二氧化钒薄膜低温制备及其太赫兹调制特性研究

针对二氧化钒(VO2)薄膜在可调谐太赫兹功能器件中的应用,利用低温磁控溅射技术,在太赫兹和光学频段透明的BK7玻璃上制备出高质量的VO2薄膜.晶体结构和微观形貌分析显示薄膜为单相VO2单斜金红石结构,具有明显的(011)晶面择优取向,结构致密,表面平整.利用四探针技术和太赫兹时域光谱系统分析了薄膜的绝缘体-金属相变特性,发现相变过程中薄膜电阻率变化达到4个数量级,同时对太赫兹透射强度具有强烈的调制作用,调制深度高达89％.通过电学相变和太赫兹光学相变特性的对比研究,证实薄膜的电阻率突变主要与逾渗通路的形成有关,而太赫兹幅度的调制则来源于薄膜中载流子浓度的变化.该薄膜制备简单,成膜质量高,太赫兹调制性能优异,可应用于太赫兹开关和调制器等集成式太赫兹功能器件.     

磁控溅射法制备二氧化钒薄膜最佳参量的研究

用X射线电子能谱仪(XPS)对不同条件下用磁控溅射法制备的VO₂薄膜进行测试,得到VO₂薄膜内部组成成份的信息.研究了获得高含量VO₂薄膜的最佳制备参量.同时还观察到V₂O₃、VO₂、V₂O₅以接近含量共存的现象,这与以前研究所给出的薄膜几乎只由V₂O₃、VO₂、V₂O₅中的两种组成的结论有所不同.     

射频磁控溅射制备氧化钒薄膜的研究

氧化钒（VOx）薄膜是一种广泛应用于红外热成像探测的薄膜材料,研究VOx薄膜的制备工艺、获取高电阻温度系数（TCR）的VOx薄膜具有重要意义。以高纯金属钒作靶材,采用射频磁控溅射的方法在室温下制备了VOx薄膜。主要研究了氩氧流量比以及功率等工艺参数对薄膜TCR的影响,获得了较好的工艺参数。采用万用表和X射线光电子能谱仪（XPS）分别测试了不同条件下射频磁控溅射法制备的VOx薄膜的电阻特性和薄膜成分,测试结果表明,采用所获得的较好工艺参数制备的VOx薄膜TCR值大于1.8%。     

金属Pt薄膜上二氧化钒的制备及其电致相变性能研究

通过引入SiO₂氧化物缓冲层, 在金属Pt电极上利用射频磁控溅射技术成功制备出高质量的VO₂薄膜. 详细研究了SiO₂厚度对VO₂薄膜的晶体结构、微观形貌和绝缘体–金属相变(MIT)性能的影响. 结果表明厚度0.2 μm以上的SiO₂缓冲层能够有效 消除VO₂薄膜与金属薄膜之间的巨大应力, 制备出具有明显相变特性的VO₂薄膜. 当缓冲层达到0.7 μm以上, 获得的薄膜具有明显的(011)晶面择优取向, 表面平整致密, 相变前后电阻率变化达到3个数量级以上. 基于该技术制备了Pt-SiO₂/VO₂-Au三明治结构, 通过在垂直膜面方向施加很小的驱动电压, 观察到明显的阶梯电流跳跃, 证实实现了电致绝缘体–金属相变过程. 该薄膜制备工艺简单, 性能稳定, 器件结构灵活可应用于集成式电控功能器件. 关键词： 二氧化钒薄膜 相变特性 电致相变 阈值电压     

直流磁控溅射制备氧化钒薄膜

讨论了在低温下以高纯金属钒作靶材,用直流磁控溅射的方法制备出了氧化钒薄膜。通过设计正交试验,分析了氩气和氧气的流量比,溅射功率,工作压强,基底温度对氧化钒薄膜沉积速率和电阻温度系数TCR的影响,采用RTP-500型快速热处理机对氧化钒薄膜样品进行了退火热处理,实验结果表明:当Ar与O2的比例为100:4,溅射功率为120W,工作压强为2Pa时,所获得薄膜TCR较大,都在-2%/K附近,最高的可达-3.6%/K。     

二氧化钒薄膜的光学特性及应用前景

本文着重介绍二氧化钒（ＶＯ２）薄膜的性质，相变原理，若干制备工艺对ＶＯ２薄膜相变特性的影响并给出ＶＯ２薄膜的应用方向。     

硅基二氧化钒相变薄膜电学特性研究

本文以原子层沉积超薄氧化铝(Al₂ O₃)为过渡层, 采用射频反应磁控溅射法在硅半导体基片上制备了颗粒致密并具有(011)择优取向的二氧化钒(VO₂)薄膜. 该薄膜具有显著的绝缘体–金属相变特性, 相变电阻变化超过3 个数量级, 热滞回线宽度约为6℃. 基于VO₂薄膜构建了平面二端器件并测试了不同温度下I-V曲线, 观测到超过2个数量级的电流跃迁幅度, 显示了优越的电致相变特性. 室温下电致相变阈值电压为8.6 V, 电致相变弛豫电压宽度约0.1 V. 随着温度升高到60℃, 其电致相变所需要的阈值电压减小到2.7 V. 本实验制备的VO₂薄膜在光电存储、开关、太赫兹调控器件中具有广泛的应用价值.     

