Novel nanomaterials based on electronic and mixed conductive glasses

Novel nanomaterials based on lithium–vanadate-phosphate (LVP) and lithium–iron-phosphate (LFP) glasses were prepared and their electrical properties were investigated by impedance spectroscopy. It was found out that the electronic conductivity of the original glasses of both systems can be considerably enhanced by appropriate annealing at temperatures close to beginning of crystallization temperatures determined by DSC/DTA methods. Increase in conductivity arises from the modification of the microstructure. It was shown by XRD and SEM studies that by appropriate heat-treatment glasses of both systems can be turned into nanomaterials consisting of crystallites smaller than 100 nm embedded in the glassy matrix. It was postulated that the major role in the conductivity enhancement of these nanomaterials is played by the developed interfacial regions between nanocrystalline and glassy phases, in which the concentration of V⁴⁺–V⁵⁺ or Fe²⁺–Fe³⁺, pairs responsible for electron hopping in those systems, is higher than inside the glassy matrix and the formed nanocrystallites.     

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.     

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.     

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.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

DC conductivity of silver vanadium tellurite glasses

The mixed electronic-ionic conduction in 0.5[xAg₂O-(1−x)V₂O₅]-0.5TeO₂ glasses with x=0.1-0.8 has been investigated over a wide temperature range (70-425 K). The mechanism of dc conductivity changes from predominantly electronic to ionic within the 30?mol% Ag₂O?40 range; it is correlated with the underlying change in glass structure. The temperature dependence of electronic conductivity has been analyzed quantitatively to determine the applicability of various models of conduction in amorphous semiconducting glasses. At high temperature, T>θ_D/2 (where θ_D is the Debye temperature) the electronic dc conductivity is due to non-adiabatic small polaron hopping of electrons for 0.1?x?0.5. The density of states at Fermi level is estimated to be N(E_F)≈10¹⁹-10²⁰ eV⁻¹ cm⁻³. The carrier density is of the order of 10¹⁹ cm⁻³, with mobility ≈2.3×10⁻⁷-8.6×10⁻⁹ cm² V⁻¹ s⁻¹ at 300 K. The electronic dc conductivity within the whole range of temperature is best described in terms of Triberis-Friedman percolation model. For 0.6?x?0.8, the predominantly ionic dc conductivity is described well by the Anderson-Stuart model.     

Effect of iron doping on the characterization and transport properties of calcium phosphate glassy semiconductors

X-ray diffraction (XRD), differential scanning calorimeter (DSC), density (d) and dc conductivity (σ) of the glasses in Fe₂O₃-CaO-P₂O₅ system were reported. The dc conductivity in the temperature range 303-453 K was measured. The overall features of these XRD curves confirm the amorphous nature of the present samples. The density of glasses increases from 2.750 to 2.892 g/cm³ with increasing Fe₂O₃ content as a result of a strengthening of cross-linking within glass network. The glass temperature values (T_g) of the present glasses were larger than those of tellurite glasses. This indicates a higher thermal stability of the glass in the present system. The glasses had conductivities ranging from 10⁻⁹ to 10⁻⁵ Sm⁻¹ at temperatures from 303 to 453 K. Electrical conduction of the glasses was confirmed to be due to non-adiabatic small polaron hopping and the conduction was primarily determined by hopping carrier mobility.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

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.     

Compositional dependence of the electrical conductivity of calcium vanadate glassy semiconductors

Scanning electron microscopy (SEM), X- ray diffraction (XRD), density (d), oxygen molar volume (V_m) and dc conductivity of different compositions of calcium vanadate glasses are reported. SEM exhibits a surface without any presence of a microstructure which is a characteristic of the amorphous phase. The overall features of these XRD curves confirm the amorphous nature of the present glasses. Density was observed to decrease with an increase in V₂O₅ content. The experimental results were analyzed with reference to theoretical models existing in the literature. It has been observed that the high-temperature conductivity data are consistent with Mott's nearest-neighbor hopping model. However, both Mott variable-range hopping (VRH) and Greaves intermediate range hopping models are found to be applicable. The hopping at high temperatures in the calcium vanadate glasses occurs by non-adiabatic process in contrast to the vanadate glasses formed with conventional network formers. The hopping model of Schnakenberg can predict the temperature dependence of the conductivity data. The percolation model of Triberis and Friedman applied to the small polaron hopping (SPH) regime is also consistent with data. The various model parameters such as density of states, hopping energy, etc., obtained from the best fits were found to be consistent with the glass compositions.     

