298 K下离子液体BMIMPF6 中电沉积制备镧金属薄膜

以无水硝酸镧、1-丁基-3-甲基咪唑六氟磷酸（BMIMPF₆）和助溶剂丙酮为电解液,在室温（298 K）下电沉积制得镧金属薄膜。电解液BMIMPF₆的电化学窗口为-2.5~1.5 V vs. Pt,La³⁺还原为La²⁺发生于-1.7 V vs. Pt,La²⁺还原为La⁰发生于-2.1 V vs. Pt。BMIMPF₆的低吸湿性有利于在空气气氛下电沉积镧。使用扫描电子显微镜和光学显微镜观察到所制备的薄膜织构致密,经能量色散谱和X射线光电子能谱对沉积薄膜进行了表征,确定了薄膜中含有大量镧元素。通过探究电压扫描速率和硝酸镧浓度对La³⁺的电化学行为的影响,证明La³⁺的还原反应是一个受物质扩散控制的不可逆过程,La³⁺在BMIMPF₆中的扩散系数为1.47×10^-9 cm²·s^-1。本研究为获得金属镧薄膜和镧氧化物薄膜提供了一种简便的方法,并且有望用于电沉积制备其它镧系元素薄膜。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

酸刻蚀处理对IrO2-Ta2O5/Ti阳极寿命的影响

通过改变腐蚀方法,研究了使用H₂C₂O₄和H₂SO₄进行钛基体表面刻蚀对金属氧化物钛阳极电化学性能和表面形貌的影响。采用扫描电子显微镜、X射线衍射仪和光电子能谱等测试方法对样品进行了结构分析。然后利用电化学工作站测试了样品的电催化活性,利用加速寿命测试研究了样品的电化学稳定性。结果表明,通过H₂C₂O₄和H₂SO₄分步腐蚀可以获得更加均匀致密的表面形貌和更好的催化稳定性。在此基础上,进一步研究了预处理对钛阳极寿命的影响原因。IrO₂-Ta₂O₅/Ti阳极的催化活性和稳定性与酸刻蚀处理的先后顺序及表面结构密切相关,并建立了预处理方法与阳极性能之间的关系。分步腐蚀使钛表面具有合适的粗糙度,因而提升了涂层附着力。在热分解过程中,经分步腐蚀形成的氢化钛在不改变表面形貌的情况下转变为金红石结构的氧化钛,有利于电子输运,从而增强涂层附着力并延长加速寿命。     

USb2单晶的生长及磁性和输运性质研究

采用Sb自助熔剂法成功生长高质量的USb₂单晶,并研究了磁化率、电阻、磁阻和比热等性质。研究表明,中等关联强度的USb₂中的5f电子具有巡游和局域双重特征。USb₂中的5f电子在260 K附近开始发生相干,203 K由顺磁态转变为反铁磁态,进行费米面的重构。在113 K以下局域的5f电子与传导电子发生第一次杂化使费米面附近电子结构发生变化。在54 K以下通过第二次杂化使得费米面附近形成了杂化能隙。在更低温度下晶体场效应对物理性质也产生了一定的影响。     

高功率脉冲磁控溅射技术制备纳米级ZrO2薄膜的高耐腐蚀性

高质量的金属氧化物薄膜在航天航空、海洋船舶等极端环境下的关键部件有着广泛的应用需求,但传统制备技术易导致薄膜疏松多孔,产生空隙裂纹等缺陷,高功率脉冲磁控溅射技术(HiPIMS)已被证明是一种有效制备无空洞和无弧滴致密薄膜的有效方法。通过 HiPIMS 技术在不锈钢表面制备超薄致密 ZrO₂ 薄膜,重点研究不同 O₂流量下耐腐蚀性能的调控规律。 通过扫描电子显微镜(SEM)、光电子能谱仪(XPS)、X 射线衍射仪(XRD)、原子力显微镜(AFM)、纳米压痕仪(Nano Test P3)、电化学设备(CS300)等对 ZrO₂薄膜的表面形貌、物相结构、力学性能、耐腐蚀性能等方面进行研究。研究结果显示, 在 O₂流量为 40 mL/ min 时,ZrO₂ 薄膜的纳米硬度 H 最高为 26.38 GPa,弹性模量 E 为 290.9 GPa;同时,在电化学腐蚀试验中,其自腐蚀电流密度 I_corr达到 45.802 pA / cm² ,与 304L 不锈钢相比降低了 4 个数量级;电化学阻抗谱(EIS)显示,随 O₂流量的增加,容抗弧半径、低频区阻抗值和相角均随之不断增大,进一步表明 O₂ 流量为 40 min / mL 制备薄膜的耐腐蚀性能最优。通过 HiPIMS 技术能够制备出高质量的 ZrO₂ 薄膜,其高耐腐蚀性对基体起到了强效的防护作用,对防腐薄膜的研究和应用具有一定参考价值。     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

