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.     

Electrical and structural properties of VO2 in an electric field

We examined the electrical and local structural properties of a VO₂ film at different electric fields using electrical resistance and x-ray absorption fine structure (XAFS) measurements at the V K edge in the temperature range of 30–100 °C. The T_c value of the metal-to-insulator transition (MIT) during both heating and cooling decreases with electric field. When the electric field exceeds a certain value, the MIT becomes sharper due to Joule heating. The MIT, the structural phase transition (SPT), and the pre-edge peak transition of the VO₂ do not congruently occur at a uniform temperature. A metallic VO₂ is observed in only the rutile (or M2) symmetry. An electric field induces a substantial amount of conduction electrons in insulating VO₂. Simultaneously measured resistance and XAFS reveal that Joule heating caused by an external electric field significantly affects the MIT and SPT of VO₂.     

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.     

The study of optimal oxidation time and different temperatures for high quality VO2 thin film based on the sputtering oxidation coupling method

The high quality Vanadium dioxide (VO₂) thin films have been fabricated successfully on sapphire by a simple novel sputtering oxidation coupling (SOC) method. All VO₂ thin film samples exhibit a good metal-insulator transition (MIT) at about 340 K. The optimal oxidation time at different temperatures has been experimentally investigated. We report on the relationship between optimal oxidation time and different temperatures of metal vanadium thin film samples of 101 nm thickness by oxidation in air. It is found that the optimal oxidation time ln(t) as a function of temperature 1/T shows a significant linear relationship among 703 K-783 K, in good agreement with the Wagner's high-temperature oxidation model.     

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)     

Design, formation and characterization of a novel multifunctional window with VO2 and TiO2 coatings

A novel multifunctional window was demonstrated using VO₂-based thermochromic films with a TiO₂ antireflection coating. A strong enhancement in luminous transmittance of VO₂ was calculated using either a single layer or a double layer of TiO₂ for antireflection, with the double layer giving the better performance. A TiO₂ (25 nm)/VO₂ (50 nm)/TiO₂ (25 nm) structure, of which the film thickness has been optimized to a maximum integrated luminous transmittance (T_lum) by calculation, was formed on SiO₂ glass by sputtering in turn a V target in Ar+O₂ for VO₂ and a TiO₂ target in Ar for TiO₂. Optical properties were measured with a spectrophotometer, and the integrated solar and luminous properties were calculated based on the measured spectra. A maximum increase in T_lum by 86% (from 30.9% to 57.6%) was obtained for VO₂ after double-layer TiO₂ antireflection coating. The deposited VO₂ film on SiO₂ exhibits good thermochromism with a sharp optical transition at 58.5 °C, which decreased slightly to 57.5 °C after TiO₂ coating. The proposed window is the most advanced among those similarly reported in being multifunctional with automatic solar/heat control, ultraviolet stopping and possibly a wide range of photocatalytic functions in addition to a high value of the luminous transmittance. PACS 42.79.Wc; 78.20.-e; 71.30.+h     

Photoassisted chemical solution deposition method for fabricating uniformly epitaxial VO2 films

Epitaxial VO₂ films were prepared on the TiO₂ (001) substrates by the excimer-laser-assisted metal–organic deposition (ELAMOD). The quality of the epitaxial films obtained by irradiation with a KrF laser was found to be affected by the film structure obtained after preheating at 500 or 300°C. When the films containing crystal domains, which were obtained by preheating at 500°C, were irradiated with the laser at room temperature under a base pressure of 250 Pa, epitaxial and polycrystalline VO₂ phases were simultaneously formed. In contrast, when the amorphous films containing organic components, which were obtained by preheating at 300°C, were irradiated with the laser at room temperature in air, a single phase of epitaxial VO₂ was formed. By using thermal simulations, we determined that the formation of the epitaxial phase was affected both by the temperature distribution within the film during the laser irradiation and by the laser intensity at the interface between the substrate and the film. The latter factor is considered to play a role in the nucleation of crystallization, causing the epitaxial phase to form preferentially compared to the polycrystalline phase in the amorphous matrix of the films. These results indicate that the ELAMOD process is effective for the fabrication of epitaxial VO₂ films at low temperature.     

