晶粒尺寸对氧化钒薄膜电学与光学相变特性的影响

采用直流对靶磁控溅射方法制备氧化钒薄膜,通过改变热处理温度获得了具有不同晶粒尺寸的相变特性氧化钒薄膜,对氧化钒薄膜相变过程中电阻和红外光透射率随温度的突变性能进行研究.结果表明:经300℃和360℃热处理后,薄膜内二氧化钒原子分数达到40%,氧化钒薄膜具有绝缘体-金属相变特性,薄膜的晶粒尺寸分别为50nm和100nm;...     

Compositional and metal-insulator transition characteristics of sputtered vanadium oxide thin films on yttria-stabilized zirconia

Vanadium dioxide (VO₂) thin films have been shown to undergo a rapid electronic phase transition near 70 °C from a semiconductor to a metal, making it an interesting candidate for exploring potential application in high speed electronic devices such as optical switches, tunable capacitors, and field effect transistors. A critical aspect of lithographic fabrication in devices utilizing electric field effects in VO₂ is the ability to grow VO₂ over thin dielectric films. In this article, we study the properties of VO₂ grown on thin films of Yttria-Stabilized Zirconia (YSZ). Near room temperature, YSZ is a good insulator with a high dielectric constant ($\epsilon _{\rm r} > 25$\epsilon _{\rm r} > 25). We demonstrate the sputter growth of polycrystalline VO₂ on YSZ thin films, showing a three order resistivity transition near 70 °C with transition and hysteresis widths of approximately 7 °C each. We examine the relationship between chemical composition and transition characteristics of mixed phase vanadium oxide films. We investigate changes in composition induced by low temperature post-deposition annealing in oxidizing and reducing atmospheres, and report their effects on electronic properties.     

钨掺杂二氧化钒薄膜的THz波段相变性能的研究

通过溶胶–凝胶法制备纯的VO₂和W掺杂的VO₂薄膜, 并且进行了XPS、AFM和XRD的分析与表征, 并观察了其微观形貌和结构. 同时研究了VO₂和W掺杂VO₂在红外光谱(λ=4 μm)和THz(0.3~1.0 THz)区域的金属–绝缘转变性能. 结果表明: 室温下W掺杂的VO₂薄膜在红外和THz区域的初始透过率都比纯的VO₂薄膜低. 在THz波段, W掺杂的VO₂表现出更低的相变温度. 同时在VO₂和W掺杂VO₂相变过程中, 观察到了金属–绝缘转变和结构转变的现象, W掺杂VO₂具有明显的峰位偏移现象.     

Structural, electrical and optical properties of thermochromic VO2 thin films obtained by reactive electron beam evaporation

We present the structural and physical characterization of vanadium dioxide (VO₂) thin films prepared by reactive electron beam evaporation from a vanadium target under oxygen atmosphere. We correlate the experimental parameters (substrate temperature, oxygen flow) with the films structural properties under a radiofrequency incident power fixed to 50 W. Most of the obtained layers exhibit monocrystalline structures matching that of the monoclinic VO₂ phase. The temperature dependence of the electrical resistivity and optical transmission for the obtained films show that they present thermoelectric and thermochromic properties, with a phase transition temperature around 68 °C. The results show that for specific experimental conditions the VO₂ layers exhibit sharp changes in electrical and optical properties across the phase transition.     

Growth and structural characterisation of vanadium oxide ultrathin films on TiO2 (110)

The research activity of our group in the last few years has mainly been devoted to the study of ultrathin vanadium oxide films deposited on a (110)-oriented TiO₂ single crystal, in order to prepare systems which may be largely thought of as simplified models for the investigation of the structure/properties relationships in real world catalysts, sensing and optical devices. The main objective of our work consists of setting up reproducible synthesis routes for the deposition of vanadium oxide ultrathin films on TiO₂ (110), through strict control of the reaction parameters. The films obtained are then characterised from a chemical, electronic and structural point of view, and their properties are compared to those of their bulk-related phases. Results are presented concerning growth procedures and structural and electronic properties of vanadium oxide ultrathin films on titania, with a stoichiometry ranging from VO₂, down to approximately VO. In particular, it will be shown that the oxidation product of metallic vanadium in an oxygen or water atmosphere (in the 10⁻⁶ mbar range) retains the rutile lattice structure typical of stoichiometric VO₂, despite the increasing degree of oxygen defectiveness and the electronic properties, very similar to those pertaining to bulk V₂O₃. The peculiar behaviour of vanadium oxide on titania demonstrates how important the epitaxial influence of the substrate is on the nature of the overlayer. These results could represent a good starting point to understand why vanadium oxides on TiO₂ show an enhanced catalytic activity and selectivity in many industrially relevant reactions.     

