Acid catalyst concentration effect on structure and ion relaxation studies of Li2O–P2O5–B2O3–SiO2 glasses synthesized by sol–gel process

Lithium phosphoborosilicate (LPBS) glasses were synthesized through the sol–gel process by varying nitric acid concentrations as a catalyst. The sol–gel process was monitored through XRD and DSC to optimize the LPBS glass forming treatment. Characterization of LPBS glasses was conducted using XRD, FTIR and DSC techniques. Impedance measurements were carried out at different temperatures on LPBS samples synthesized by sol–gel process with various nitric acid concentrations and impedance data were analyzed using Boukamp equivalent circuit software. The conductivity of LPBS samples was calculated from analyzed impedance data and it was found that sample synthesized with 2.5 N nitric acid concentration showed the high conductivity σ = 2.28(±0.02) × 10⁻⁷ S cm⁻¹ at 443 K. Activation energy (E_a) is obtained from Arrhenius plots of dc conductivity and it is found to be 0.39 (±0.02) eV for the high conductance sample. Ac conductivity data were analyzed using Jonscher’s power law (JPL) and the power law exponent (s) exhibits a low s value for high conducting LPBS sample and a non-linear behavior with temperature. The electric modulus data were fitted with Kohlraush–William–Watts (KWW) stretched exponential function and modulus formalism is used to study the ionic relaxation behavior at different temperatures in LPBS glasses synthesized with varying nitric acid concentrations.     

Electrical conductivity and dielectric relaxation in non-crystalline films of tungsten trioxide

Amorphous tungsten trioxide (a-WO₃) thin films were prepared by thermal evaporation technique. The electrical conductivity and dielectric properties of the prepared films have been investigated in the frequency range from 100 Hz to 100 kHz and in the temperature range 293–393 K. In spite of the absence of the dielectric loss peaks, application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation. The frequency dependence of σ(ω) follows the Jonscher’s universal dynamic law with the relation σ(ω) = σ_dc + Aω^s, where s is the frequency exponent. The conductivity in the direct regime, σ_dc, is described by the small polaron model. The electrical conductivity and dielectric properties show that Hunt’s model is well adapted to a-WO₃ films.     

Electrical characterizations of silver chalcogenide glasses

We present a study of the electrical properties of silver chalcogenide glasses ‘40AgI’–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂ and 50AgI–25Ag₂S–25GeS₂ in the 77–400 K temperature and the 20 Hz to 1 MHz frequency ranges. In our temperature range, a large variation of the real permittivity is observed, in relation with an electrodes polarization effect. As the amount of silver iodide increases in the Ag₂S–GeS₂ matrix, the glass transition temperature and the activation energies decrease, the electrical conductivity increases and reaches 4 Ω⁻¹ m⁻¹ at room temperature for the glass with 50% AgI. The study of the conductivity shows a behavior due to a high ionic conductivity, thermally activated with E_dc = 0.21 eV, E₁ = 0.075 eV (40AgI–30Ag₂S–30GeS₂, 45AgI–27.5Ag₂S–27.5GeS₂), E_dc = 0.17 eV, E₁ = 0.055 eV for 50AgI–25Ag₂S–25GeS₂. For these glasses, we have seen three conductivity regimes. The first two terms are thermally activated. The third term cannot be actually clearly identified because either it is thermally activated with a very low activation energy and frequency dependent, or it is almost non-thermally activated and frequency dependent.     

Electrical properties of annealed a-SiC:H thin films

In the present work the dependence of electrical properties of a-SiC:H thin films on annealing temperature, T_a, has been extensively studied. From the measurements of dark dc electrical conductivity, σ_D, in the high temperature range (from 283 up to 493 K), was found that the conductivity activation energy, E_a, is invariant for T_a ⩽ 673 K and equal to 0.64 eV, whereas for T_a from 673 up to 873 K, E_a increases at about 0.2 eV reaching to a maximum value 0.85 eV at T_a = 873 K, suggesting the optimum material quality. This behavior of E_a as a function of T_a is mainly attributed to relaxation of the strain in the amorphous network, which is possibly combined with weak hydrogen emission for temperatures up to 873 K. For further increase of T_a (>873 K) the phenomenon of hydrogen emission, causes rapid decrease of E_a down to 0.24 eV at T_a = 998 K, deteriorating the material quality. These results are also supported by the measurements of dark dc electrical conductivity in the low temperature range (from 133 up to 283 K), where the dependence of the density of gap states at the Fermi level, N(E_F), on annealing temperature presents the minimum value at T_a = 873 K. The Meyer–Nelder rule was found to hold for the a-SiC:H thin films for annealing temperatures up to 873 K. Finally, the dependence of dark dc electrical conductivity at room temperature, σ_DRT, on T_a showed to reflect directly the dependence of E_a on T_a.     

