compared with its pure counterpart. In the cells using 60 nm pure and vanadium-doped TiO2 layers, the cell using the doped layer showed much higher efficiency. It is remarkable that the external quantum efficiency of vanadium-doped TiO2 thin film was better in all wavelengths.

Microstructure and Oxidation Resistance of V Thin Films Deposited by Magnetron Sputtering at Room Temperature

Vanadium films were deposited on Si(100)substrates at room temperature by direct current(DC)magnetron sputtering.The microstructure and surface morphology were studied using scanning electron microscopy(SEM)and atomic force microscope(AFM).The oxidation resistance of films in air was studied using X-ray photoelectron spectroscopy(XPS)and transmission electron microscopy(TEM).The results showed that the amorphous vanadium film with a flatter surface had higher oxidation resistance than the crystalline film when exposed to atmosphere.The rapid formation of the thin oxide layer of amorphous vanadium film could protect the film from sustained oxidation,and the relative reasons were discussed.

Electrochemical impedance spectra of V_2O_5 xerogel films with intercalation of lithium ion

Vanadium pentoxide xerogel films used for lithium rechargeable batteries were prepared from crystalline c-V2O5 by melt quenching method,then the electrochemical process of lithium intercalation into vanadium pentoxide xerogel films was simulated with an equivalent circuit model, which was derived from the mechanism of electrode reactions. Measured electrochemical impedance spectra at various electrode potentials were analyzed by using the complex non-linear least-squares fitting method. The results show that impedance spectra consist of 2 high-to- medium frequency depressed arcs and a low frequency straight line. The high frequency arc is attributed to the absorption reaction of lithium ions into the oxide film, the medium frequency arc is attributed to the charge transfer reaction at the vanadium oxide/electrolyte interface and the low frequency is characterized by a straight line with a phase angle of 45° corresponding to the diffusion of lithium ion through vanadium oxide phase. The experimental and calculated results are compared and discussed focusing on the electrochemical performance and the state of charge of the electrode. Moreover, the high consistence of the fitted values of the model to the experimental data indicates that this mathematical model does give a satisfying description of the intercalation process of vanadium pentoxide xerogel films.

Infrared Thermochromic Properties of VO_2 Thin Films Prepared through Aqueous Sol-gel Process

The stoichiometric vanadium（IV） oxide thin films were obtained by controlling the temperature, time and pressure of annealing. The thermochromic phase transition and the IR thermochromic property of 400 nm and 900 nm VO2 thin films in the 7.5 μm-14 μm region were discussed. The derived VO2 thin film samples were characterized by Raman, XRD, XPS, AFM, SEM, and DSC. The resistance and infrared emissivity of VO2 thin films under different temperature were measured, and the thermal images of films were obtained using infrared imager. The results show that the VO2 thin film annealed at 550 ℃ for 10 hours through aqueous sol-gel process is pure and uniform. The 900 nm VO2 thin film exhibits better IR thermochromic property than the 400 nm VO2 thin film. The resistance of 900 nm VO2 film can change by 4 orders of magnitude and the emissivity can change by 0.6 during the phase transition, suggesting the outstanding IR thermochromic property. The derived VO2 thin film can control its infrared radiation intensity and lower its apparent temperature actively when the real temperature increases, which may be applied in the field of energy saving, thermal control and camouflage.

Preparation of narrow band gap V_2O_5/TiO_2 composite films by micro-arc oxidation

V2Os/TiO2 composite films were prepared on pure titanium substmtes via micro-arc oxidation （MAO） in electrolytes consisting of NaVO3. Their morphology and dements were characterized by scanning electron microscopy （SEM） and energy-dispersive X-ray （EDX） analysis. Phase composition and valence states of species in the films were characterized by X-ray diffraction （XRD） and X-ray photoelec- tron spectroscopy （XPS）. Ultraviolet-visible diffuse reflectance spectra （UV-Vis DRS） were also employed to evaluate the photophysical property of the films. The VEOs/TiO2 composite films show a sheet-like morphology. Not only V205 phase appears in the films when the NaVO3 concentration of the electrolyte is higher than 6,10 g/L and is loaded at the surface of anatase, but also V4＋ is incorporated into the crystal lattice of anatase. In comparison with pure TiO2 films the V2Os/TiO2 composite films exhibit significantly narrow band gap energy. The film prepared in an electrolyte consisting of NaVO3 with a concentration of 8.54 g/L exhibits the narrowest band gap energy, which is approximately 1.89 eV. The V2Os/TiO2 composite films also have the significantly enhanced visible light photocatalytic activity. The film prepared in an electrolyte consisting of NaVO3 with a concentration of 8.54 g/L exhibits the best photocatalytic activity and about 93% of rhodamine is degraded after 14 h visible light radiation.

