Charge transport mechanism of vanadium pentoxide xerogel-polyaniline nanocomposite

The nanocomposites of conducting polyaniline are prepared by intercalating into the layers of vanadium pentoxide (V₂O₅) xerogel. The intercalation is confirmed by the observation of lattice expansion of V₂O₅ xerogel. Dc conductivity of the gel follows Arrhenius type temperature dependence while the nanocomposites exhibit three dimensional variable range hopping. The ac conductivity and dielectric properties are extensively studied at low temperature up to the frequency of 10 MHz. Two semicircles in Cole-Cole plot of impedance are found for the nanocomposites. The ac conductivity spectra reveal three frequency regions. The frequency exponent in the lower frequency region is nearer to 2. The dielectric response exhibit broad spectra which are analyzed by Cole-Cole distribution function. The peak frequency of dielectric spectra appears at the first cross over frequency of conductivity spectra.     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.     

Transport properties of lead phosphate glass doped by cobalt,vanadium and chromium oxides

The electrical transport properties were investigated of a glass system of basic composition 50?mol. % Pb₃O₄–50?mol. % P₂O₅ containing CoO, Cr₂O₃ or V₂O₅ dopanys. The ac conductivity and the thermoelectric power were measured as a function of temperature. Properties such as dielectric constant, loss factor tangent and electrical conductivity are reported in the frequency range 200?Hz–100?kHz and temperature range 300–450?K. The variation in electrical conductivity with temperature was found to depend on the types of transition metal ions involved. The temperature dependence of the frequency exponent, s, was analyzed using different theoretical models. The variation of the thermoelectric power with temperature indicated the presence of more than one conduction mechanism for the investigated samples. This result was confirmed with the results of the dielectric properties at different frequencies. The introduction of cobalt ions in glass formers improves the electrical properties of non-crystalline ionic conductors.     

Dielectric relaxation in vanadium phosphate glasses

An asymmetric distribution of relaxation times has been inferred from an increase in the Cole-Cole distribution parameter α with increasing values of ωτ in 62% v₂O₅–38% P₂O₂ glass. The conventional Debye type relaxation loss peaks in the frequency range 10²–10⁵ Hz are observed in this sample above 85°K. The extrapolated values of dielectric constant and relaxation time below 100°K seem unexpectedly large while the high temperature extrapolated values of ?' are close to ?_∞ as expected. Probably the conventional dielectric loss peaks are observed only above a critical temperature at which the carriers gain sufficient energy to be excited to the conduction band edge. Below this temperature hopping of carriers within kT of the Fermi level may dominate and conventional Debye type dielectric loss peaks may lose their significance as envisaged in the models of frequency dependent ac conductivity.     

Electrical conduction and dielectric properties of vanadium phosphate glasses doped with lithium

AC conductivity and dielectric studies on vanadium phosphate glasses doped with lithium have been carried out in the frequency range 0.2-100 kHz and temperature range 290-493 K. The frequency dependence of the conductivity at higher frequencies in glasses obeys a power relationship, σ_ac=Aω^s. The obtained values of the power s lie in the range 0.5≤s≤1 for both undoped and doped with low lithium content which confirms the electron hopping between V⁴⁺ and V⁵⁺ ions. For doped glasses with high lithium content, the values of s≤0.5 which confirm the domination of ionic conductivity. The study of frequency dependence of both dielectric constant and dielectric loss showed a decrease with increasing frequency while they increase with increasing temperature. The results have been explained on the basis of frequency assistance of electron hopping besides the ionic polarization of the glasses. The bulk conductivity increases with increasing temperature whereas decreases with increasing lithium content which means a reduction of the V⁵⁺.     