Electron back-scattered diffraction of crystallized vanadium dioxide thin films on amorphous silicon dioxide

Crystalline films and isolated particles of vanadium dioxide (VO₂) were obtained through solid phase crystallization of amorphous vanadium oxide thin films sputtered on silicon dioxide. Electron back-scattered diffraction (EBSD) was used to study the crystals obtained in the thin films, to differentiate them from different vanadium oxide stoichiometries that may have formed during the annealing process, and to study their phase and orientation. EBSD showed that the crystallization process yielded crystalline vanadium dioxide thin films, semi-continuous thin films, and films of isolated particles, and did not show evidence of other vanadium oxide stoichiometries present. Indexing of the crystals for the orientation study was performed using EBSD patterns for the tetragonal phase of vanadium dioxide, since it was observed that EBSD patterns for the monoclinic and tetragonal phases of vanadium dioxide are not distinguishable by computer automated indexing. Using the EBSD patterns for the tetragonal phase of vanadium dioxide, orientation maps showed that all VO₂ crystals that were measurable (approximately the thickness of the film) had a preferred orientation with the c-axis of the tetragonal phase parallel to the plane of the specimen.     

Metal-semiconductor transition in nonstoichiometric vanadium dioxide films

Undoped and tungsten-doped nonstoichiometric vanadium dioxide films have been prepared by a modified sol-gel process, and the effect of synthesis conditions on the parameters of the metal-semiconductor transition in the films has been studied. In particular, it is shown that the temperature of the metal-semiconductor transition in vanadium dioxide decreases with increasing W content and that no phase transition occurs at doping levels above 6 at %. The composition of the films has been evaluated by x-ray diffraction, and their surface morphology has been examined by atomic force microscopy. The parameters of electrical switching in the films can be stabilized by reducing the transition temperature.     

Properties of tungsten-doped vanadium oxide films

The structure and properties of tungsten-doped vanadium pentoxide and dioxide films grown by the sol-gel method have been studied. The data of x-ray diffraction investigation and the temperature dependences of conductivity measured in a broad temperature range (50–380 K) are presented. The temperature of the metalsemiconductor phase transition in vanadium dioxide decreases with an increase in the dopant concentration. The phase transition is not observed in the films with tungsten concentrations above 6%. The radius of electron localization on vanadium ions in V_1?x W _x O₂ has been estimated. The results of the investigation of the switching effect in tungsten-doped vanadium pentoxide hydrate are reported.     

Synthesis and thermal stability of W-doped VO2 nanocrystals

Pure and W-doped vanadium dioxide nanocrystals have been synthesized by using V₂O₅ and oxalic acid as precursors via a thermolysis method. The VO₂ nanocrystals have a nearly spherical morphology with size ranging from 50 to 100 nm. The metal-insulator transition (MIT) temperature of the nanocrystals decreases with increasing W-doping content. The successive heat-induced fatigue character of the MIT in W-doped VO₂ nanocrystals was investigated by DSC analysis together with structural study, and a high stability upon heating–cooling cycles was found with respect to MIT temperature, peak temperature and latent heat of the phase transition.     

Giant phase transition properties at terahertz range in VO₂ films deposited by sol-gel method

VO(2) films were fabricated on high-purity single-crystalline silicon substrate by the sol-gel method, followed by rapid annealing. The composition and microstructure of the films were investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The results indicated a polycrystalline nature with high crystallinity and compact nanostructure for the films, and the concentration of +4 valence vanadium is 79.85%. Correlated with these, a giant transmission modulation ratio about 81% of the film was observed by terahertz time domain spectroscopy. The experimentally observed transmission characteristics were reproduced approximately, by a simulation at different conductivities across the phase transition. According to the effective-medium theory, we assumed that it is important to increase the concentration of +4 valence vanadium oxide phases and improve the compactness of the VO(2) films for giant phase transition properties. The sol-gel-derived VO(2) films with giant phase transition properties at terahertz range, and the study on their composition and microstructure, provide considerable insight into the fabrication of VO(2) films for the application in THz modulation devices.     

