Size effects upon phase transitions in vanadium oxide nanocomposites

A phenomenological model has been proposed for the formation of the major thermal hysteresis loop of optical parameters upon the semiconductor-metal phase transition in vanadium oxide nanocomposites. It has been demonstrated that the effects associated with the influence of nanocrystallite sizes on the phase transition temperature in an individual nanocrystallite, which is determined by the width of the elementary hysteresis loop and the position of the phase equilibrium temperature on the temperature scale, manifest themselves in the form of pronounced features in the loop shape. In particular, the size effects for VO₂ polycrystalline films are observed in the formation of a trapezoidal shape of the optical thermal hysteresis loop with a wide lower base, whereas these effects for nanocomposites based on porous glasses with VO₂ nanocrystals are revealed in the form of the optical hysteresis loop with a narrow lower base (wide upper base). The proposed model also explains the symmetric shape of the major hysteresis loop for vanadium oxide nanocomposites based on opals. The size effects in opal nanocomposites with strictly fixed sizes of pores and, therefore, nanocrystallite sizes manifest themselves in the form of well-defined steps in the heating and cooling branches of the major hysteresis loop.     

Optical data recording with vanadium dioxide-based film reversible media

Thermally induced semiconductor-metal phase transitions taking place in Al/VO₂/insulator and VO₂/insulator film systems upon recording optical data are investigated. Experiments show that the rate of the processes depends on thermophysical parameters of the films, as well as on the energy exposure. The dynamic range of the energy exposure sensitivity is defined by the hysteresis loop width. The shape and width of the hysteresis loop depends on the VO₂ film thickness and the nonstoichiometric ratio profile across the film.     

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.     

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.     

Structural and magnetic properties of bulk and thin films of Mg0.95Mn0.05Fe2O4

We present here a comparative study on structural and magnetic properties of bulk and thin films of Mg_0.95Mn_0.05Fe₂O₄ ferrite deposited on two different substrates using X-ray diffraction (XRD) and dc magnetization measurements. XRD pattern indicates that the bulk sample and their thin films exhibit a polycrystalline single phase cubic spinel structure. It is found that the film deposited on indium tin oxide coated glass (ITO) substrate has smaller grain size than the film deposited on platinum coated silicon (Pt–Si) substrate. Study of magnetization hysteresis loop measurements infer that the bulk sample of Mg_0.95Mn_0.05Fe₂O₄ and its thin film deposited on Pt–Si substrate shows a well-defined hysteresis loop at room temperature, which reflects its ferrimagnetic behavior. However, the film deposited on ITO does not show any hysteresis, which reflects its superparamagnetic behavior at room temperature.     

Effect of deformation on the metal-semiconductor phase transition in vanadium dioxide thin films

It has been demonstrated that a small plastic deformation of aluminum substrates with vanadium dioxide thin films deposited on the substrate surfaces is accompanied by the appearance of elastic stresses in the films. Depending on the deformation technique, the elastic stresses can have different signs and the range of the metal-semiconductor phase transition in VO₂ shifts toward higher or lower temperatures as compared to the equilibrium phase temperature.     

Comparison of VO<Subscript>2</Subscript> thin films prepared by inorganic sol-gel and IBED methods

VO₂ thin films with semiconductor-to-metal phase-transition properties were prepared by inorganic sol-gel and IBED (ion-beam-enhanced deposition) methods on SiO₂/Si substrate. The crystalline phase and the shape and width of the hysteresis curves of these VO₂ films were significantly different. For sol-gel VO₂ films, the transition started at close to 62 °C upon heating. The temperature interval needed to complete the phase transition was 8 °C, the ratio of resistance (R_{20 °C}/R_{80 °C}) reached three orders and the hysteresis width was 6 °C. However, the IBED film post-annealed in Ar at 700 °C underwent a phase transition from 45 °C to 80 °C, the ratio of resistance was more than two orders and the hysteresis width was 2 °C. In addition, the TCR (temperature coefficient of resistance) at 22 °C of the IBED film was 3.5%/K, much larger than the 0.7%/K TCR of the sol-gel film. PACS 73.50.F; 73.66.E; 81.20; 81.05.Z; 81.15     

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.     

The characteristics of Au:VO2 nanocomposite thin film for photo-electricity applications

Au nanoparticles have been fabricated on normal glass substrates using nanosphere lithography (NSL) method. Vanadium dioxide has been deposited on Au/glass by reactive radio frequency (rf) magnetron sputtering. The structure and composition were determined by X-ray diffraction and X-ray photoelectron spectroscope. Electrical and optical properties of bare VO₂ and Au:VO₂ nanocomposite thin films were measured. Typical hysteresis behavior and sharp phase transition were observed. Nanopartical Au could effectively reduce the transition temperature to 40 °C. The transmittance spectrum for both Au:VO₂ nanocomposite thin film shows high transmittance under transition temperature and low transmittance above transition temperature. The characteristics present the Au:VO₂ nanocomposite thin film can be used for applications, such as “smart window” or “laser protector”.     

Thermally tunable optical constants of vanadium dioxide thin films measured by spectroscopic ellipsometry

Smart materials with reversible tunable optical constants from visible to near-infrared wavelengths could enable excellent control over the resonant response in metamaterials, tunable plasmonic nanostructures, optical memory based on phase transition and thermally tunable optical devices. Vanadium dioxide (VO₂) is a promising candidate that exhibits a dramatic change in its complex refraction index or complex dielectric function arising from a structural phase transition from semiconductor to metal at a critical temperature of 70 °C. We demonstrated the thermal controllable reversible tunability of optical constants of VO₂ thin films. The optical/dielectric constants showed an abrupt thermal hysteresis which confirms clearly the electronic structural changes. Temperature dependence of dielectric constants as well as optical conductivity of sputtered VO₂ thin films was also reported and compared to previous theoretical and experimental reports.     

