Thermal and low energy electron bombardment induced oxygen loss of V2O5 single crystals: Transition into V6O13

Thermal treatment in UHV of clean V₂O₅ single crystals results in homogeneous oxygen loss, involving a rate-limiting surface reaction. Depending upon the pretreatment, aircleaved samples transform topotactically into V₆O₁₃, or into what we call a phase Q of probable composition V₄O₉ or V₆O_13.5. Low energy electron bombardment of clean UHV-cleaved V₂O₅(010) surfaces produces the transition V₂O₅ → V₆O₁₃ at room temperature. This effect is attributed to electron beam stimulated reactions. The influence on the transition of carbon-containing impurities is discussed. The nucleation of V₆O₁₃ on V₂O₅ is explained by a model based on a surface reaction, the rate of which is enhanced by the interaction with contaminating molecules and low energy electron bombardment. The presence of shear planes at the boundary between V₂O₅ and the V₆O₁₃ nuclei locally enhances the oxygen loss rate and allows the V₆O₁₃ nuclei to grow into the bulk.The enhanced mobility of the oxygen at these boundaries is thought to influence favorably the oxidation-regeneration rate of the V₂O₅-catalyst.     

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.     

Insulator-metal transition in V3O5

The results of a study of the insulator-metal phase transition in V₃O₅ occuring at T = 450 K are presented. Conductivity, thermopower, magnetic, structural and optical data are reported. On a basis of the data obtained we conclude that the high-temperature phase is a poor metal with strong electron correlations and localized magnetic moments. The metal-non-metal transition is presumably driven by the spatial ordering of V³⁺ and V⁴⁺ ions.     

Crystallization kinetics of Li2O-PbO-V2O5 glasses

Lead vanadate glasses of the system 5Li₂O−(45−x) PbO−(50+x) V₂O₅, with x=0, 5, 10, and 15 mol% have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC using continuous-heating techniques. In addition, from dependence of the glass-transition temperature (T_g) on the heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined and the crystallization mechanism was characterized. The results reveal the increase of the activation energy for glass transition which was attributed to the increase in the rigidity, the cross-link density and the packing density of these glasses. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of Li_0.30V₂O₅, Li_0.67O₅V₂, LiV₆O₁₅, Li₄O₄Pb, and O₇Pb₂V₂ in a remaining amorphous matrix.     

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.     

Static susceptibility and heat capacity studies on V3O7·H2O7 nanobelts

V₃O₇·H₂O nanobelts were prepared by a hydrothermal method at 190 °C using V₂O₅·nH₂O gel and H₂C₂O₄·2H₂O as starting agents. The obtained nanobelts have diameters ranging from 40 to 70 nm with lengths up to several micrometers. Measurements of the static magnetic susceptibility and the specific heat show a discontinuous phase transition at around T=145 K, which separates two regions of paramagnetic behavior.     

L'etude cristallographique et par effet mössbauer des solutions solides V2O5Fe2O3

Using the Mössbauer effect, we analyse the behaviour of (V₂O₅)_1?x(Fe₂O₃)_x solid solutions with the starting composition x = 1?15 mol.% Fe₂O₃. The number of iron ions dissolved in V₂O₅ lattice depends on the initial composition x of Fe₂O₃ and tends to a maximum value corresponding to 4 mol.% Fe₂O₃. The composition dependence of the quadrupole splitting and isomer shifts is presented.     

Lattice parameters variation with temperature of Ti2O3 and (Ti0.98V0.02)2O3 from single crystal X-ray data

The lattice parameters of Ti₂O₃ and (Ti_0.98V_0.02)₂O₃ have been measured as a function of temperature (24–670°C for Ti₂O₃ and 24–440°C for V-doped Ti₂O₃) from single crystal X-ray data. The high temperatures were attained by blowing hot argon directly on the crystal mounted on an automatic Philips diffractometer. This experimental set-up gives standard deviations which are at least 10 times better than those of the previous measurements and allows to keep Ti₂O₃ as such well above the transition. The variations of a, c, $\text{c}\text{a}$ (hexagonal axes) for pure Ti₂O₃ are in agreement with the previous results. On the contrary we did not observe any transition in the unit cell volume. The V-doping seems to attenuate the transition which is visible only on the a vs T curve     

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.     

Thermochemistry of the high and ambient temperature lithium vanadium bronze phases LixV2O5

The enthalpies of formation of a series of high and low temperature phases in the ternary oxide system Li_xV₂O₅ have been determined by solution calorimetry. Samples of the former, α-Li_0.04V₂O₅, β-Li_0.30V₂O₅, β'-Li_0.48V₂O₅ and γ-LiV₂O₅, were prepared by solid state reaction at 650°C. The ambient temperature materials Li_0.1V₂O₅(I), Li_0.45V₂O₅(II) and Li_1.03V₂O₅(III) were prepared by n-butyl lithiation in hexane. The thermochemistries of the two classes of material were examined and related to structural features and to the observed behaviour of V₂O₅ as a battery cathode material in lithium cells.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

High pressure study of BaPb0.7Bi0.3O3 films

The resistance R, the superconducting transition temperature T_c and the energy gap Δ(T) have been measured on the BaPb_0.7Bi_0.3O₃ films up to 14 kbar. We have found that up to 14 kbar: (1) pressure suppresses T_c and Δ(T) while enhances R, (2) the value of 2Δ(0)/kT_c is 3.8±0.1, independent of pressure, and (3) the Δ(T)/Δ(0) varies with T/T_c in a BCS fashion but only for T/T_c<0.75 and independent of pressure. The results show that BaPb_1?xBi_xO₃ is a weak-coupling superconductor, but fail to provide information about the cause for the high T_c of the compound.     