Raman analyses of co‐phasing and hysteresis behaviors in V2O3 thin film

We present the studies of the phase transition behaviors of V₂O₃ thin film using temperature‐dependent Raman scattering spectroscopy. Our results show that in both the cooling and heating processes of V₂O₃ thin film, the phase transition occurs gradually but not suddenly, contrary to that in single crystal. The coexistence of both the metal and insulator phases with co‐phasing ΔT_c larger than 30 K is observed in both the cooling and heating processes. We discuss that this large co‐phasing ΔT_c should be distinguished with the large hysteresis ΔT_h reported in nanostructures. In addition, our discussions indicate that co‐phasing ΔT_c and hysteresis ΔT_h would be mainly correlated with stress and defect states in sample, respectively. Furthermore, our Raman analyses suggest that stress would also induce phase transitions in V₂O₃, and the stress (pressure)‐induced phase transitions would behave differently comparing with the temperature‐induced transitions under normal pressure. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxygen pressure induced structure,morphology and phase-transition for VO2/c-sapphire films by PLD

To investigate the effects of oxygen pressure on the structural and phase transition properties for VO₂/c-sapphire, highly orientated VO₂ thin films were grown on (0001) sapphire substrates by pulsed laser deposition (PLD) with different oxygen pressures. The crystal structure, morphology and component of the films were systematically investigated. The temperature-dependent resistance (R-T) measurement was conducted, which showed the distinct phase transition characteristic for the prepared films. The results indicate that the oxygen pressure plays an important role for the VO₂ film preparation. The film grown at 1.7 Pa has lower phase transition temperature, higher film strain, and smaller grain size than that at 5.4 Pa, while no obvious crystal phase transition is observed. The experiment suggests that even a small change in oxygen pressure can influence the structure, morphology and phase-transition behavior of VO₂ films obviously, and its potential causes are mainly attributed to the reduction of the kinetic energy to the substrate for target atoms caused by the oxygen pressure, the resulting grain aggregation and interfacial stress.     

In-plane magnetoresistance of electron-doped superconducting thin films Pr0.9LaCe0.1CuO4

We measured the in-plane magnetoresistance of Pr_0.9LaCe_0.1CuO₄ (PLCCO) epitaxial thin films under various magnetic fields H applied parallel to the tetragonal c-axis. The measurements were performed at the superconducting state as well as the normal state. As the magnetic field is between the low critical field H_c1 and upper critical field H_c2, a critical scaling behavior of electrical resistivity is found. We analyze the electrical transport properties and show the magnetic field H dependence of glass transition temperature T_g and the characteristic temperature T^* for the PLCCO film, which may shed some light on vortex behavior in electron-doped superconductors.     

YBa2Cu3O7-δ外延薄膜的有效钉扎势

在0—7T磁场范围内，测量了不同测量电流密度下YBa₂Cu₃O_7-δ外延薄膜的电阻温度关系.实验结果表明，临界温度以下，混合态的耗散电阻率能很好地用热激活磁通蠕动描述.有效钉扎势的电流密度关系遵守Zeldov等人提出的对数关系，有效钉扎势的温度和磁场关系遵守U∝(1-T/T_c)H^-α关系，其中α=0.63，与热激活磁通点阵位错运动模型相一致，表明样品具有2D涡旋性质. 关键词：     

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.     

Growth of b-axis oriented VO2 thin films on glass substrates using ZnO buffer layer

VO₂ thin films are grown on glass substrates by pulsed laser deposition using vanadium metal as a target. In this study, a ZnO thin film was used as a buffer layer for the growth of VO₂ thin films on glass substrates. X-ray diffraction studies showed that the VO₂ thin film had b-axis preferential orientation on a c-axis oriented ZnO buffer layer. The thickness of the ZnO buffer layer and the oxygen pressure during VO₂ deposition were optimized to grow highly b-axis oriented VO₂ thin films. The metal-insulator transition properties of the VO₂ film samples were investigated in terms of infrared reflectance and electrical resistance with varying temperatures.     

