On the high temperature transition in V2O3

Magnetic susceptibility measurements on V₂O₃ powder sample using a vibrating sample magnetometer and microbalance with special attention to the region of 500–530K are reported. The high temperature transition in this compound is discussed in the framework of two interacting Hubbard bands obtaining a good qualitative agreement with thermal variations of the properties of V₂O₃.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Dielectric dispersion in PbO-Sb2O3-As2O3:V2O5 glasses

Dielectric properties, viz. dielectric constant ε′, loss tan δ and a.c conductivity σ_ac (over a wide range of frequency and temperature) and dielectric breakdown strength of PbO-Sb₂O₃-As₂O₃ glasses doped with V₂O₅ (ranging from 0 to 0.5 mol%) are studied. Analysis of these results, based on optical absorption and ESR spectra, indicates that the insulating strength of the glasses is comparatively high when the concentration of V₂O₅ is about 0.3 mol% in the glass matrix.     

Semiconductor-metal transition in v-doped Ti3O5

The semiconductor-metal transition in Ti₃O₅ is significantly affected by vanadium doping. The unit cell volume, ΔH, Δ? as well as Δ_χM decrease markedly up to 0.1% V₃O₅ and gradually thereafter until at ～ 10% V₃O₅, the transition disappears.     

碳热还原法制备V2O3-C双层包覆磷酸铁锂及其电化学性能

通过V₂O₅的碳热还原反应制备了具有优异倍率性能和循环稳定性的V₂O₃-C双层包覆的磷酸铁锂正极材料. 粉末X射线衍射、元素分析、高分辨投射电镜和拉曼光谱研究表明V2O3相与碳层共包覆于磷酸铁锂颗粒表面. 在V₂O₅的碳热还原反应后,碳含量明显降低,但石墨化程度未发生明显改变. 电化学测试结果表明少量V₂O₃显著改善了磷酸铁锂正极材料的倍率性能和高温循环性能,包含1%氧化钒的复合正极材料在0.2 C放电容量为167 mAh/g,5 C时放电容量为129 mAh/g,并且循环稳定性优异;在55 oC和1 C时放电容量为151 mAh/g,循环100次后无明显容量衰减.     

Epitaxial strain effects on the metal-insulator transition in V2O3 thin films

Effects of epitaxial stress on the metal-insulator transition of V₂O₃ have been studied for in the form of epitaxial thin films grown on α-Al₂O₃ (0001) and LiTaO₃ (0001) substrates. A metallic phase is stabilized down to 2 K in the V₂O₃ thin film on α-Al₂O₃ (0001), where the a-axis is compressed by 4% owing to large epitaxial stress. On the other hand, the transition temperature T_MI is raised by 20 K from the value of 170 K in bulk samples in the film on LiTaO₃ (0001), where the a-axis is expanded. These results suggest an intimate relationship between the a-axis length and T_MI in V₂O₃. The conductivity of the metallic ultrathin films shows logarithmic temperature dependence below 20 K, probably due to the Anderson localization in two-dimensional systems.     

基于旋涂法和电子束蒸发法制备的V2O5/Ag/V2O5叠层透明导电薄膜

利用溶胶-凝胶技术与电子束蒸镀相结合的方法在常温下制备了叠层V₂O₅/Ag/V₂O₅（VAV）透明导电薄膜,研究了各层薄膜厚度对叠层结构光电特性的影响。用原子力显微镜、紫外-可见光分光光度计、四探针电阻仪及开尔文探针对样品的表面形貌、光电性能及功函数等性质进行了表征。实验结果表明,该薄膜具有良好的光学和电学性质,可见光（380~780 nm）平均透过率达75%,迁移率为16.89 cm²/（V·s）,载流子浓度为－1.043×10²² cm^-3,方块电阻值为15.1 Ω/□,功函数为5.17 eV。该制备方法降低了V₂O₅薄膜的工艺制备难度,为该材料在太阳能电池中的应用创造了良好的前期基础。     