二氧化钒薄膜的变温红外光学特性研究

基于二氧化钒在约68℃出现的半导体到金属的可逆相变,伴随有电学和光学特性的改变。因为相变机制的复杂性,很难从理论上推导出相变前后光学常数随波长和温度变化的解析表达式。研究了二氧化钒薄膜的折射率和消光系数的色散规律,借助于Sellmeier色散模型通过数值拟合,得出了二氧化钒变温的光学常数色散表达式。通过薄膜矩阵理论计算,获得了在不同温度和波长条件下的薄膜光学透射率和反射率。采用磁控溅射方法分别在玻璃、蓝宝石和二氧化硅衬底上制备了不同厚度的二氧化钒薄膜,测量了这些薄膜的光学透射率和反射率,结果表明,实验曲线与计算模拟曲线符合得很好。     

氧空穴导致二氧化钒低温相带隙变窄

具有一定能量的光照导致低温绝缘二氧化钒(VO_2)发生绝缘体金属转变.本文通过密度泛函理论的Heyd-Scuseria-Ernzerhof杂化泛函方法对含氧空穴的低温绝缘VO_2非磁M1相进行第一性原理研究.研究发现,含氧空穴的M1的晶格参数几乎不变,但氧空穴附近的长的V—V键长却变短了.进一步研究发现,尽管纯的非磁M1的带隙是0.68 eV,但含O1和O2位的氧空穴非磁M1带隙分别为0.23 eV和0.20 eV,同时含有O1和O2位氧空穴非磁M1带隙为0.15 eV,这很好地解释了实验结果.     

纳米二氧化钒薄膜的电学与光学相变特性

采用双离子束溅射氧化钒薄膜附加热处理的方式制备了纳米二氧化钒薄膜。在热驱动方式下,分别利用四探针测试技术和傅里叶变换红外光谱技术对纳米二氧化钒薄膜的电学与光学半导体-金属相变特性进行了测试与分析。实验结果表明,电学相变特性与光学相变特性之间存在明显的偏差,电学相变温度为63 ℃,高于光学相变温度,60 ℃;电学相变持续的温度宽度较光学相变持续温度宽度宽;在红外光波段,随着波长的增加,纳米二氧化钒薄膜的光学相变温度逐渐增大,由半导体相向金属相转变的初始温度逐渐升高,相变持续的温度宽度变窄。在红外光波段,纳米二氧化钒薄膜的光学相变特性可以通过光波波长进行调控,电学相变特性更适合表征纳米VO₂薄膜的半导体-金属相变特性。     

Structural and optical properties of tungsten-doped vanadium dioxide films

Thin films of tungsten(W)-doped thermochromic vanadium dioxide(VO2) were deposited onto soda-lime glass and fused silica by radio frequency magnetron sputtering.The doped VO2 films were characterized by X-ray diffraction,optical transmittance measurement,and near field optical microscopy with Raman spectroscopy.X-ray diffraction patterns show that the(011) peak of W-doped thermochromic VO2 film shifts to a lower diffraction angle with the increase of W concentration.The optical measurements indicated that the transmittance change(△T) at wavelength of 2500 nm drops from 65%(T at 35℃ and 80℃ for undoped VO2 film) to 38%(T at 30℃ and 42℃ for the doped VO2 film).At the same time,phase transition temperature drops from 65℃ to room temperature or lower with the increase of W concentration.Near field optical microscopy image shows that the surface of W-doped VO2 film is smooth.Raman results show that the main Raman modes of W-doped VO2 are centered at 614 cm1,the same as that of undoped VO2,suggesting no Raman mode changes for lightly W-doped VO2 at room temperature,due to no phase transition appearing under this condition.     

Preparation and properties of vanadium dioxide thermochromic thin films

Deposition of vanadium dioxide and the study of its electrical and optical properties at varying deposition conditions have been presented. The materials have been deposited by reactive r.f. magnetron sputtering technique in Ar, O₂ ambient followed by annealing post-treatment. Electrical conductivity measurements indicate that oxygen pressure plays an important role in obtaining VO₂ and atP _{O 2}=2.4% stoichiometric VO₂ can be obtained. The deposition rate of oxides decreases with increasing O₂ pressure and the rate of VO₂ was about 130Å/min. Optical studies show that VO₂ films exhibit thermochromism and it has the potential application for energy efficient solar energy utilization.     

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.     

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.     

Fabrication of low phase transition temperature vanadium oxide films by direct current reactive magnetron sputtering and oxidation post-anneal method

Vanadium oxide thin films were deposited on ordinary glass substrates by direct current (DC) magnetron sputtering from a vanadium metal target and subsequent oxidation annealing. The deposition and annealing parameters were given in detail. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). The phase transitions of films were observed by measuring their electrical and optical property variations at different temperature. The results indicated that the films fabricated had a semiconductor–metal phase transition temperature of about 30 °C.     