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.     

VO2-WO3 nanocomposite thin films synthesized by pulsed laser deposition technique

Pure VO₂ and VO₂-WO₃ composite thin films were grown on quartz substrate by pulsed laser deposition (PLD) technique. The influence of varying WO₃ molar concentration in the range from x = 0.0 to x = 0.4 on structural, electrical and optical properties of VO₂-WO₃ nanocomposite thin films has been systematically investigated. X-ray diffraction studies reveal the single crystalline monoclinic VO₂ phase (m-VO₂) up to 10% of WO₃ content whereas both m-VO₂ as well as h-WO₃ (hexagonal WO₃) phases were present at higher WO₃ content (0.2 ≤ x ≤ 0.4). Optical transmittance spectra of the films showed blue shift in the absorption edge with increase in WO₃ content. Temperature dependence of resistivity (R-T) measurements indicates significant variation in metal-insulator transition temperature, width of the hysteresis, and shape of the hysteresis curve. Cyclic Voltammetry measurements were performed on VO₂-WO₃ thin films. A direct correlation between V/W ratio and structure-property relationship was established. The present investigations reveal that doping of WO₃ in VO₂ is effective to increase the optical transmittance and to reduce the semiconductor to metal phase transition temperature close to room temperature.     

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.     

The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Thermally- or optically-biased memristive switching in two-terminal VO2 devices

We investigated thermally- or optically-biased memristive switching in two-terminal micro devices based on vanadium dioxide (VO₂) thin films. For the preparation of multi-level resistance switching, the device was kept at a specific temperature or an optical illumination power so that it fell into the thermal or optical hysteresis region of the device resistance during the switching. With the application of external current pulses, the device resistance decreased in a discrete manner showing multiple resistance levels, each of which was maintained as long as the temperature (or optical) bias excited the device. In particular, in the optically-biased case, the effect of the pulse-free interval between current pulses on the device resistance was also examined with respect to three intervals including 10, 15, and 30 s. It was observed that a longer pulse-free interval and higher optical bias reduced the rate of current-induced change in the device resistance. Finally, in order to explore a trend of grain resistance change in the VO₂-based device, we carefully suggested a grain network model explaining a percolative transition in inhomogeneous VO₂ film.     

Pulse laser deposition of vanadium dioxide films

Thin amorphous and crystalline films of VO₂ are obtained on (0001) sapphire substrates via pulsed laser deposition with the speed separation of particles under a variety of deposition conditions. The electrical and optical properties of the films in the vicinity of the phase transition in the temperature range of 20 to 100°C are studied. The temperature of transition (T_c) and the width of the hysteresis are found to be 67.5 and 3°C, respectively.     

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.     

Effect of low-angle boundaries on the dielectric properties of epitaxial Ba0.8Sr0.2TiO3 films

The effect of low-angle boundaries on the dielectric properties of epitaxial Ba_0.8Sr_0.2TiO₃ films is studied by comparing films differing in crystalline-block size. It is found that the permittivity diminishes considerably when the block sizes are reduced. The maximum of the temperature-dependent permittivity is shifted towards lower temperatures, and the sensitivity of the permittivity to an electric field is reduced. Moreover, it is found that the maximum in the permittivity temperature dependence is displaced towards lower temperatures when the applied measured voltage is increased and becomes higher than the coercive voltage. The width of a hysteresis loop decreases significantly when the frequency of the controlling field is reduced. The reasons for the observed behavior are analyzed.     

Study of nanocrystalline VO2 thin films prepared by magnetron sputtering and post-oxidation

Nanocrystalline VO2 thin films were deposited onto glass slides by direct current magnetron sputtering and postoxidation. These films undergo semiconductor-metal transition at 70°C, accompanied by a resistance drop of two magnitude orders. The crystal structures and surface morphologies of the VO2 films were characterized by x-ray diffraction (XRD) and atomic force microscope (AFM), respectively. Results reveal that the average grain size of VO2 nanograins measured by XRD is smaller than those measured by AFM. In addition, Raman characterization indicates that stoichiometric VO2 and oxygen-rich VO2 phases coexist in the films, which is supported by x-ray photoelectron spectroscopy (XPS) results. Finally, the optical properties of the VO2 films in UV-visible range were also evaluated. The optical band gap corresponding to 2p-3d inter-band transition was deduced according to the transmission and reflection spectra. And the deduced value, E opt2p-3d = 1.81 eV, is in good agreement with that previously obtained by theoretical calculation.     

Observation of mechanical fracture and corresponding domain structure changes of polycrystalline PbTiO3 nanotubes

PbTiO₃ (PTO) nanotubes (NTs) were synthesized at various temperatures by gas phase reaction between PbO gas and anatase TiO₂ NTs and characterized by piezoresponse force microscopy (PFM). PTO ferroelectric phase was synthesized at as low as 400 °C as evidenced by PFM domain images and piezoresponse hysteresis loop measurement. Furthermore, the PTO NTs fabricated at above 500 °C underwent mechanical fracture through development of nanocracks due to grain growth, leading to ferroelectric domains with larger size and lower aspect ratio. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)