InOx semiconductor films deposited on glass substrates for transparent electronics

Transparent undoped semiconductor indium oxide films were deposited by radio frequency (rf) plasma enhanced reactive thermal evaporation (rf-PERTE) of indium at low substrate temperature. It was experimentally verified that the variation of rf power density has a strong influence on the electrical and structural properties of the films. The thickness of the InO_x films is of about 100 nm. Results show that InO_x films show an average visible transmittance of about 85% and energy gap of about 2.6 eV. Structural and electrical conductivity measurements show that films are polycrystalline and there exists a linear variation of conductivity logarithm vs reciprocal of temperature. Electrical conductivity variation of 17.6 to 5.8 × 10⁻³ (Ω cm)⁻¹ for films produced at rf power densities ranging from 3.9 to 78.1 mW cm⁻³ was obtained. This controllable semiconductor behavior can therefore satisfy the requirement of a particular application for these type of films.     

ac conductivity in a-Ge–Se–Bi glasses

In the present paper the effect of Bi impurity (low ∼4 at.% and high ∼10 at.%) on the ac conductivity (σ_ac) of a-Ge₂₀Se₈₀ glassy alloy is studied and the experimentally deduced values are fitted with theoretically deduced values by using correlated barrier hopping model (CBH). Frequency dependent ac conductance of the samples over a frequency range of 100–50 kHz has been taken in the temperature range (268–360 K). At frequency 2 kHz and temperature 298 K, the value of ac conductivity (σ_ac) decreases at low concentration of Bi (4 at.%). However, the value of σ_ac increases at higher concentration of Bi (10 at.%). The ac conductivity is proportional to ω^s for undoped and doped samples. The value of frequency exponent (s) decreases as the temperature increases. These results have been explained on the basis of some structural changes at low and high concentration of Bi impurity.     

Electrical properties of A2.6+xTi1.4−xCd(PO4)3.4−x (A = Li,K; x = 0.0–1.0) phosphate glasses

Electrical properties of A_2.6+xTi_1.4−xCd(PO₄)_3.4−x (A = Li, K; x = 0.0–1.0) phosphate glasses are investigated over a frequency range from 42 Hz to 1 MHz at different temperatures. Impedance spectroscopy is used to separate the bulk conductivity from electrode effect of electrical conductivity data. The bulk dc conductivity is Arrhenius activated, with activation energies and pre-exponential factors following the Meyer–Neldel rule. The real part of ac conductivity shows universal power law feature. The variation of dielectric constant with frequency is attributed to ion diffusion and polarization occurring in the phosphate glasses. The frequency dependent imaginary part of electric modulus M″(ω) plot shows non-Debye feature in conductivity relaxation. The Kohlrausch–Williams–Watts stretched exponential function was used to describe the modulus spectra and the stretching exponent β is found to be temperature independent. Scaling in M″(ω) shows that the electrical relaxation mechanisms are independent of temperature for given composition at different temperatures.     

Effects of hydration,annealing, and melting on heat transport properties of fused quartz and fused silica from laser-flash analysis

Thermal diffusivity (D) at high temperature (T) was measured from 15 samples of commercial SiO₂ glasses (types I, II, and III with varying hydroxyl contents) using laser-flash analysis (LFA) to isolate vibrational transport, in order to determine effects of impurities, annealing, and melting. As T increases, D_glass decreases, approaching a constant (~ 0.69 mm²s^? 1) above ~ 700 K. From ~ 1000 K to the glass transition, the slope of D is small but variable. Increases of D with T of up to 6% correlate with either low water and/or low fictive temperature and are attributed to removal of strain and defects during annealing. Upon crossing the glass transition, D substantially decreases to 0.46 mm²s^? 1 for the anhydrous melt. Hydration decreases D_glass, makes the glass transition occur over wider temperature intervals and at lower T, and promotes nucleation of cristobalite from supercooled melt. Due to the importance of thermal history, a spread in D of about 5% occurs for any given chemical type. Combining prior steady-state, cryogenic data with our average results on type I glass provides thermal conductivity (k_lat = ρC_PD) for type I: k_lat increases from ~ 0 K, becoming nearly constant above 1500 K, and drops by ~ 30% at T_g. We find that D^? 1(T) correlates with thermal expansivity times temperature from ~ 0 K to melting due to both properties arising from anharmonicity.     

