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)     

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.     

二氧化钒纳米棒的相变行为

研究了VO₂(M)纳米棒的金属绝缘体相变(MIT)行为．在VO₂(M)纳米棒的DSC分析曲线上发现了两个MIT,分别位于低温和高温区．低温MIT总是伴随出现VO₂(B)纳米棒,而独立的高温MIT出现在纯VO₂(M)纳米棒．分析和讨论了这两个MIT的机制．     

Structural and electrical properties of VO2/ZnO nanostructures

We examined the structural and electrical properties of uniformly-oriented VO₂/ZnO nanostructures. VO₂ was deposited on ZnO templates by using a direct current-sputtering deposition. Scanning electron microscope and transmission electron microscope measurements indicated that b-oriented VO₂ were uniformly crystallized on ZnO templates with different lengths. VO₂/ZnO formed nanorods on ZnO nanorods with length longer than 250 nm. X-ray absorption fine structure at the V K edge of VO₂/ZnO showed M₁ and R phases of VO₂ at 30 and 100 °C, respectively, suggesting structural-phase transition occurring between the two temperatures. Temperature-dependent resistance measurements of VO₂/ZnO nanostructures revealed metal-to-insulator transition at 65 °C and 55 °C during a heating and a cooling, respectively, regardless of ZnO length. Asymmetry behavior of resistance curves from VO₂/ZnO nanostructure during a heating and a cooling was attributed from a strong bond of VO₂ and ZnO.     

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.     

Metal insulator transition characteristics of macro-size single domain VO2 crystals

The metal insulator transition (MIT) characteristics of macro-size single-domain VO₂ crystal were investigated. At the MIT, the VO₂ crystal exhibited a rectangular shape hysteresis curve, a large change in resistance between the insulating and the metallic phases, in the order of ～10⁵, and a small transition width (i.e. temperature difference before and after MIT) as small as 10^?3°C. These MIT characteristics of the VO₂ crystals are discussed in terms of phase boundary motion and the possibility of controlling the speed of the phase boundary, with change in size of crystal, is suggested.     

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.     

Monoclinic and correlated metal phase in VO(2) as evidence of the Mott transition: coherent phonon analysis

In femtosecond pump-probe measurements, the appearance of coherent phonon oscillations at 4.5 and 6.0 THz indicating the rutile metal phase of VO2 does not occur simultaneously with the first-order metal-insulator transition (MIT) near 68 degrees C. The monoclinic and correlated metal (MCM) phase between the MIT and the structural phase transition (SPT) is generated by a photoassisted hole excitation, which is evidence of the Mott transition. The SPT between the MCM phase and the rutile metal phase occurs due to subsequent Joule heating. The MCM phase can be regarded as an intermediate nonequilibrium state.     

Temperature dependent structural,electrical and electronic investigation of VO2 (B) thin film

Vanadium dioxide can exist in several polymorphs and among these the layered polymorph VO₂ (B) with monoclinic symmetry has numerous applications. In this work, VO₂ (B) phase thin film was prepared on quartz substrate via sputtering technique and its temperature dependent structural, electrical and electronic properties were investigated. We have witnessed a broader structural phase transition around 220 K; which encounter significant changes in the lattice constants yet the monoclinic symmetry is retained over a temperature range from 100 K to 380 K. Temperature dependent resistance measurement also exhibited a semi-metal to insulator like transition near 220 K displaying over 2 order of magnitude change in resistance across the transition. Small changes in the oxygen K-edge x-ray absorption spectrum were seen with change in temperature. At low temperature, an additional peak (d_|| band) has emerged in the XAS spectra at energy higher than the σ* peak. The appearance of d_|| band density of states is associated to the enhanced electron correlation effects driven by the localization of V–V pair's interactions at low temperature.     