W18O49@Cu2O纳微米复合材料的制备及其光催化性能研究

本文首先用热蒸发方法制备得到了W₁₈O₄₉纳微米棒,然后经醋酸铜饱和溶液浸泡后再热处理的办法成功在W₁₈O₄₉纳微米棒表面负载Cu₂O制得得到了W₁₈O₄₉@Cu₂O纳微米复合材料;采用X-射线衍射仪、扫描电子显微镜、X-射线能谱分析及透射电子显微镜对样品进行分析表征;最后选用亚甲基蓝溶液作为目标降解物模拟污水处理测试材料的光催化性能。实验结果表明,W₁₈O₄₉纳微米棒在饱和醋酸铜溶液中浸泡时间越长,所得到的催化剂中Cu₂O的负载量越多,且所制备的W₁₈O₄₉@Cu₂O的纳微米复合材料相对于纯W₁₈O₄₉纳微米棒,其光催化效率得到了显著提高。     

SnO2 增强相对AgCuOIn2O3 电触头材料显微组织与性能的影响

采用反应合成法结合塑性变形工艺制备了不同SnO₂含量的AgCuOIn₂O₃SnO₂电触头材料,利用扫描电镜和金相显微镜表征了材料的微观形貌及显微组织,分析对比了不同SnO₂含量的材料金相组织及其增强相的分布均匀性,并利用X射线衍射分析了材料的物相结构。测量了材料的抗拉伸强度、硬度、电阻等性能。结果表明：添加适量的SnO₂能使组织中的孔隙尺寸缩小、其他缺陷明显减少。氧化物弥散分布在银基体中,极大地改善了AgCuOIn₂O₃电触头材料的显微组织均匀性。在SnO₂含量不变时,材料的电阻率随塑性变形程度增加而有所降低;随着SnO₂含量增多,电阻率呈现先降低后升高的趋势,最后趋于定值,约为2.4 μΩ·cm。添加SnO₂后各试样材料的硬度均显著升高,SnO₂含量为1%（质量分数）的材料具有最优的抗拉伸强度和延伸率。     

MgB2/Mo多层膜的制备与超导性质的研究

本文采用磁控溅射技术(MS)和混合物理化学气相沉积法(HPCVD)在单晶Al₂O₃基底上制备MgB₂/Mo多层膜。通过扫描电子显微镜(SEM)、X射线衍射(XRD)和标准四线法对样品的表面形貌、晶体结构和超导特性进行了测量研究。实验结果表明随着后续MgB₂沉积温度的增加各膜层结晶程度进一步提高,晶粒尺寸不断增大,各自保持着良好的物质稳定性。在730℃温度下生长的MgB₂薄膜的超导转变温度T_con和零电阻温度T_c0分别为39.73K~39.53K,剩余电阻率~0.77μΩcm,表明样品处于干净极限。     

非平衡磁控溅射La-Ti/WS2 自润滑薄膜的摩擦磨损行为

要满足航天器机械转动部件在恶劣工况下的工作,需研制高硬度、低摩擦系数的固体润滑薄膜。采用非平衡磁控溅射法分别制备了纯WS₂薄膜、Ti掺杂WS₂复合薄膜和La-Ti掺杂WS₂复合薄膜。分析了薄膜的微观形貌、成分、硬度和摩擦学性能。结果表明,与纯WS₂薄膜和Ti/WS₂复合薄膜相比,La-Ti/WS₂复合薄膜的微观结构更加致密。La-Ti/WS₂复合薄膜的硬度H和弹性模量E也显著提高。此外,La-Ti/WS₂复合薄膜的摩擦系数减小,并且H/E比值增大,La-Ti/WS₂复合薄膜的磨损率降低。结果表明,La的掺杂有助于在摩擦接触表面形成稳定的转移膜,提高La-Ti/WS₂复合薄膜的耐磨性和承载能力。     

Synthesis-structure relations for reactive magnetron sputtered V2O5 films

V₂O₅ films were grown onto MgO (100) substrates by reactive magnetron sputtering between 26 °C to 300 °C to establish a detailed synthesis-structure relation. The effect of deposition temperature on structural characteristics and surface morphology was characterized using X-ray diffraction, Raman spectroscopy, atomic force microscopy and scanning and transmission electron microscopy. Films prepared at room temperature are amorphous while those deposited above 80 °C exhibit a polycrystalline structure with the orthorhombic symmetry of the V₂O₅ phase.     

Effect of annealing on pulsed laser deposited zirconium oxide thin films

Zirconium oxide thin films were deposited using pulsed laser ablation from a ceramic ZrO₂ target on unheated substrates. Subsequently, the films were annealed in air in the temperature range 400-800 °C. The films were characterized by X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and optical spectroscopy to investigate the variation of the structural, chemical, and optical properties upon annealing. As-deposited films were amorphous and had a large surface density of ablated particles. Annealing resulted in the growth of monoclinic nano-crystalline, uniform, and transparent films that were slightly sub-stoichiometric. The annealed films were compact and had high values of the refractive index. Extinction coefficients were small, and may be related to the presence of defects. The films exhibited the presence of an indirect band gap, related to defects, and a direct band gap, related to fundamental absorption.     