Oxidation potential control of VO2 thin films by metal oxide co-sputtering

For metal-to-insulator transition (MIT) in vanadium oxide thin film, a thermodynamically stable vanadium dioxide (VO₂) phase is essential. In VO₂ films sputter-deposited on a quartz substrate from a V₂O₅ target, a radio-frequency (RF) magnetron sputter system at working pressure of 7 mTorr is used. Due to the lower sputtering yield of oxygen compared to vanadium leading to oxygen-ion deficiency, the reduction of V ions is resulted to compensate charge with the oxygen ions. Under lower working pressures, the deposition rate increases, but a simultaneous oxygen-ion deficiency causes the destabilization of VO₂. To prevent this, titanium oxide co-deposition is suggested to enrich the oxygen source. When TiO₂ is used, it is found that the Ti ion has a stable +4 charge state so that the use of extra oxygen in sputtering prevents the destabilization of VO₂. However, this is not the case for TiO. For the latter, Ti ions are oxidized from the +2 state to the +3 and +4 states, and V ions with less oxidation potential are reduced to +3 or so. Pure VO₂ thin film exhibits MIT at 66 °C and a large resistivity ratio of four orders of magnitude from 30 to 90 °C. The (V₂O₅ + TiO₂) system under working pressure as low as 5 mTorr yields fairly good films comparable to pure VO₂ deposited at 7 mTorr, whereas the use of TiO yields films with MIT absent or considerably weakened.     

Significant control of metal-insulator transition temperature through catalytic excessive oxygen doping in high-performance vanadium dioxide nanobeam channel

The strategy of a reliable transition temperature control of vanadium dioxide(VO_2) is reported. Rectangular VO_2 nanobeams were synthesized by a thermal chemical vapor deposition(TCVD) system. The metal-insulator transition(MIT) temperature increases to above 380 K when the TiO_2 ratio of the source is 5 at.%, although the Ti source is not physically doped into VO_2 nanobeams. The XPS spectra of the V 2 p orbital reveal the excessive oxidation of V after the TCVD processes with a higher TiO_2 ratio, indicating that the TiO_2 precursor is important in the O-doping of the surface V O bonds when forming volatile Ti-O gas species. Thus, TiO_2 reactants can be used as a VO_2 surface chemical modifier to manipulate the MIT transition temperature and maintain a homogenous VO_2 phase, which is useful for a Mott device application with a record on/off switching ratio 10~4 and Mott transition temperature 380 K.     

Optical properties of thin films of amorphous vanadium oxides

The results of an experimental investigation of the optical properties of anodic vanadium oxide films are presented. It is shown that films of different phase composition (VO₂, V₂O₅, or a mixture of two phases) can be obtained, depending on the oxidation regime, and that the absorption and transmission spectra are modified significantly in accordance. The optical properties of the oxides, whose composition is close to stoichiometric vanadium dioxide, demonstrate the occurrence of a metal-semiconductor phase transition in the amorphous films. The results presented are important both from the standpoint of technical applications of thin film systems based on anodic vanadium oxides and for more detailed understanding of the physical mechanism of the metal-semiconductor phase transition and the influence of structural disorder on the transition. Pis’ma Zh. Tekh. Fiz. 25, 81–87 (April 26, 1999)     

In situ nanomechanical behaviour of coexisting insulating and metallic domains in VO<Subscript>2</Subscript> microbeams

Measuring the electrical and mechanical responses of coexisting phases at nanoscale provides a platform to engineer micro-/nanoscale pattern of metallic and insulating domains with control over properties to make novel devices. Here, we employ several in situ characterization techniques, namely Raman, optical imaging and electrical measurements, to identify the phase coexistence of metallic and insulating domains. Further, we performed site-specific in situ nanoindentation to address the spatial variation in nanomechanical properties in vanadium dioxide (VO₂) single-crystal microbeams in proximity to metal–insulator transition temperature. We also investigated load or contact depth dependence on elastic modulus at various temperatures to avoid the interference of indentation size effect on nanomechanical properties across the phase transition. The obtained results confirm the abrupt increase in elastic modulus (~17 GPa) and nanohardness (1 GPa) across the transition from monoclinic (insulator) to rutile (metal) phase.     

Porous nano-structured VO2 films with different surfactants: synthesis mechanisms, characterization, and applications

Porous nano-structured vanadium dioxide (VO₂) thin films have been prepared on mica substrates via sol–gel process using surfactant cetyltrimethyl ammonium bromide, nonionic surfactant polyethylene glycol, and anionic surfactant sodium dodecyl sulfate as nano-structure directing agents. Models concerning the structure forming were proposed to explain the synthesis mechanisms between V₂O₅ colloid and different surfactants. Porous nano-structured VO₂ films with sphere-shaped, island-shaped and strip-shaped nanocrystals are synthesized in the experiments, and the optical properties and thermochromic properties of these films are compared. The porous nano-structured VO₂ films showed excellent infrared transmittance (nearly 70 %), low transition temperature (59.7 °C without doping), wide hysteresis width (37.8 °C), and different optical transmittance difference before and after the phase transition (39–67 %). The results suggest that these porous nano-structured VO₂ films have significant importance in practical application in VO₂-based optical and electronic devices.     