Study of depth-dependent tetragonal distortion of quaternary AlInGaN epilayer by Rutherford backscattering/channeling

A 240-nm thick Al_0.4In_0.02Ga_0.58N layer is grown by metal organic chemical vapour deposition, with an over 1-μ m thick GaN layer used as a buffer layer on a substrate of sapphire (0001). Rutherford backscattering and channeling are used to characterize the microstructure of AlInGaN. The results show a good crystalline quality of AlInGaN (χ_min=1.5%) with GaN buffer layer. The channeling angular scan around an off-normal <12^{-13> axis in the {101-0} plane of the AlInGaN layer is used to determine tetragonal distortion e_T, which is caused by the elastic strain in the AlInGaN. The resulting AlInGaN is subjected to an elastic strain at interfacial layer, and the strain decreases gradually towards the near-surface layer. It is expected that an epitaxial AlInGaN thin film with a thickness of 850 nm will be fully relaxed (e_T = 0).}     

Direct photoemission spectroscopy and electronic properties of in situ grown,strained high-Tc and related oxide films

We have optimized laser ablation thin film deposition and transfer procedures within synchrotron vault, specifically to perform angle-integrated and angle-resolved photoemission spectroscopy (ARPES) on high-T_c and related films without cleaving the samples. However, the chain-containing phases like YBCO-123 easily loose surface oxygen and do not exhibit stable Fermi edge, hence are not suitable for ARPES studies. Direct in situ ARPES studies on strained LSCO-214 films show striking strain effects on the electronic structure. The Fermi surface (FS) of LSCO evolves with doping, yet changes even more significantly with strain. The strain changes the FS topology from hole-like to electron-like, and causes band dispersion along k_x and the Fermi level crossing before the Brillouin zone boundary, in sharp contrast to the ‘usual’ flat band remaining ≈30 meV below E_F measured on unstrained samples. The associated reduction of the density of states does not diminish the superconductivity; T_c is enhanced in all our strained samples. Implications for the evolving high-T_c theory and studies of nano-engineered film heterostructures are briefly discussed.     

Direct angle resolved photoemission spectroscopy and superconductivity of strained high-T c films

Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (<30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-T _c superconductors (HTSC) under different degrees of epitaxial (compressive vs. tensile) strain. In overdoped and underdoped in-plane compressed (the strain is induced by the choice of substrate) ≈15 nm thin La_{2 − x} Sr _x CuO₄ (LSCO) films we almost double T _c to 40 K, from 20 K and 24 K, respectively. Yet the Fermi surface (FS) remains essentially two-dimensional. In contrast, ARPES data under tensile strain exhibit the dispersion that is three-dimensional, yet T _c drastically decreases. It seems that the in-plane compressive strain tends to push the apical oxygen far away from the CuO₂ plane, enhances the two-dimensional character of the dispersion and increases T _c, while the tensile strain acts in the opposite direction and the resulting dispersion is three-dimensional. We have established the shape of the FS for both cases, and all our data are consistent with other ongoing studies, like EXAFS. As the actual lattice of cuprates is like a ‘Napoleon-cake’, i.e. rigid CuO₂ planes alternating with softer ‘reservoir’, that distort differently under strain, our data rule out all oversimplified two-dimensional (rigid lattice) mean field models. The work is still in progress on optimized La-doped Bi-2201 films with enhanced T _c.      

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.     

A novel sputtering oxidation coupling (SOC) method to fabricate VO2 thin film

VO₂ thin film synthesized by a novel sputtering oxidation coupling (SOC) method has been successfully fabricated. The experimental results show that the optimum oxidation time is 285 s and the thin film exhibits a good metal-insulator transition (MIT) approximately at 340 K. The corresponding structures and surface compositions of the films have been characterized by X-ray diffractometer and X-ray photoelectron spectroscopy separately.     

Laser reactivation of Room-Tc ferromagnetism in Mn-doped insulating TiO2 thin films

Room-T _c ferromagnetic insulating Mn-doped TiO₂ thin films were prepared by plasma assisted molecular beam epitaxy (PAMBE). The thin films show obvious decay of ferromagnetism when aged in air at room temperature for one year without any special treatment. A distinct reactivation of ferromagnetism, together with a decrease in coercive force is achieved in these samples under laser irradiation treatment. The possible mechanism for the phenomena is also discussed. It is suggested that the bound magnetic polaron (BMP) forming via photo-generated defect-bound carriers accounts for the laser reactivation of room-T _c ferromagnetism.     

高温超导薄膜中的涨落超导电性及其维度

对RBa₂Cu₃O_7-δ(R=Y,Gd)超导薄膜电阻温度关系的仔细测量,观察到在T_c附近有相当强的超导涨落现象,研究发现,多晶和外延的YBa₂Cu₃O_7-δ薄膜在T_c以上均呈现出2D涨落超导电性;而当温度趋向于T_c时,有—2D向3D的转变发生,这与Lawrence-Doniach理论很好地相符,实验中还发现,一 关键词：