Fabrication of VO_2 thin film by rapid thermal annealing in oxygen atmosphere and its metal–insulator phase transition properties

Vanadium dioxide thin films have been fabricated through sputtering vanadium thin films and rapid thermal annealing in oxygen. The microstructure and the metal–insulator transition properties of the vanadium dioxide thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and a spectrometer. It is found that the preferred orientation of the vanadium dioxide changes from(1ˉ11) to(011) with increasing thickness of the vanadium thin film after rapid thermal annealing. The vanadium dioxide thin films exhibit an obvious metal–insulator transition with increasing temperature, and the phase transition temperature decreases as the film thickness increases. The transition shows hysteretic behaviors, and the hysteresis width decreases as the film thickness increases due to the higher concentration carriers resulted from the uncompleted lattice. The fabrication of vanadium dioxide thin films with higher concentration carriers will facilitate the nature study of the metal–insulator transition.     

电触发二氧化钒纳米线发生金属-绝缘体转变的机理

二氧化钒(VO_2)是一种强关联相变材料,在341 K下发生金属-绝缘体转变.尽管对于VO_2相变的物理机理进行了大量研究,但科学家仍未形成统一认识.与热致VO_2相变相比,电触发VO_2相变应用前景更为广阔,但其机理也更为复杂.本文利用原位通电杆和超快相机技术,在透射电镜下原位观察了单晶VO_2纳米线通电时的相转变过程,记录了相变过程中对应的电压-电流值,并在毫秒尺度下捕捉到了VO_2的过渡相态.发现VO_2电致相变并非由焦耳热引起,推断其机理是载流子注入.同时观察到电子结构相变和晶体结构相变存在解耦现象,进一步支持了上述推断.将VO_2纳米线两端施加非接触式电场,观察到VO_2纳米线在电场中的极化偏移,而未观察到相变发生,该现象同样支持相变的载流子注入机理.研究表明VO_2的金属-绝缘体转变遵循电子-电子关联机理,即根据电子关联的Mott转变进行.     

电场诱导二氧化钒绝缘-金属相变的研究进展

二氧化钒(VO_2)是电子强关联体系的典型代表,其晶体结构在特定阈值的温度、电场、光照和压力等物理场作用下会发生由单斜金红石结构向四方金红石结构的可逆转变,从而引发绝缘-金属相变.其中,电场诱导VO_2绝缘-金属相变后的电导率可提高2-5个数量级,在可重构缝隙天线、太赫兹辐射以及智能电磁防护材料等领域具有广阔的应用前景,成为近年来人们的研究热点.首先,简要概述了VO_2发生绝缘-金属相变时晶体结构和能带结构的变化,进而从电场诱导VO_2绝缘-金属相变的研究方法、响应时间、临界阈值场强调控以及相变机理几个方面系统总结和评述了近年来国内外学者在该领域的重要发现和研究进展.最后,指出了当前VO_2绝缘-金属相变研究存在的问题,并展望了未来的发展方向.     

VO2金属-绝缘体相变机理的研究进展

VO₂是一种热致相变金属氧化物. 在341 K附近, VO₂发生由低温绝缘体相到高温金属相的可逆转变, 同时伴随着光学、电学和磁学等性质的可逆突变, 这种独特的性质使得VO₂在光电开关材料、智能玻璃、存储介质材料等领域有着广阔的应用前景. 因此, VO₂金属-绝缘体可逆相变一直是人们的研究热点, 但其相变机理至今未有定论. 首先, 简要概述了VO₂相变时晶体结构和能带结构的变化情况: 从晶体结构来讲, 相变前后VO₂从低温时的单斜相VO₂(M)转变为高温稳定的金红石相VO₂(R), 在一定条件下此过程也可能伴随着亚稳态单斜相VO₂(B)与四方相VO₂(A)的产生; 从能带结构来看, VO₂处于低温单斜相时, 其d_//能带和π^*能带之间存在一个禁带, 带宽约为0.7 eV, 费米能级恰好落在禁带之间, 表现出绝缘性, 而在高温金红石相时, 其费米能级落在π^*能带与d_//能带之间的重叠部分, 因此表现出金属导电性. 其次, 着重总结了VO₂相变物理机理的研究现状. 主要包括: 电子关联驱动相变、结构驱动相变以及电子关联和结构共同驱动相变的3种理论体系以及支撑这些理论体系的实验结果. 文献报道争论的焦点在于, VO₂是否是Mott绝缘体以及结构相变与MIT相变是否精确同时发生. 最后, 展望了VO₂材料研究的发展方向.     

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     

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.     

Controllable synthesis of highly ordered Ag nanorod arrays by chemical deposition method

Highly ordered Ag nanorod arrays were successfully fabricated using a simple chemical deposition method with the assistance of porous alumina membrane (PAM) template. The products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ag⁺ ions in the PAM nanochannels were reduced by acetaldehyde reagent and resulting in the formation of rod array structures. It is found that the diameter of the Ag nanorods is determined by the PAM template, and the length of the Ag nanorods is depended on the reaction temperature. The growth mechanism of the Ag nanorod arrays is investigated in the study.     