Effect of nanocrystallization on the electronic conductivity of vanadate–phosphate glasses

Electronically conducting glasses of the composition xV₂O₅·(100 − x)P₂O₅ for 60 < x < 90 were prepared. The glasses of the composition corresponding to x = 90 exhibited the highest electrical conductivity and they were studied in more detail. The effects of the annealing of the samples on their electrical conductivity, structure and other characteristics were studied by impedance spectroscopy, X-ray diffractometry, DSC and SEM microscopy. It was shown that, at temperatures close to the crystallization temperature T_c (determined from DSC), these glasses turned into nanomaterials consisting of crystalline grains of V₂O₅ (average size 25–35 nm) embedded in the glassy matrix. Their electrical conductivity was higher and the temperature stability was better than those of the starting glasses. It is postulated that the major role in this conductivity enhancement is played by the interfacial regions between crystalline and amorphous phases. The annealing at temperatures exceeding T_c led to massive crystallization and to a conductivity drop. The XRD and SEM observations have shown that the material under study undergoes structural changes: from amorphous at the beginning, to partly crystalline after the annealing at 340 °C and to polycrystalline after the annealing at 530 °C.The obtained results are in agreement with those of our earlier studies on mixed electronic–ionic conducting glasses of the ternary Li₂O–V₂O₅–P₂O₅ system.     

Electrical properties of nickel-doped arsenic trisulphide

Results of temperature and frequency dependent a.c. conductivity of pure and nickel-doped a-As₂S₃ are reported. The a.c. conductivity of pure As₂S₃ obeys a well-known relationship: σ_ac ∝ω ^s. Frequency exponents is found to decrease with increasing temperature. Correlated barrier hopping (CBH) model successfully explains the entire behaviour of a.c. conductivity with respect to temperature and frequency for pure As₂S₃. But a different behaviour of a.c. conductivity has been observed for the nickel doped As₂S₃. At higher temperatures, distinct peaks have been observed in the plots of temperature dependence of a.c. conductivity. The frequency dependent behaviour of a.c. conductivity (σ_ac ∝ω ^s) for nickeldoped As₂S₃ is similar to pure As₂S₃ at lower temperatures. But at higher temperatures, ln σ_ac vs lnf curves have been found to deviate from linearity. Such a behaviour has been explained by assuming that nickel doping gives rise to some neutral defect states (D ^0′) in the band gap. Single polaron hopping is expected to occur between theseD ^0‘ andD ⁺ states. Furthermore, allD ⁺,D ^0′ pairs are assumed to be equivalent, having a fixed relaxation time at a given temperature. The contribution of this relaxation to a.c. conductivity is found to be responsible for the observed peak in the plots of temperature dependence of a.c. conductivity for nickel-doped As₂S₃. The entire behaviour of a.c. conductivity with respect to temperature and frequency has been explained by using CBH and “simple pair” models. Theoretical results obtained by using these models, have been found to be in agreement with the experimental results.     

Low-temperature electrical conductivity of congruent lithium niobate crystals

The electrical conductivity of lithium niobate crystals was investigated at temperatures between 80 and 450 K as a function of the oxidation-reduction annealing conditions. The results are interpreted in terms of polaron electrical conductivity at room temperature and above. A reduction in the measurement temperature leads to “freezing out” of small-radius polarons, and hopping of Heitler-London bipolarons via unfilled Nb_Li sites becomes the main mechanism responsible for the electrical conductivity. Fiz. Tverd. Tela (St. Petersburg) 40, 1307–1309 (July 1998)     

Non-adiabatic small-polaron hopping conduction in VN–PbO–TeO2 glasses

The dc conductivity of VN–PbO–TeO₂ glasses with different mole percentages of VN, PbO and TeO₂ has been measured in the temperature range 125–450?K. The conductivity of the glasses increases with increasing VN content for a fixed mole percentage of PbO. Neither Mott's variable-range hopping (VRH) model at low temperatures (T<Θ_D/4, where Θ_D is the Debye temperature) nor Greaves’ VRH model at intermediate temperatures (Θ_D/?4<T<Θ_D/2) describe the dc conductivity data for these glasses. Multiphonon tunnelling transport of strongly coupled electrons is also unable to account for the carrier transport. However, at high temperatures (T?>?Θ_D/2), conduction is shown to be due to small-polaron hopping in the non-adiabatic regime. Alteration of the VN content causes a change in the model parameters achieved from best-fitting curves for the glasses. Modulated differential scanning calorimetry analysis shows that the glass transition temperatures T _g in this system vary from 269 to 302°C.     