Effect of surface roughness on nucleation and growth of vanadium pentoxide nanowires

The effect of surface roughness on subsequent growth of vanadium pentoxide (V₂O₅) nanowires is examined. With increasing surface roughness, both the number density and aspect ratio of V₂O₅ nanowires increase. Structures and morphology of obtained nanowires were characterized by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The nanowires are approximately 40-90 nm in diameter and 2 μm in length. X-ray diffraction (XRD) analysis indicates that the obtained nanowires are orthorhombic structure with (0 0 1) out-of-plane orientation. The luminescence property of V₂O₅ nanowires has been investigated by photoluminescence (PL) at 150 K and 300 K. PL results show intense visible emission, which is attributed to different inter-band transitions between the V 3d and O 2p band. This simple fabrication approach might be useful for fabrication of large area V₂O₅ nanowires arrays with high density.     

Proton and electron conduction in polymer intercalated vanadium pentoxide xerogel

A comprehensive proton and electron conduction in vanadium pentoxide xerogel-conducting polymer nanocomposites are analyzed by the impedance spectroscopy. The complex impedance plots are used to estimate the proton and electron conductivity. Both protonic and electronic conductivities follow Arrhenius type behavior with temperature. Protonic conductivity increases with the increase of intercalated conducting polypyrrole. The highly ordered conducting polypyrrole (PPY) molecule enhances the diffusion of H₃O⁺ ions into the host lattice. Broad dielectric loss peaks are found in a wide range of frequency domain (KHz–MHz). The intercalated water within the oxide network of vanadium pentoxide remains supercooled up to lowest measured temperature 137 K.     

Electrical characterization and Raman spectroscopy of individual vanadium pentoxide nanowire

We measured I–V characteristics, electrical resistance, and Raman spectra in the temperature range from room temperature to above 600 K to obtain nanodevices. Measurements were taken on a single V₂O₅ nanowire deposited on a Si template, where two- and four-point metallic contacts were previously made using e-beam lithography. In both two- and four-point probe measurements, the I–V curves were clearly linear and symmetrical with respect to both axes. Drastic reduction in electrical resistance and deviation from single valued activation energy with increasing temperature indicated phase transitions taking place in the nanowire. From temperature-dependent HR-Micro Raman measurements, reductions from V₂O₅ to VO₂/V₂O₃ phases took place at a temperature as low as 500 K, when electrons were injected to the nanowire through electrical contacts.     

Dielectric and AC conductivity behavior of BaBi2Nb2O9 ceramics

The complex dielectric and AC conductivity response of BaBi₂Nb₂O₉ relaxor ferroelectric ceramics were studied as a function of frequency (100 Hz-10 MHz) at various temperatures. The observed dielectric behavior was characterized by two types of relaxation processes which were described by the ‘universal relaxation law’. The frequency dependence of conductivity which showed a classical relaxor behavior followed the Jonscher's universal law σ(ω)=σ₀+Aωⁿ. The exponent n exhibited a minimum in the vicinity of temperatures of dielectric anomaly while the pre-factor A showed a maximum. The temperature dependence of n followed the Vogel-Fulcher relation with activation energy of about 0.14 eV.     

Transport and dielectric properties of V2O5-MnO-TeO2 glasses

The frequency (1-10 kHz) and temperature (80-350 K) dependences of the ac conductivity and dielectric constant of the V₂O₅-MnO-TeO₂ system, containing two transition-metal ions, have been measured. The dc conductivity _dc measured in the high-temperature range (200-450 K) decreases with addition of the oxide MnO. This is considered to be due to the formation of bonds such as V--O--Mn and Mn--O--Mn in the glass. The conductivity arises mainly from polaron hopping between V^4+M and V⁵⁺ ions. It is found that a mechanism of adiabatic small-polaron hopping is the most appropriate conduction model for these glasses. This is in sharp contrast with the behaviour of the Mn-free V₂O₅-TeO₂ glass, in which non-adiabatic hopping takes place. High-temperature conductivity data satisfy Mott's small-polaron hopping model and also a model proposed by Schnakenberg in 1968. A power-law behaviour ( _ac = Aω^s , with s < 1) is well exhibited by the ac conductivity σ_ac data of these glasses. Analysis of dielectric data indicates a Debye-type relaxation behaviour with a distribution of relaxation times. The MnO-concentration-dependent σ_ac data follow an overlapping large-polaron tunnelling model over the entire range of temperatures studied. The estimated model parameters are reasonable and consistent with changes in composition.     