Microstructure and characterization of La2O3 and CeO2 doped diamond-like carbon nanofilms

Seven kinds of hydrogen-free La₂O₃ and CeO₂ doped DLC films with thickness of 220-280 nm were deposited on Si (100) substrates by unbalanced magnetron sputtering. Nanoparticles with diameter of 20-30 nm are formed on the surface of films. The surface roughness Ra of films is in the range of 1.5-2.0 nm. C, La, Ce and O elements distribute uniformly along the depth direction, and C, La, and Ce elements diffuse into the Si substrate at the interface. X-ray photoelectron spectroscopy confirms that the La₂O₃ and CeO₂ form within the DLC amorphous films, and Raman spectra indicate the obvious amorphous characteristics of DLC films. High-resolution transmission electron microscopy shows the nanocrystallines structure with diameter of 2-3 nm of 16% La₂O₃ and 10% CeO₂ doped DLC films, and Fourier transformation spectroscopy also exhibits the obvious crystalline characteristics. In this work, the microstructure of two kinds of rare earth oxides doped DLC composite films is measured and analyzed.     

Growth and characterization of chemical bath deposited Cd1−xZnxS thin films

Cd_1−xZn_xS (0 ≤ x ≤ 1) thin films have been deposited by chemical bath deposition method on glass substrates from aqueous solution containing cadmium acetate, zinc acetate and thiourea at 80 ± 5 °C and after annealed at 350 °C. The structural, morphological, compositional and optical properties of the deposited Cd_1−xZn_xS thin films have been studied by X-ray diffractometer, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), photoluminescence (PL) and UV-vis spectrophotometer, respectively. X-ray diffraction analysis shows that for x < 0.8, the crystal structure of Cd_1−xZn_xS thin films was hexagonal structure. For x > 0.6, however, the Cd_1−xZn_xS films were grown with cubic structure. Annealing the samples at 350 °C in air for 45 min resulted in increase in intensity as well as a shift towards lower scattering angles. The parameters such as crystallite size, strain, dislocation density and texture coefficient are calculated from X-ray diffraction studies. SEM studies reveal the formation of Cd_1−xZn_xS films with uniformly distributed grains over the entire surface of the substrate. The EDX analysis shows the content of atomic percentage. Optical method was used to determine the band gap of the films. The photoluminescence spectra of films have been studied and the results are discussed.     

Microwave ECR plasma CVD of cubic Y2O3 coatings and their characterization

Yttrium oxide (Y₂O₃) thin films are deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process at a substrate temperature of 350 °C using indigenously developed metal organic precursors (2,2,6,6-tetra methyl-3,5-heptane dionate) yttrium, commonly known as Y(thd)₃ synthesized by ultrasound method. The deposited coatings are characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction, scanning electron microscopy, EDS and infrared spectroscopy. The characterization results indicate that it is possible to deposit non-porous coatings with excellent uniformity of a single phase cubic Y₂O₃ on various substrates by this process at reasonably low substrate temperature that is desirable in various manufacturing processes.     

Preparation and photocatalytic properties of sillenite Bi12TiO20 films

Sillenite Bi₁₂TiO₂₀ thin films with high photocatalytic activity have been successfully fabricated by means of chemical solution decomposition, and characterized by X-ray diffraction, energy-dispersive spectroscopy, atomic force microscopy, scanning electron microscopy and UV-Vis spectrophotometry. The photocatalytic activity of Bi₁₂TiO₂₀ thin films has been evaluated by photodegrading methyl orange solution and the effect of processing conditions on the photocatalytic activity has been studied in detail.     

Influence of heat treatment on the particle size of nanobrookite TiO2 thin films produced by sol-gel method

Pure nanobrookite titania (TiO₂) thin films were deposited on glass substrates by the spin-coating method using titanium butoxide and acetic acid. The particle sizes of TiO₂ films were controlled by heat treatment temperatures. The activation energy for particle growth was calculated as 23.1 kJ/mol. The structural and optical properties of the nanobrookite TiO₂ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), ultraviolet-visible absorption spectroscopy (UV-vis), and Fourier transform infrared spectroscopy (FTIR).     

Optical floating zone method growth and photoluminescence property of MgNb2O6 crystal

MgNb₂O₆ single crystals are grown by the optical floating zone method. The as-grown crystals are dark brown and have dimensions of Ø 4-6 mm × L 87 mm, with the largest crystal domain being Ø 5 mm × L 32 mm. After being annealed, the crystals fade to light brown. The powder X-ray diffraction analysis shows that the crystals have a columbite-type MgNb₂O₆ structure. The crystal grows along the c-axis and the cleavage plane is the (0 1 0) plane. Transmission polarized light microscopy measurements show that the crystal is free of low-angle grain boundaries and inclusions. The crystals have been characterized by Raman scattering, which reveals the change of Nb-O band in annealed and non-annealed samples. The photoluminescence spectra exhibit a broad and strong blue emission band centered at 435 nm.