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.     

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.     

Correlation between the high temperature anomalies in V2O3 and the lattice parameters

A single phase corundum type structure was observed in V₂O₃ from 165 to 1100K. An anomalous behaviour of the lattice parameters of the rhombohedral unit cell was found in the high temperature region where V₂O₃ undergoes a broad electrical transition. The unit cell edge a_R contracts above 165 K, reaching a minimum at 533 K, after which there is a sharp increase. Above 595 Ka_R expands continuously and then almost linearly above 775 K. The temperature dependence of the rhombohedral angle shows two distinct regions, and the volume expansion follows the variation of angle; the change of the rate of expansion coincides with the minimum of a_R. The contraction of a_R corresponds to a reduction in certain second-neighbor VV distances.Our results show that a gradual transition is taking place in V₂O₃ from an α type structure to a β type characteristic of the Cr-doped V₂O₃ compounds. In addition, the sharp dip of the a_R curve occurs at nearly the same temperature as the peak previously observed in small angle scattering of neutrons. It is presumed that the two effects are related, and that the critical-like behaviour of a_R is due to some dynamic magnetoelastic effect involving second neighbor VV interactions.     

A revisit of photoluminescence property for vanadate oxides AVO3 (A:K, Rb and Cs) and M3V2O8 (M:Mg and Zn)

We revisited the vanadium oxide phosphors, AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg and Zn) for a revaluation of possibility of these compounds for lighting applications, and the internal quantum efficiency (η) and luminescent colour properties for AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg, and Zn) have been presented. The AVO₃ showed the broadband emission from 380 to 800 nm, and the η for the KVO₃, RbVO₃ and CsVO₃ were 4%, 79% and 87%, respectively. The CIE colour coordinates are located at white region on the chromaticity diagram. The M₃V₂O₈ (A:Mg and Zn) also exhibited a quite broadband emission between 410 and 900 nm, indicating yellow luminescent colour. The Zn₃V₂O₈ showed high η value, 52%, compared to that of the Mg₃V₂O₈ (η=6%). This enhancement of η in the Zn₃V₂O₈ could be due to the increasing exciton diffusion assisted by the hybridizations of Zn 3d and O 2p orbitals for the valence band, and Zn 4s and Ti 3d orbitals for the conduction band.     

Vanadium-Al2O3 nanostructured thin films prepared by pulsed laser deposition: Optical switching

The formation and optical response of VO_x nanoparticles embedded in amorphous aluminium oxide (Al₂O₃) thin films by pulsed laser deposition is studied. The thin films have been grown by alternate laser ablation of V and Al₂O₃ targets, which has resulted in a multilayer structure with embedded nanoparticles. The V content has been varied by changing the number of pulses on the V target. It is found that VO_x nanoparticles with dimensions around 5 nm have been formed. The structural analysis shows that the vanadium nanoparticles are oxidized, although probably there is not a unique oxide phase for each sample. The films show a different optical response depending on their vanadium content. Optical switching as a function of temperature has been observed for the two films with the highest vanadium content, at transition temperatures of about −20 °C and 315 °C thus suggesting the presence of nanoparticles with compositions V₄O₇ and V₂O₅, respectively.     

Influence of lithium phosphate concentration and temperature on the electrical conduction of (76V2O5-24P2O5)1−X (Li3PO4)X glasses

Characterization of the (76V₂O₅-24P₂O₅)_1−X (Li₃PO₅)_X, where X=0.0,0.01,0.02,0.10 and 0.15, glass has been done using X-ray diffraction and differential thermal analysis (DTA). The dc conductivity of the glass samples was studied over a temperature range from 300 to 593 K. The temperature dependence of dc conductivity shows two regions. One at relatively high temperature range, above θ_D/2, and the other at relatively low temperature range, below θ_D/2. The I-V characteristics of the glasses have been studied as a function of both temperature and Li₃PO₄ content. The I-V characteristics exhibits threshold switching with differential negative resistance. It's found that both the threshold voltage (V_th) and threshold current (I_th) are dependent on the temperature and lithium phosphate concentration.     

Adsorption behaviors of V2O5 nanowires on binary mixed self-assembled monolayers

The adsorption behaviors of V₂O₅ nanowires on binary mixed self-assembled monolayers (SAMs) were investigated with variation of the mixing ratio of two differently terminated thiolates on Au. Hydroxyl-covered V₂O₅ nanowires showed a preferential adsorption on amine (NH₂)-terminated thiolates over methyl (CH₃)-terminated ones. However, on the binary mixed SAM of NH₂- and CH₃-terminated thiols, the adsorption behavior did not follow a simple expectation based upon the electrostatic interaction. The total number of adsorbed V₂O₅ nanowires increased with the mole fraction of NH₂-terminated thiolates up to χNH₂∼0.5, then it decreased with further increase of χNH₂. The height distribution of adsorbed nanowires showed that the relative portion of the agglomerated wires thicker than 3.5 nm to individual wires thinner than 3.5 nm increased up to χNH₂∼0.75 and then it decreased with further increase of χNH₂. The dispersion of molecules with polar-functional groups as well as the molecular ordering of mixed SAMs is attributed to such adsorption behaviors of V₂O₅ nanowires.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.