五氧化二钒薄膜材料制备方法研究进展

由于V^(5+)的饱和氧化态,五氧化二钒成为钒体系中最稳定的氧化物。作为功能材料,五氧化二钒薄膜在众多科学领域有着巨大的应用潜力,因而受到越来越多的关注。这主要归功于其特殊的层状结构、高能量密度、良好的化学和热稳定性以及优异的光学和电学性能。五氧化二钒薄膜的制备方法很多,采用不同的实验方法在不同衬底上制备的五氧化二钒薄膜因化学成分和组织结构差异而造成其电学、光学性能也存在显著的差异。本文详细阐述了五氧化二钒薄膜现有的制备技术,并对五氧化二钒薄膜材料应用的发展趋势进行了展望,以期为五氧化二钒薄膜产业的发展提供参考。

VO_(2)薄膜材料的变温光学性质及1550 nm激光防护性能研究

具有半导体-金属态相变性质的二氧化钒材料可用于光电探测器的激光致盲防护。本文报道了基于磁控溅射法制备二氧化钒薄膜材料的结构、形貌特性,以及在不同温度下的光学性质。使用椭偏光谱法测量了20~100℃下可见-近红外波段二氧化钒材料的椭偏参数,利用Gaussian、Lorentz模型获取了薄膜在相变前的光学性质,结合Drude模型拟合获取了材料在相变后的光学特性,获取了材料在300~1700 nm之间的变温折射率和消光系数等参数。变功率下1550 nm红外激光透射率的实验测试研究表明,VO_(2)薄膜样品的相变阈值功率为12 W/cm^(2),相变前后透射率由51%减小到15%~17%,开关率为69%。

掺钨VO_(2)纳米粉双相界面自组装成膜及微结构的光学性质

VO_(2)的相变温度68℃限制了其在室温环境中的应用和安全性,采用W^(6+)离子掺杂的方法可有效降低VO_(2)相变温度。利用涂有真空硅脂的聚苯乙烯模具和添加表面活性剂的W_(x)V_(1-x)O_(2)纳米溶液,在玻璃基底上通过双相界面自组装方法将水热法合成的W_(x)V_(1-x)O_(2)纳米粉末制备成薄膜,在此基础上加装直径1μm的聚乙烯线制备W_(x)V_(1-x)O_(2)/glass微结构。直接观察到液/固双相界面上毛细管流的运动过程,以及微结构两侧对称出现半月形的现象。液-固-气系统复杂的动态变化的过程,遵循流体动力学和热力学的规律。X射线衍射表征结果表明,自组装W_(x)V_(1-x)O_(2)薄膜为多晶结构,主要成分为M相VO_(2)和少量钒的其他价态氧化物及少量钨钒的氧化物(WVO_4);近红外透过率测试显示W_(x)V_(1-x)O_(2)/glass薄膜随温度变化规律与理论模拟计算的趋势吻合;其温度-透过率曲线“突变”特性优于旋涂法制备的薄膜;可见光的微结构衍射图样类似光栅衍射图样,表明此种薄膜和微结构制备方法可行。研究结果可应用于防护涂层制备和微结构光学调控领域。