Wet‐Etching Induced Abnormal Phase Transition in Highly Strained VO2/TiO2 (001) Epitaxial Film

The metal–insulator transition (MIT) behavior in vanadium dioxide (VO₂) epitaxial film is known to be dramatically affected by interfacial stress due to lattice mismatching. For the VO₂/TiO₂ (001) system, there exists a considerable strain in ultra‐thin VO₂ thin film, which shows a lower T_c value close to room temperature. As the VO₂ epitaxial film grows thicker layer‐by‐layer along the “bottom‐up” route, the strain will be gradually relaxed and T_c will increase as well, until the MIT behavior becomes the same as that of bulk material with a T_c of about 68 °C. Whereas, in this study, we find that the VO₂/TiO₂ (001) film thinned by “top‐down” wet‐etching shows an abnormal variation in MIT, which accompanies the potential relaxation of film strain with thinning. It is observed that even when the strained VO₂ film is etched up to several nanometers, the MIT persists, and T_c will increase up to that of bulk material, showing the trend to a stress‐free ultra‐thin VO₂ film. The current findings demonstrate a facial chemical‐etching way to change interfacial strain and modulate the phase transition behavior of ultrathinVO₂ films, which can also be applied to other strained oxide films.     

Electrical,optical and structural properties of pure and gold-coated VO2 thin films on quartz substrate

In the present study, vanadium dioxide films were grown on quartz glass substrate by reactive KrF laser ablation technique using a vanadium dioxide target. The gold films of various thicknesses were then deposited on the VO₂ film by sputtering technique. Films were characterized by X-ray diffraction to determine crystallography, by four-point probe to determine the electrical property and by double-beam spectrophotometry to determine optical reflection and transmission behaviour in the 200–2500 nm spectral region. The resistance per square of VO₂ thin film decreases by two orders of magnitude across the metal insulator transition (MIT). The optical transmittance and reflectance exhibits, strong temperature dependence in the infrared region without a significant change in the visible region for VO₂ thin films. The presence of gold layer on VO₂ films significantly reduces the resistance per square, the critical temperature and percentage transmittance of the materials.     

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.     

Electric field induced metal–insulator transition in VO2 thin film based on FTO/VO2/FTO structure

A VO₂ thin film has been prepared using a DC magnetron sputtering method and annealing on an F-doped SnO₂ (FTO) conductive glass substrate. The FTO/VO₂/FTO structure was fabricated using photolithography and a chemical etching process. The temperature dependence of the I–V hysteresis loop for the FTO/VO₂/FTO structure has been analyzed. The threshold voltage decreases with increasing temperature, with a value of 9.2 V at 20 °C. The maximum transmission modulation value of the FTO/VO₂/FTO structure is 31.4% under various temperatures and voltages. Optical modulation can be realized in the structure by applying an electric field.     

Contribution of weak localization, electron-electron interaction, and Zeeman spin-splitting effects in corrective term “mT” of the metallic conductivity in n-type GaAs

We present measurements of the electrical conductivity of barely metallic n-type GaAs that are driven to the metal-insulator transition (MIT) by magnetic field. The experiments were carried out at low temperature in the range (4.2-0.066 K) and in magnetic field up to 4 T. We have determined the magnetic field for which the conductivity changes from the metallic behavior to insulator regime. On the metallic side of the MIT, the electrical conductivity is found to obey σ=σ₀+mT^1/2 down to 66 mK. Physical explanation to the temperature dependence of the conductivity is given in metallic side of the MIT using a competition between different effects involved in the mechanisms of conduction, like electron-electron interaction effect, Zeeman spin-splitting effect, and weak localization effect.     

Magnetic field and temperature-induced first-order transition in Gd5(Si1.5Ge2.5): a study of the electrical resistance behavior

Magnetic field (0–4 T) and temperature dependencies (4.2–320 K) of the electrical resistance of Gd₅(Si_1.5Ge_2.5), which undergoes a reversible first-order ferromagnetic↔paramagnetic phase transition, have been measured. The electrical resistance of Gd₅(Si_1.5Ge_2.5) indicates that the magnetic phase transition can be induced by both temperature and magnetic field. The temperature dependence of the electrical resistance, R(T), for heating at low temperatures in the zero magnetic field has the usual metallic character, but at a critical temperature of T_cr=216 K the resistance shows a 20% negative discontinuity due to the transition from the low-temperature high-resistance state to the high-temperature low-resistance state. The R(T) dependence for cooling shows a similar but positive 25% discontinuity at 198 K. The isothermal magnetic field dependence of the electrical resistance from 212T224 K indicates the presence of temperature-dependent critical magnetic fields which can reversibly transform the paramagnetic phase into the ferromagnetic phase and vice versa. The critical magnetic fields diagram determined from the isothermal magnetic field dependencies of the electrical resistance of Gd₅(Si_1.5Ge_2.5) shows that the FM↔PM transition in zero magnetic field on cooling and heating occurs at 206 and 213 K, respectively. The full isothermal magnetic filed hysteresis for the FM↔PM transition is 2 T, and the isofield temperature gap between critical magnetic fields is 7 K.     