Polarons in boron doped iron phosphate glasses

The electrical conductivity and dielectric properties of xB₂O₃–(40 ? x)Fe₂O₃–60P₂O₅ (x = 6–20, mol%) glasses were investigated in the frequency range from 0.01 Hz to 1 MHz and the temperature range from 303 K to 523 K. At temperatures below 523 K an ac conductivity and the dielectric constant follow the universal dielectric response (UDR), being typical for hopping or tunneling of localized charge carriers. A detailed analysis of the temperature dependence of the UDR parameter s in terms of the theoretical model for tunneling of small polarons revealed that below 523 K this mechanism governs the charge transport in these glasses. The comparison of the values of characteristic coefficients W_∞ and α determined by two different methods confirms the polaronic behavior of boron doped iron phosphate glasses.     

Novel feature of the universal power law dispersion of the ac conductivity in disordered matter

The ac conductivity σ_ac of different types of materials as a function of angular frequency ω is approximated by a ‘universal’ power law σ_ac = Aωⁿ, A and n are fitting parameters .The exponent and the pre-exponential factor depend on temperature, in general. In the present Letter, we suggest an empirical law that states that the temperature evolution of log A is proportional to the temperature evolution of n. Data reported on different materials ascertain that the ratio −log A/n is constant, regardless the nature of the material and the type of conductivity.     

Ion transport studies in CuI-doped silver borovanadate glassy system

In the present report, ionic transport properties and microstructural investigations of superionic materials in a cost-effective glassy system xCuI–(100 ? x)[2Ag₂O–0.7V₂O₅–0.3B₂O₃], where x = 30, 40, 45, 50 and 60, have been described. The temperature dependent electrical conductivity studies were carried out by ac impedance analysis. The microstructure of the materials studied by SEM indicated the presence of dispersed CuO and AgI micro-crystals in the silver oxysalt glass matrix. High room temperature electrical conductivity of 3.58 × 10^?3 S cm^?1 and low activation energy of 0.24 eV were obtained for the best conducting composition. The ac impedance data were analyzed using impedance and modulus formalisms. These materials show extremely high t_i value of 0.999 and the ionic conductivity is apparently due to Ag⁺ ions only. The use of two glass formers helped to form materials with higher T_g, higher thermal stability and better ionic transport properties.     

Influence of structural disorder on the dynamics of mobile oxygen ions in Dy2(Ti1−yZry)2O7

We report on the influence of structural disorder on the oxide-ion conductivity of Dy₂(Ti_1−yZr_y)₂O₇ (y = 0.55 and 0.90). A significant disorder is induced by mechanical milling synthesis of the samples, and, depending on the Zr/Ti, a partial and progressive structural ordering can be achieved by subsequent annealing at temperatures between 800 and 1500 °C. Ionic conductivity is relatively high for both compositions (up to 10⁻⁴ S/cm at 900 K), and the activation energies for dc conductivity (in the range 1.02–1.32 eV) are found to be larger in samples with more structural disorder. This result is quantitatively explained, by using Ngai’s coupling model, in terms of the enhancement of interactions between mobile oxygen vacancies in a more disordered structure.     

Molecular dynamics in glass-forming poly(phenyl methyl siloxane) as investigated by broadband thermal,dielectric and neutron spectroscopy

The molecular dynamics of glass-forming poly(methyl phenyl siloxane) (PMPS) is studied by thermal (10⁻³–5 × 10² Hz), dielectric (10⁻³–10⁹ Hz) and neutron (5 × 10⁸–10¹² Hz) spectroscopy. Because of the broad frequency range of 15 orders of magnitude the study provides a precise determination of glassy dynamics in a wide temperature range using different probes. The relaxation rates extracted from the different methods agree quantitatively in both their absolute values and in their temperature dependencies. A detailed analysis of the temperature dependence of the relaxation rate f_p by a derivative technique shows that the α-relaxation of PMPS has to be characterized by a high and a low temperature branch separated by a crossover temperature T_B = 250 K. In both temperature ranges the temperature dependence of f_p has to be described by Vogel/Fulcher/Tammann laws with different Vogel temperatures. Also the analysis of the dielectric strength in its temperature dependence gives a crossover behavior from a low to a high temperature region with a similar value of T_B. T_B can be interpreted as onset of cooperative fluctuations and the formation of dynamical heterogeneities. The dependence of the relaxation rate on the scattering vector Q extracted from neutron scattering obeys a power law τ ∼ Q^−Slope, where the power Slope varies between Slope = 2 and Slope = 3.5 with increasing temperature. This anomalous dependence of the relaxation time on the momentum transfer is discussed in terms of dynamic heterogeneities in the underlying motional processes even at temperatures above T_B. Besides the segmental dynamics the fast Methyl group rotation is considered as well. The relaxation rates of this process have an activated temperature dependence with an activation energy of 8.3 kJ/mol. The data were discussed in the framework of the threefold jump model were the incoherent elastic scattering from ‘fixed’ atoms which are frozen on the time scale of the Methyl group rotation was taken into account.     