溅射制备Ge,Nb共掺杂窄光学带隙和低电阻率的TiO2薄膜

采用射频磁控溅射技术制备了Ge,Nb共掺杂的锐钛矿结构TiO₂薄膜,详细探讨了薄膜的结构、电阻率及光学带隙等性质随Ge,Nb掺杂量、溅射功率和热处理温度等参数的变化,发现Ge,Nb共掺杂可以同时调节TiO₂薄膜的光学带隙和电阻率.体积分数约为6%Nb和20%Ge的共掺杂TiO₂薄膜电阻率由10⁴Ω/cm减小至10^-1Ω/cm,光学带隙由3.2 eV减小至1.9 eV.退火后掺杂TiO₂薄膜不仅显示更低的电阻率,还表现出更强的可见-红外光吸收.结果表明,改变Ge,Nb的掺杂量和退火条件能够制备出电阻率和带隙都可调的TiO₂薄膜.     

射频反应磁控溅射法制备的氟化类金刚石薄膜摩擦特性研究

以高纯石墨做靶,CHF3和Ar气为源气体,采用射频反应磁控溅射法在不同流量比条件下制备了氟化类金刚石(F-DLC)薄膜.利用原子力显微镜、纳米压痕仪、拉曼光谱和红外光谱、摩擦磨损测试仪对薄膜的表面形貌、硬度、键结构以及摩擦性能做了具体分析.表面形貌测试结果表明,制备的薄膜整体均匀致密,表现出了良好的减摩性能.当CHF3与Ar气流量比r为1:6时,所得薄膜的摩擦系数减小至0.42,而纳米压痕结果显示,此时薄膜的硬度也最高.拉曼和红外光谱显示,随着r的增加,薄膜中的F浓度呈上升趋势,薄膜中的芳香环比例减小.研究表明,F原子的键入方式是影响F-DLC薄膜摩擦系数的一个重要因素,CF2反对称伸缩振动强度的减弱和CC中适量碳氢氟键的形成都能导致薄膜具有相对较低的摩擦系数.     

退火温度对ZnO薄膜结构和发光特性的影响

采用反应射频磁控溅射法在 Si(100)基片上制备了高c轴择优取向的ZnO薄膜，研究了退火温度对ZnO薄膜的晶粒尺度、应力状态、成分和发光光谱的影响，探讨了ZnO薄膜的紫外发光光谱和可见发光光谱与薄膜的微观状态之间的关系.研究结果显示,在600—1000℃退火温度范围内，退火对薄膜的织构取向的影响较小，但薄膜的应力状态和成分有比较明显的变化.室温下光致发光光谱分析发现，薄膜的近紫外光谱特征与薄膜的晶粒尺度和缺陷状态之间存在着明显的对应关系；而近紫外光谱随退火温度升高所呈现的整体峰位红移是各激子峰相对比例变 关键词： ZnO薄膜 退火 光致发光 射频反应磁控溅射 可见光发射     

Effects of oxygen content on the microstructures and optical properties of thermochromic vanadium oxide thin films

Reactive direct current magnetron sputtering and in situ thermal oxidation were used to prepare vanadium oxide (VO _X ) thin films with different oxygen contents. X-ray diffraction, Fourier transform infrared spectroscopy and a field emission scanning electron microscope were employed to characterize the films. The optical properties of the VO _X films at room temperature and 90 °C were investigated by applying an spectroscopic ellipsometer with a three-layer model of BEMA/Brendel–Bormann oscillator/substrate. It was demonstrated that the vanadium–oxygen bonds were strengthened, the film thickness and roughness decreased, while the grain size increased with increasing oxygen content. The increase in oxygen content had the effect of decreasing the near-infrared reflectance and free-electron concentration of the film at 90°C due to the decrease in the amount of VO₂.     

高压退火对0.65PMN-0.35PT薄膜结构、形貌及电学性能的影响

利用射频磁控溅射技术在LaNiO₃/SiO₂/Si(100)基底上制备了厚 度约为250 nm的0.65PMN-0.35PT(PMN-PT)薄膜. 研究高压氧氛围退火方式对PMN-PT薄膜晶体结构、形貌以及电学性能的影响. 经过XRD测试发现,在高压氧气氛围中, 温度为400℃下退火后的PMN-PT薄膜具有纯的钙钛矿相结构, 具有完全的(100)择优取向, 且衍射峰尖锐, 表明经过高压退火后的薄膜结晶极为充分. SEM表面形貌测试结果显示, 经高压退火处理的PMN-PT薄膜表面呈现出棒状或泡状的形貌. 铁电性能测试表明: 氧气氛围压强4 MPa, 退火时间4h的PMN-PT薄膜样品具有较好的铁电性能, 其剩余极化强度P_r达到10.544 μC/cm², 且电滞回线形状较好, 但漏电流较大, 这可能是由于其微结构所导致.同时介电测试发现: PMN-PT薄膜样品具有极好的介电性能, 其在1 kHz下测试的介电常数ε_r达到913, 介电损耗tgδ 较小, 仅为0.065. 关键词： 射频磁控溅射 高压退火 0.65PMN-0.35PT 介电