Drift mobility and kinetics of transport of excess charge carriers in glassy CdGexAs2

Conclusions We tried to measure transient conductivity response to pulse strongly absorbed excitation (light, accelerated electrons) in sandwich type samples of glassy CdGe _x As₂ compounds. We observed the signal due to transport of free excess carriers. From analysis of experimental results we conclude that in our materials strong trapping effects are present, so the range of excited carriers is very short (10^–4-10^–3 cm) even in the highest electrical fields used (to 10⁴ V. cm^–1). Estimates of upper limit of drift mobility give the values 10^–1- 1 cm² V^–1 sec^–1. We did not succeed in determining the type of carriers which are responsible for the observed effects.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

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⁺.     

Formation of thermally stable low-resistance Ti/W/Au ohmic contacts on n-type GaN

A Ti(12 nm)/W(20 nm)/Au(50 nm) metallization scheme has been investigated for obtaining thermally stable low-resistance ohmic contacts to n-type GaN (4.0×10¹⁸ cm^-3). It is shown that the current–voltage (I–V) characteristics of the samples are abnormally dependent on the annealing temperature. For example, the samples that were annealed at temperatures below 750 °C for 1 min in a N₂ ambient show rectifying behavior. However, annealing the samples at temperatures in excess of 850 °C results in linear I–V characteristics. The contact produces a specific contact resistance as low as 8.4×10^-6 Ω cm² when annealed at 900 °C. It is further shown that the contacts are fairly thermally stable even after annealing at 900 °C; annealing the samples at 900 °C for 30 min causes insignificant degradation of the electrical and structural properties. Based on glancing angle X-ray diffraction and Auger electron microscopy results, the abnormal temperature dependence of the ohmic behavior is described and discussed. PACS 72.80.Ey; 73.40.Cg; 73.20.At; 79.60Bm; 73.40.Gk     

Electrical properties of doped 3-tetradecylpolypyrrole/metal devices

The electrical properties of devices made of doped 3-tetradecylpolypyrrole (PPy-C₁₄) thin films sandwiched between indium-tin-oxyde (ITO) and gold metal electrodes are reported. The current density–voltage (J–V) curves are asymmetric and nonlinear implying a non Ohmic rectifying contact. Using standard thermionic emission theory (Schottky) J–V characteristics were satisfactorily fitted with a saturation current of J₀=1.5×10^-5 A cm^-2, a barrier height of ϕ_b=0.7 eV, and an ideality factor of n=5.3. Characteristics from the plot of J–V versus 1/T show that the activation energy of the thermionic emission process is higher below the glass transition temperature of PPy-C₁₄ (T_g=45 °C) than above, which seems to indicate that the hopping conduction process is enhanced at T>T_g. The carrier concentration has been calculated from capacitance–voltage (C-V) measurements (N=1.9×10¹⁷ cm^-3) allowing estimation of the carrier mobility μ=2.6×10^-2 cm² V^-1 s^-1. PACS 73.61.Ph; 73.40.Sx; 73.30.+y     

Electrical properties of a-antimony selenide

This paper reports conduction mechanism in a-Sb₂Se₃ over a wide range of temperature (238 to 338 K) and frequency (5 Hz to 100 kHz). The d.c. conductivity measured as a function of temperature shows semiconducting behaviour with activation energy ΔE=0.42 eV. Thermally induced changes in the electrical and dielectric properties of a-Sb₂Se₃ have been examined. The a.c. conductivity in the material has been explained using modified CBH model. The band conduction and single polaron hopping is dominant above room temperature. However, in the lower temperature range the bipolaron hopping dominates.