氧化钒晶体的半导体至金属相变的理论研究

本文利用第一性原理方法研究了金红石相和单斜相VO₂晶体的电子结构和热力学性质.在计算中采用局域密度近似结合Hubbard U模型(LDA+U)描述电子的局域强关联效应,同时也利用微扰密度泛函方法计算了两种相结构的声子谱.计算结果表明V原子3d电子轨道中x²-y²轨道能级分裂决定了VO₂晶体在不同相结构下的金属和绝缘体特性.零温状态方程计算揭示了在68 GPa时可以发生从单斜结构 关键词： 2')" href="#">VO₂ 相变 第一性原理     

Room-temperature epitaxial growth of V2O3 films

Herein we report the room-temperature epitaxial growth of V2O3 films by laser molecule beam epitaxy. X-ray diffraction profiles show the room-temperature epitaxial V2O3 films orient in the [110] direction on α-Al2O3(0001) substrates. Atomic force microscopy measurements reveal that the ultra-smooth surfaces with root-mean-square surface roughness of 0.11 nm and 0.28 nm for 10-nm-thick and 35-nm-thick V+2O3 film, respectively. X-ray photoelectron spectroscopy results indicate the V3 oxidation state in the films. Typical metal-insulator transition is observed in films at about 135 K. The resistivities at 300 K are approximately 0.8 mΩ cm and 0.5 mΩ cm for 10-nm-thick and 35-nm-thick V2O3 film, respectively.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals

VO₂ single crystals with unprecedented quality, exhibiting a first‐order metal–insulator transition (MIT) at 67.8 °C and an insulator –insulator transition (IIT) at ～49 °C, are grown using a self‐flux evaporation method. Using synchrotron‐based X‐ray microdiffraction analysis, it is shown that the IIT is related to a structural phase transition (SPT) from the monoclinic M2 phase to the M1 phase upon heating while the MIT occurs together with a SPT of M1 to the rutile R phase. All previous reports have shown that VO₂ exists in the M1 phase at room temperature in contrast to the M2 phase observed in this work. We suggest that internal strain inside single crystal VO₂ may generate the previously unobserved IIT and the unusual room temperature structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Compare the phase transition properties of VO2 films from infrared to terahertz range

VO₂ with reversible semiconductor–metal phase transition properties is particularly available for the application in smart opto-electrical devices. However, there are rare reports on comparing its phase transition properties at different ranges. In this study, the VO₂ films are designed with the similar crystalline structure and stoichiometry, but different morphologies by inorganic and organic sol-gel methods, and their phase transition characteristics are compared both at infrared and terahertz range. The results indicate that the VO₂ film prepared by inorganic sol-gel method shows more compact nanostructure. It results in larger resistivity change, infrared and terahertz switching ratio in the VO₂ film. Moreover, it presents that the phase transition intensity of VO₂ film in terahertz range is more sensitive to its microstructure. This work is helpful for understanding the susceptibility of terahertz switching properties of VO₂ to its microstructure. And it can provide insights for the applications of VO₂ in terahertz smart devices.     

VO2光学薄膜的脉冲激光损伤特性测试

为评价VO2光学薄膜在光电器件中的工作可靠性,搭建了可输出连续渐变激光能量密度的脉冲激光照射实验平台,运用1对1与s对12种激光损伤测试手段进行激光辐射照射实验,采用线性外推法和测量计算法2种方法对实验结果进行了处理并得出VO2薄膜在重复频率10 kHz、中心波长532 nm、脉冲宽度15 ps脉冲激光辐射下的损伤特性。结果表明:VO2薄膜损伤几率与脉冲激光的单脉冲能量密度呈线性关系,重复辐射的激光脉冲对VO2薄膜造成的损伤具有积累效应,且重复辐射的激光脉冲次数越多损伤积累效果越明显。     

Oxygen stoichiometry controlled sharp insulator-metal transition in highly oriented VO2/TiO2 thin films

The insulator-metal transition (IMT) in vanadium dioxide (VO₂) which occurs above room temperature (67 °C) is highly sensitive to atomic defects caused by oxygen stoichiometry. The strained growth and the degree of oxygen deficiency in VO₂ epitaxial films result in lowering of transition temperature below room temperature as well as the broadening of transition parameters such as transition width and hysteresis width, which limit its application potential. Here we demonstrate the growth of highly oriented strain-relaxed VO₂ thin films on (001)-oriented TiO₂ substrates at various oxygen partial pressures, exhibiting the narrow transition and hysteresis width. The cross-sectional transmission electron microscopy and x-ray diffraction analyses of the films reveal the highly oriented growth of insulating monoclinic VO₂. The IMT parameters associated with temperature-dependent phase transition vary with the oxygen partial pressure used during the deposition. The presence of multiple and mixed valence states of vanadium in the films was confirmed by Raman and XPS analyses. We have achieved a narrow transition width (2.3 °C) and hysteresis width (1.2 °C) through controlling the oxygen stoichiometry during the growth of VO₂/TiO₂ films.     