Electrical conductivity of transition metal oxide glasses in the system V2O5B2O3TeO2 at high temperatures

Bulk d.c. conductivities of the electronically conducting transition metal oxide glasses in the system xV₂O₅50B₂O₃(50?x)TeO₂ were measured at different temperatures in the range 310–623 K. The dependence of conductivity on composition is explained on the basis of the role of TeO₂ as a modifier or impurity. The observed kink in the log σ vs 1/T characteristic of the glasses is interpreted as being due to switching over of the conduction mechanism from one type to the other. The activation energies are fitted in a linear relation of the type E_g = A ? BP, where A and B are constants and P, the composition parameter. Comparing the results obtained with those of previous workers in the V₂O₅P₂O₅ and V₂O₅B₂O₃ systems, a physical analysis is presented.     

Evidence of small-polaron conduction in V2O5-MoO3 solid solutions

Electrical resistivity and thermoelectric power measurements on V₂O₅-MoO₃ solid solutions with 1, 2, 5 and 10 mol.% MoO₃ are reported. The experimental data are in agreement with the prediction of the model involving non-adiabatic small polarons.     

基于旋涂法和电子束蒸发法制备的V_2O_5/Ag/V_2O_5叠层透明导电薄膜

利用溶胶-凝胶技术与电子束蒸镀相结合的方法在常温下制备了叠层V2O5/Ag/V2O5(VAV)透明导电薄膜,研究了各层薄膜厚度对叠层结构光电特性的影响。用原子力显微镜、紫外-可见光分光光度计、四探针电阻仪及开尔文探针对样品的表面形貌、光电性能及功函数等性质进行了表征。实验结果表明,该薄膜具有良好的光学和电学性质,可见光(380~780 nm)平均透过率达75%,迁移率为16.89 cm2/(V·s),载流子浓度为-1.043×1022cm-3,方块电阻值为15.1Ω/□,功函数为5.17 eV。该制备方法降低了V2O5薄膜的工艺制备难度,为该材料在太阳能电池中的应用创造了良好的前期基础。     

Electronic properties of single-walled V2O5 nanotubes

Atomistic models of quasi-one-dimensional vanadium pentoxide nanostructures—single-walled nanotubes formed by rolling (010) layers of V₂O₅ are constructed and their electronic properties and bond indices are studied using the tight-binding band method. We show that all zigzag (n,0)- and armchair (n,n)-like nanotubes are uniformly semiconducting, and the band gap trends to vanish as the tube diameters decrease. The V-O covalent bonds were found to be the strongest interactions in V₂O₅ tubes, whereas V-V bonds proved to be much weaker.     

Molecular model for interstitial impurities in V2O5

A simple molecular model, including the four nearest vanadium and oxygen neighbours of an interstitial impurity in V₂O₅, is presented. The main result of the present model calculations are the symmetry of the ground state, and an order of magnitude for the defect level energies with respect to the bottom of the conduction band. These two results allow for an interpretation of the infrared spectrum of V₂O₅ doped with Cu or alkali-ions.     

Characterization and electrical properties of V2O5-CuO-P2O5 glasses

Characterization and electrical properties of vanadium-copper-phosphate glasses of compositions xV₂O₅-(40−x)CuO-60P₂O₅ have been reported. X-ray diffraction (XRD) confirms the amorphous nature of these glasses. It was observed that, the density (d) decreases gradually while the molar volume (V_m) increases with the increase of the vanadium oxide content in such glasses. This may be due to the effect of the polarizing power strength, PPS, which is a measure of ratio of the cation valance to its diameter. The dc conductivity increases while the activation energy decreases with the increase of the V₂O₅ content. The dc conductivity in the present glasses is electronic and depends strongly upon the average distance, R, between the vanadium ions. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron.     

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.     