Characterization and transport properties of intercalated polypyrrole-vanadium pentoxide xerogel nanocomposite

Layered vanadium pentoxide (V₂O₅) xerogel is used as host material for the synthesis of conducting polypyrrole intercalated nanocomposites. Powder X-ray diffraction spectra show the increase of interlayer space of V₂O₅ xerogel indicating the formation of polypyrrole in the interlayer space of the host. Thermal stability of intercalated polypyrrole is superior compared to bulk polypyrrole. Dc conductivity of the xerogel follows Arrhenius type temperature dependence while the nanocomposites exhibit Mott's three-dimensional variable range hopping. Optical band gap decreases with intercalation of polypyrrole.     

Structural and transport properties of Li-intercalated vanadium pentoxide nanocrystalline films

The X-ray diffraction (XRD), transmission electron microscopy, density, electrical and thermoelectric power (TEP) properties of nanocrystalline Li _x V₂O₅ ? nH₂O xerogel films (0 ≤ x ≤ 22 mol.%) were investigated. The films were produced by the sol–gel technique (colloidal route), which was used to enable high-purity, uniform preparation. The relative intensity of the (002) XRD line increased with increasing Li content. The particle size was found to be about 6.0 nm. Electrical conductivity and thermoelectric power were measured parallel to the substrate surface in the temperature range 300–480 K for the as-prepared films. The electrical conductivity showed that all the samples were semiconductors and that conductivity increased with increasing Li content. The conductivity of the present system was primarily determined by hopping carrier mobility, which was found to vary from 6.81 × 10^?6 to 0.33 × 10^?6 cm² V^?1 s^?1 at 380 K. The carrier density was evaluated to be 8.73 × 10¹⁹–1.118 × 10²¹ cm^?3. The conduction was confirmed to obey non-adiabatic small polaron hopping. The thermoelectric power, or Seebeck effect, increased with increasing Li content. The results obtained indicate an n-type semiconducting behavior within the temperature range investigated.     

Electrical conductivity and complex electric modulus of titanium doped nickel-zinc ferrites

The samples Ni_1+x−yZn_yTi_x Fe_2−2xO₄; y=0.1, 0.0≤x≤0.5 were prepared in a single-phase spinel structure as indicated from X-ray analysis. Electrical conductivity and dielectric measurements at different temperatures from 300 K to 600 K in the frequency range from 42 Hz to 5 MHz have been analyzed. The relation of conductivity with temperature revealed a semiconductor to semimetallic behavior as Ti⁴⁺ concentration increases. The conduction mechanism depends mainly on the valence exchange between the different metal ions in the same site or in different sites. The dielectric constant as a function of temperature and frequency showed that there is a strong dependence on the compositional parameter x. The electrical modulus has been employed to study the relaxation dynamics of charge carriers. The result indicates the presence of correlation between motions of mobile ion charges. The activation energies extracted from M′(ω) and M″(ω) peaks are found to follow the Arrhenius law. The electrical conductance of the samples found to be dependent on the temperature and frequency.     

Effect of the metal-insulator transition on vanadium K-photoabsortion spectrum in V2O3

The effect of the metal-insulator phase transition on the X-ray K-absorption spectrum of V in V₂O₃ was measured by synchrotron radiation. A different behavior of the transition to 3d vs 4p states in the two phases was observed. These results have been correlated with the change in the screening of the 1s hole due to the variation of the dielectric constant ?(q, ω) in the two phases.     