脉冲激光沉积法制备VO_2热致变色薄膜研究进展

基于半导体和金属间的相变特性,伴随着温度、电场、压力的变化,具有相关智能特性的VO_2薄膜材料具有较大的应用潜力.本文主要阐述脉冲激光沉积技术在制备金属氧化物方面的物理过程和技术特点,详细介绍脉冲激光沉积制备VO_2薄膜材料的工艺参数和国内外研究进展,并与几种常规制备方法进行对比,给出脉冲激光沉积掺杂对VO_2薄膜材料特性的影响,以及采用脉冲激光沉积制备VO_2纳米材料,讨论了脉冲激光沉积制备具有智能特性的VO_2薄膜材料存在的问题和发展方向.     

Preparation of anatase TiO2 thin films for dye-sensitized solar cells by DC reactive magnetron sputtering technique

Anatase titanium dioxide (TiO₂) thin films are prepared by DC reactive magnetron sputtering using Ti target as the source material. In this work argon and oxygen are used as sputtering and reactive gas respectively. DC power is used at 100 W per 1 h. The distance between the target and substrate is fixed at 4 cm. The glass substrate temperature value varies from room temperature to 400 °C. The crystalline structure of the films is determined by X-ray diffraction analysis. All the films deposited at temperatures lower than 300 °C were amorphous, whereas films obtained at higher temperature grew in crystalline anatase phase. Phase transition from amorphous to anatase is observed at 400 °C annealing temperature. Transmittances of the TiO₂ thin films were measured using UV-visible NIR spectrophotometer. The direct and indirect optical band gap for room temperature and substrate temperature at 400 °C is found to be 3.50, 3.41 eV and 3.50, 3.54 eV respectively. The transmittance of TiO₂ thin films is noted higher than 75%. A comparison among all the films obtained at room temperature showed a transmittance value higher for films obtained at substrate temperature of 400 °C. The morphology of the films and the identification of the surface chemical stoichiometry of the deposited film at 400 °C were studied respectively, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The surface roughness and the grain size are measured using AFM.     

Electronic and optical properties of monoclinic and rutile vanadium dioxide

The electronic and optical properties of vanadium dioxide are investigated in the frameworks of density functional theory and GGA+U, in detail. It is found that, the metal–insulator transition in VO₂ is induced by the on-site correlation effects, accompanied with a distinct charge-transfer. Unlike that in rutile phase, the energy gap in the monoclinic phase opens suddenly and abruptly, which is consistent with the experimental observation. The calculated indirect energy gap (0.32 eV) and the direct energy gap (0.58 eV) can be used to theoretically interpret the experimental optical transmission at 0.31 eV and the optical energy gap 0.6 eV, respectively. Consequently, both of them are confirmed by our optical calculation. Furthermore, our calculated optical absorption peaks agree with the experiment very well.     

Large phase-transition hysteresis for nanostructured VOx film prepared on ITO conductive glass by DC reactive magnetron sputtering

Nanostructured vanadium oxide (nano-VO_x) films were prepared on indium-tin oxide (ITO) glass substrate at low temperature by means of direct current (DC) reactive magnetron sputtering from pure vanadium target in Ar + O₂ atmosphere. Field emission scanning electron microscope (SEM) reveals that the VO_x film is composed of spheroidal nanoparticles whose diameters are in the range of 20–40 nm. This nano-VO_x film shows a broad hysteresis loop whose width is as large as 41.6 °C. Moreover, the metal-insulator transition (MIT) can also be triggered by Joule heat produced by electrical current through the ITO sublayer. Compared to traditional heating of the sample by heating plate, this Joule heating is more efficient and convenient, which enables potential applications of this nano-VO_x film on ITO conductive glass in compact storage devices.     

Metal-semiconductor phase transition in transplanted thin polycrystalline vanadium dioxide films

A method for transfer of vanadium dioxide films from one substrate to another is proposed. This transplantation reveals a significant influence of elastic stresses arising during the film synthesis and as a result of the structural phase transition in the film on the temperature and shape of hysteresis of the optical reflectance.