Substrate effects on V2O3 thin films

We apply density functional theory and the augmented spherical wave method to analyze the electronic structure of V₂O₃ in the vicinity of an interface to Al₂O₃. The interface is modeled by a heterostructure setup of alternating vanadate and aluminate slabs. We focus on the possible modifications of the V₂O₃ electronic states in this geometry, induced by the presence of the aluminate layers. In particular, we find that the tendency of the V 3d states to localize is enhanced and may even cause a metal-insulator transition.     

Empirical band scheme for rhombohedral V2O3

The available optical and soft X-ray data are shown to yield a consistent picture of band separations in V₂O₃. The resulting band scheme is in accord with the band model for this material.     

A simple statistical model for V2O5 catalysis

In this work we propose a model to describe the selective oxidation of hydrocarbons at the surface of the V₂O₅ catalyst. The main ingredients of the model are the concentration of vanadium active sites, the surface and bulk diffusion rates of oxygen vacancies and the probability rate of a hydrocarbon reaction. The reactions take place at the free V₂O₅ (0 1 0) surface, and the diffusion of vacancies occur along the [0 1 0] (bulk) and [0 0 1] (surface) directions. The coupling between V₂O₅ and a given metal oxide support determines the concentration of the active vanadium sites, where the reactions can occur. Only the oxygen atoms, which are coordinated to three vanadium sites, take part of the oxidation process. In our calculations we employed two different approaches, single site and pair approximations, and some Monte Carlo simulations. We have found the dependence of the critical concentration of vacancies on the diffusion rates, probability of reaction, and fraction of active vanadium sites, for the catalyst to operate in an active steady state.     

Metal-like to insulator transition in Lu3Fe5O12

Polycrystalline Lu₃Fe₅O₁₂, prepared using the solid state reaction method, has Fe in the mixed valence state as inferred from the X-ray photoelectron spectroscopy. A spectral change in the impedance plot at 343 K is attributed to metal-like to insulator transition (MIT), which is analyzed in terms of localized and delocalized _eg$e_g$ electrons. The change in the slope at 343 K in the DC conductivity plot also proves the MIT. The dependence of Z^′${\mathrm{Z}}^{\prime }$ on temperature and Z^″${\mathrm{Z}}^{″}$ on frequency clearly substantiates the presence of localized electrons up to 343 K and delocalized electrons above 343 K.     

Weak field magnetic transition in Tb3Fe5O12

A jump like magnetic transition is observed at relatively weak field in Tb₃Fe₅O₁₂ when the magnetic field is applied along the hard axis and no transition is observed with the field applied along the easy axis. We believe that this evolution is related to the ”Umbrella” type magnetic structure known to exist in Tb₃Fe₅O₁₂ at low temperatures.     

A Brillouin study of the temperature-dependence of the acoustic modes across the insulator-metal transitions in V2O3 and Cr-doped V2O3

Brillouin scattering studies have been carried out on high-quality single crystals of undoped and 0.9% Cr-doped V₂O₃. The observed modes in both the samples at ∼12 and ∼60 GHz are associated with the surface Rayleigh wave (SRW) and bulk acoustic wave (BAW), respectively. In the undoped sample, the mode frequencies of the SRW and BAW modes decrease as the temperature is lowered from room temperature to the insulator-metal transition temperature (T_IM=T_N=∼130 K). Below the transition, the modes show hardening. In the doped sample, the SRW mode shows a similar temperature-dependence as the undoped one, but the BAW mode shows hardening from room temperature down to the lowest temperature (50 K). This is the first measurement of the sound velocity below T_IM in the V₂O₃ system. The softening of the SRW frequency from 330 K to T_IM can be qualitatively understood on the basis of the temperature-dependence of C₄₄, which, in turn, is related to the orbital fluctuations in the paramagnetic metallic phase. The hardening of the mode frequencies below T_IM suggests that C₄₄ must increase in the antiferromagnetic insulating phase, possibly due to the orbital ordering.