Study of (Bi2O3)(BaxMo1−xO3) polycrystalline ceramic as relaxor ferroelectric

Solid solutions of bismuth layered (Bi₂O₃)(Ba_xMo_1−xO₃) (0.2≤x≤0.8, x is in step of 0.2) ceramics were prepared by conventional solid-state reaction of the constitutive oxides at optimized temperatures with a view to study its electrical properties. Powder X-ray diffraction has been employed for physical characterization and an average grain size of ∼16 to 22 nm was obtained. XRD study reveals the single phase structure of the samples. Dielectric properties such as dielectric constant (ε′), dielectric loss (tanδ) and ac electrical conductivity (σ_ac) of the prepared ceramics sintered at various temperatures in the frequency range 10¹–10⁷ Hz have been studied. A strong dispersion observed in the dielectric properties shows the relaxor type behavior of the ceramic. The presence of maxima in the dielectric permittivity spectra indicates the ferroelectric behavior of the samples. Impedance plots (Cole–Cole plots) at different frequencies and temperatures were used to analyze the electric behavior. The value of grain resistance increases with the increase in Ba ion concentration. The conductivity mechanism shows a frequency dependence, which can be ascribed to the space charge mainly due to the oxygen vacancies. The relaxation observed for the M″ (ω) or Z″ (ω) curves is correlated to both localized and long range conduction. A single ‘master curve’ for the normalized plots of all the modulus isotherms observed for a given composition indicates that the conductivity relaxation is temperature independent.     

Magnetic interactions and electronic structure of $$\hbox {Pt}_{2}\hbox {Mn}_{1-x}\hbox {Y}_{x} \hbox {Ga (Y = Cr and Fe)}$$ system: An ab-initio calculation

Structural, optical, electrical conductivity and dielectric relaxation properties of bulk 4-amino-3-mercapto-6-(2-(2-thienyl)vinyl)-1,2,4-triazin-5(4H)-one donor (AMT) are studied. The structure of AMT in its powder form was analysed by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and atomic force microscopy (AFM). AC measurements (impedance, capacitance and phase angle) are done over the temperature range 303–373 K and in the frequency range from 42 Hz to 5 MHz. Analytical approaches for the experimental results of the σ _AC(ω, T) and the temperature behaviour of the frequency exponent show that the correlated barrier hopping (CBH) model is a good model to explain the AC electrical conductivity of bulk AMT organic semiconductor material. Application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation. The activation energy from the DC conductivity and the relaxation time are quite similar suggesting a hopping mechanism for AMT. The optical band gap of AMT is investigated using spectrophotometric measurement of transmittance at normal incidence of light in the wavelength range 300–1100 nm.     

Dielectric constant and microwave conductivity of the vanadium bronze Na0.33V2O5

Measurements of the dielectric constant and microwave conductivity are reported for the vanadium bronze Na_0.33V₂O₅. The dielectric constant is highly anisotropic and very large parallel to the highly conducting direction, while the conductivity is strongly dispersive. The results can be consistently interpreted by considering Na_0.33V₂O₅ as a quasi-one-dimensional conductor in which, at low temperatures, a pseudo-gap opens in the open-electron density of states due to inter-site correlations.     

Specific features of electrical conductivity of the insulating phase of vanadium dioxide doped with niobium

The electrical conductivity of V_{1 – x}Nb_xO₂ single crystals have been investigated over a wide temperature range covering regions of the existence of the metallic and insulating phases. It has been shown that, with an increase in the niobium concentration, the electrical conductivity of the metallic phase becomes below the Mott limit for the minimum metallic conductivity. Immediately after the metal–insulator transition, the electrical conductivity is determined by a large amount of free electrons that gradually localized with a decrease in the temperature. The temperature dependence of the electrical conductivity in the insulating phase of V_{1 – x}Nb_xO₂ has been explained in the framework of the hopping conductivity model that takes into account the effect of thermal vibrations of atoms on the resonance integral.     

Frequency dependence of ionic conductivity and dielectric relaxation studies in Na3H(SO4)2 single crystal

Electrical impedance measurements of Na₃H(SO₄)₂ were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO₄ tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ω^s. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.