Metal-insulator transition in SrTiO(3-x) thin films induced by frozen-out carriers

We report optical, electrical and magnetotransport properties of oxygen deficient SrTiO(3) (SrTiO(3-x)) thin films fabricated by pulsed laser deposition technique. The oxygen vacancies (O(vac)) in the thin film are expected to be uniform. By comparing its electrical properties to those of bulk SrTiO(3-x), it was found that O(vac) in bulk SrTiO(3-x) is far from uniform over the whole material. The metal-insulator transition (MIT) observed in the SrTiO(3-x) film was found to be induced by the carrier freeze-out effect. The low temperature frozen state can be reexcited by Joule heating, electric and intriguingly magnetic field.     

Non-hysteretic metal-insulator transition of VO2 films grown by excimer-laser-assisted metal organic deposition process

We examined the correlation between thickness of an epitaxial VO₂ phase grown on a TiO₂ (0 0 1) substrate by the excimer-laser-assisted metal organic deposition (ELAMOD) process and the metal-insulator transition (MIT) property of it. The abrupt and hysteretic MIT was observed for the epitaxial films (thickness: t ≥ 6 nm), and the epitaxial film (t ≤ 4 nm) showed semiconductor behavior. When an amorphous VO_x layer was prepared on the ultrathin epitaxial phase (t ≤ 4 nm) by the ELAMOD, a non-hysteretic MIT was successfully observed. The non-hysteretic MIT was found to be owing to roughened interface between the epitaxial phase and the amorphous phase, where there would be a number of structural defects.     

The specific heat of potassium holmium double tungstate

The results of measurements of thermal properties (specific heat) of potassium holmium double tungstate KHo(WO₄)₂ as a function of temperature (from 0.5 to 300?K) and magnetic field (up to 2?T) are presented. The total specific heat without the phonon and Schottky contributions is found to have the anomaly with maximum at T _SPT?～?5?K. This anomaly is likely related with the structural phase transition (SPT) caused by the cooperative Jahn–Teller effect. The increase of specific heat at very low temperatures and its shift towards high temperatures with increasing magnetic field are observed. The origin of this behaviour can be connected with possible magnetic phase transition induced by magnetic field.     

The suppression of structural phase transformation in LaVO3 and La1−xSrxVO3 thin films fabricated by pulsed laser deposition

Highly oriented (100) thin films of LaVO₃ and La_1−xSr_xVO₃ have been fabricated by pulsed laser deposition in a reducing atmosphere. The films show a transition from insulating to metallic behaviour in the composition region of x, 0.175<x<0.200. In the single crystals of the antiferromagnetic insulating phase, a first-order structural phase transition is observed few degrees below the magnetic transition, which manifests itself as a kink in the temperature dependence of resistivity. In the highly oriented thin films of LaVO₃ and La_1−xSr_xVO₃ fabricated on lattice matched substrates in this study, the structural phase transformation in the insulating phase has been suppressed. The electrical conduction is found to take place via hopping through localized states at low temperatures. The metallic compositions show a non-linear (T^1.5) behaviour in the temperature dependence of resistivity. V (2p) core level spectra of these films show a gradual change in the relative intensities of V³⁺ and V⁴⁺ ions as the value of x increases.     

The character of metal-insulator phase transition in V2O3 from the plasmon behaviour

The metal-to-insulator transition (MIT) in V₂O₃ has been studied by thermoreflectance spectroscopy. The behaviour of the plasmon resonance as a function of crystal temperature has been measured. This experimental method is a sensitive probe of the effects of electron-electron correlation and/or of the band gap opening at the MIT phase transitions. A blue shift of the plasmon energy in cooling the sample throught the phase transition temperature has been found. This behaviour, with a shift in the opposite direction of that found in VO₂, provides a direct experimental evidence that the electron-electron interaction plays a minor role in driving the V₂O₃ phase transition.