Synthesis and bactericidal ability of Ag/TiO2 composite films deposited on titanium plate

In this study, we develop a bactericidal coating material for micro-implant, TiO₂ films with Ag deposited on were prepared on titanium plates by sol-gel process. Their anti-microbial properties were analyzed as a function of the annealed temperature using Escherichia coli as a benchmark microorganism. Ag nanoparticles deposited on TiO₂ film were of metallic nature and could grow to larger ones when the annealed temperature increased. The results indicated that the smaller size of Ag nanoparticles, the better bactericidal ability. On the other hand, the positive antibacterial effect of TiO₂ enhanced the bactericidal effect of Ag.     

α-SiN:H薄膜的光学声子与VO2基Mott相变场效应晶体管的红外吸收特性

从器件构成材料中α-SiN:H，VO₂，Al薄膜介电常数弥散特性的Lorentz多谐振模型出发，研究了器件在金属表面等离子体与VO₂，特别是α-SiN:H薄膜光学声子共同作用下的红外吸收特性；得到了在不同的光谱范围器件的红外吸收特性随着α-SiN: H钝化层几何厚度的变化关系，与中心工作波长10μm对应的且经过位相修正以后钝化层的几何厚度为λ/4n时的红外吸收光谱、以及VO₂的相变对吸收光谱的影响. 关键词： 红外吸收特性 Mott相变 场效应晶体管 二氧化钒     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals [Phys. Status Solidi RRL 5, No. 3, R107–R109 (2011)]

In our article, we reported the observation of monoclinic M2 to M1 structural phase transition in VO₂ single crystal near the temperature of ～49 °C. However, the re‐examination of Laue patterns reveals that previously defined monoclinic M1 and M2 phases can be interpreted as monoclinic M2 and triclinic T phases instead. Careful experimental geometry calibration and further refinement of the lattice parameter ratios and angles show that monoclinic M2 and triclinic T phases fit better with the experimental data. On the other hand, our previous misidentification of the insulating phases does NOT affect the conclusions of our article. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Direct comparison of the electrical,optical, and structural phase transitions of VO2 on ZnO nanostructures

We examined the temperature-dependent electrical, optical, and structural properties of VO₂ on ZnO nanorods with different lengths in the temperature range from 30 to 100 °C. ZnO nanorods with a uniform length were grown on Al₂O₃ substrates using a metal organic chemical vapor deposition, and subsequently, VO₂ was ex-situ deposited on ZnO nanorods/Al₂O₃ templates using a sputtering deposition. The optical properties of the VO₂/ZnO nanorods were measured simultaneously with direct current (DC) resistance using the reflectivity of an infrared (IR) laser beam with a wavelength of 790 nm. The local structural properties around V atoms of VO₂/ZnO nanorods were simultaneously measured with the DC resistance using x-ray absorption fine structure at the V K edge. Direct comparison of the temperature-dependent resistance, IR reflectivity, and local structure reveals that an optical phase transition first occurs, a structural phase transition follows, and an insulator-to-metal transition finally appears during heating.     

The metal‐insulator transitions of VO2: A band theoretical approach

The results of first principles electronic structure calculations for the metallic rutile and the insulating monoclinic phase of vanadium dioxide are presented. In addition, the insulating phase is investigated for the first time. The density functional calculations allow for a consistent understanding of all three phases. In the rutile phase metallic conductivity is carried by metal orbitals, which fall into the one‐dimensional band, and the isotropically dispersing bands. Hybridization of both types of bands is weak. In the phase splitting of the band due to metal‐metal dimerization and upshift of the bands due to increased p‐d overlap lead to an effective separation of both types of bands. Despite incomplete opening of the optical band gap due to the shortcomings of the local density approximation, the metal‐insulator transition can be understood as a Peierls‐like instability of the band in an embedding background of electrons. In the phase, the metal‐insulator transition arises as a combined embedded Peierls‐like and antiferromagnetic instability. The results for VO₂ fit into the general scenario of an instability of the rutile‐type transition‐metal dioxides at the beginning of the d series towards dimerization or antiferromagnetic ordering within the characteristic metal chains. This scenario was successfully applied before to MoO₂ and NbO₂. In the compounds, the and bands can be completely separated, which leads to the observed metal‐insulator transitions.     

硅基VO2纳米薄膜光致绝缘体—金属相变的THz时域频谱研究

利用THz时域频谱技术(THz-TDS)研究了硅基二氧化钒(VO₂)纳米薄膜的光致绝缘体—金属相变特性.在连续光激发下前后,观察到了非常明显的THz透过率变化,并通过薄膜近似计算出了THz波段金属态VO₂薄膜的电导率.根据实验结果建立了金属态VO₂薄膜的等效Drude模型,得到了复电导率,复电容率以及复折射率等相关的基本参数,并通过基于时域有限积分法模拟了THz波穿透硅基金属态VO₂薄膜的过程,验证了所建立的模型的正确 关键词： 二氧化钒 光致相变 Drude模型 THz时域频谱技术