化学气相沉积法制备智能窗用热致变色VO_(2)薄膜的研究进展

热致变色智能窗是通过在玻璃上沉积温度刺激响应型材料,实现根据环境温度调控窗户玻璃的太阳光透过率,减少建筑物能耗的节能窗户。二氧化钒(VO_(2))是一种典型的热致相变材料,在~68℃发生金属-绝缘体相变,相变前后伴随光学性能的显著变化,在智能窗等多个领域有潜在的技术应用。然而,当前VO_(2)基热致变色智能窗的应用仍存在着相变温度(τc)偏高、可见光透过率(Tlum)低和太阳能调节效率(ΔTsol)不足等问题,无法满足实际建筑节能的需求。为了解决这些问题,研究人员开展了广泛而深入的工作。化学气相沉积法(Chemical vapor deposition,CVD)能够以合理的成本生产高质量、大面积的VO_(2)薄膜,受到研究者青睐。本文总结了近年来利用CVD技术制备VO_(2)薄膜的研究进展,系统介绍常压化学气相沉积、气溶胶辅助化学气相沉积、低压化学气相沉积、金属有机物化学气相沉积、原子层沉积和等离子体增强化学气相沉积等CVD工艺,分析了反应物种类及比例、反应温度、压力、载体流量等因素对VO_(2)薄膜质量的影响,并结合元素掺杂、纳米复合薄膜、多层膜结构等对VO_(2)薄膜的性能调控与优化进行总结,最后对未来等离子体增强化学气相沉积制备VO_(2)薄膜的研究前景做出展望。

V_2O_5薄膜制备、结构及光学性质研究

Ｖ２Ｏ５薄膜是全固态电致变色器件中锂离子储存层的很好候选材料之一。本研究采用反应蒸发，优化实验条件，在加热基片上沉积了性能理想的Ｖ２Ｏ５薄膜，分别采用ＸＲＤ，ＡＥＳ，ＸＰＳ和紫外－近红外分光光度计研究了薄膜的晶态结构、组份、钒离子价态和光学等特性。研究结果表明，刚制备的薄膜为非晶结构，经过一定温度热处理后开始结晶，薄膜的组分为ＶＯ２．４６，含有少量的Ｖ＋４；吸收光谱存在两个不同的变化区域，高能区域对应于电子的带间跃迁，吸收边缘在２．１１ｅＶ。

关于退火温度对VO_2薄膜制备及其电学性质影响的研究

采用真空蒸发-真空退火工艺由V2O5粉末制备VO2薄膜,研究了退火温度对薄膜的影响.经XRD,XPS及电阻-温度测试发现,随退火温度的升高,VO2薄膜先后经历了单斜晶系VO2(B)型→单斜晶系VO2(A)型→四方晶系VO2的变化,在3种类型的薄膜中V均以V4+为主,且在VO2(A)型薄膜中V4+含量最高.薄膜电阻以退火温度460℃时为分界线,低于460℃时,VO2(B)型薄膜电阻和电阻温度系数随退火温度的升高而增大;高于460℃时,四方晶系VO2薄膜的电阻及其电阻温度系数随退火温度的升高呈现相反的趋势.

五氧化二钒薄膜结构与电致变色效应

采用反应蒸发制备Ｖ２Ｏ５ 薄膜，用Ｘ射线衍射分析和分光光度计分别测量薄膜晶体结构和光谱特性，利用标准三电极法从锂离子电解质溶液中向Ｖ２Ｏ５ 薄膜注入锂离子。实验结果表明：刚制备的薄膜为非晶结构，热处理使得膜结晶；Ｖ２Ｏ５ 薄膜呈较强的阳极电致变色和较弱的阴极电致变色双重效应；薄膜晶体结构影响致色效率和响应速度。对实验结果进行了分析，提出并验证了改善Ｖ２Ｏ５ 薄膜致色时光学性能的方法。

溶胶-凝胶法制备氧化钒薄膜的结构及特性研究

利用溶胶-凝胶法制备了氧化钒薄膜,在大气环境及400℃下、对产物进行不同时间的退火处理。利用扫描电子显微镜、X射线衍射仪、高阻仪、紫外-可见分光光度计和傅里叶红外光谱仪,对薄膜的形貌、晶态、电学和光学特性等进行了系统的分析。结果表明,退火时间明显地影响溶胶-凝胶法制备氧化钒薄膜的化学结构及光电性能:退火时间过短,薄膜中有机成分不能完全分解、并且结晶度低;退火1h时,薄膜主要成分为V2O5和VO2,此时薄膜电阻低、但光吸收性弱;退火2h以上,薄膜中的主要成分为V2O5,此时薄膜电阻变大、但光吸收性有所加强。研究了退火时间对溶胶-凝胶制备氧化钒薄膜的化学结构及光电特性的影响,揭示了相关的微观机理。