Effect of silver doping on the electrical properties of a-Sb2Se3

This paper reports the effect of Ag-doping on electrical properties of a-Sb₂Se₃ in the temperature range 230–340 K and frequency range 5–100 kHz. The variation of transport properties with thermal doping has been studied. Ag-doping produces two homogeneous phases in the sample, which are found to be voltage dependent in the temperature range studied and frequency dependent in lower frequency region (0.1–10 kHz). Activation energy E_g and C′ [= σ₀ exp (γ/k), where γ, is the temperature coefficient of the band gap] calculated from dc conductivity has been found to vary from (0.42 ± 0.01) eV to (0.26 ± 0.01) eV and (4.11 ± 0.01) × 10⁻⁵ to (2.90 ± 0.02) × 10⁻⁶ Ω⁻¹ cm⁻¹ respectively. Ag-doping can be used to make the sample useful in device applications.     

Electrical conductivity and single oscillator model properties of amorphous CuSe semiconductor thin film

The structural, optical dispersion and electrical conductivity properties of the CuSe thin film have been investigated using X-ray diffraction, electrical and optical characterization methods. X-ray diffraction results indicate that CuSe thin film has an amorphous structure. The electrical conductivity of the CuSe film increases with increasing temperature. The activation energy and room temperature conductivity values of the film were found to be 1.32 meV and 3.89 × 10⁻³ S/cm, respectively. The refractive index dispersion of the thin film obeys the single oscillator model and single oscillator parameters were determined. The E_o, n_∞, and S_o values of the CuSe thin film were found to be 5.08 eV, 3.55 and 1.92 × 10¹⁴ m⁻², respectively. The obtained results suggest that CuSe film is an amorphous semiconductor.     

Investigation of the conductivity of the lithium borosilicate glass system

The lithium borosilicate system (Li₂O)_0.4(B₂O)_(0.6x)(Si₂O₄)_0.6(1−x) with x = 0, 0.2, 0.3, 0.4, 0.6, and 0.8 was investigated using impedance spectroscopy. Impedance spectra were taken in the frequency range from 50 Hz to 1 MHz and in the temperature range from 100 to 280 °C. The ac- and dc-conductivity, relaxation frequency and activation energy of the dc-conductivity were extracted from the impedance spectra. The dc-conductivity of the investigated glass samples increases almost linearly from silica rich (x = 0) to the boron rich (x = 0.8) samples. Activation energy (E_a) was found to be 0.65 eV for high conducting sample and 0.8 eV for low conducting sample, respectively. The mixed glass-former effect was not observed on the samples studied. The effect of temperature scaling of ac-conductivity was observed, which indicates, that ionic conductivity relaxation mechanism is temperature independent for samples with x = 0, 0.2, 0.3. However, some deviations from scaling were found for the samples with higher x (x = 0.4, 0.6, 0.8).     

Conductivity percolation transition of Agx(Ge0.25Se0.75)100−x glasses

The ionic conductivity of several chalcogenide glasses increases abruptly with mobile ion addition from values typical of insulating materials (10⁻¹⁶–10⁻¹⁴ Ω⁻¹ cm⁻¹) to values of fast ionic conductors (10⁻⁷–10⁻¹ Ω⁻¹ cm⁻¹). This change is produced in a limited concentration range pointing to a percolation process. In a previous work [M. Kawasaki, J. Kawamura, Y. Nakamura, M. Aniya, Solid State Ionics 123 (1999) 259] the transition from semiconductor to fast ionic conductor of Ag_x(Ge_0.25Se_0.75)_100−x glasses was detected at x¹ ≅ 10 at.% in the form of a steep change in the conductivity. Ag_x(Ge_0.25Se_0.75)_100−x glasses with x ⩽ 25 at.%, prepared by a melt quenching method, are investigated by impedance spectroscopy in the frequency range 5 Hz–2 MHz at different temperatures, T, from room temperature to 363 K and by DC measurements at room temperature. The conductivity of the glasses, σ, was obtained as a function of silver concentration and temperature. For x ⩾ 10 at.% our results are in agreement with those reported by Kawasaki et al. [M. Kawasaki, J. Kawamura, Y. Nakamura, M. Aniya, Solid State Ionics 123 (1999) 259]. The percolation transition was observed in the range 7 ⩽ x ⩽ 8. The temperature dependence of the ionic conductivity follows an Arrhenius type equation σ = (σ_o/T) · exp(−E_σ/kT). The activation energy of the ionic conductivity, E_σ, and the pre-exponential term, σ_o, are calculated. The results are discussed in connection with other chalcogenide and chalcohalide systems and linked with the glass structures.     

Magnetic and magnetoelastic properties of cobalt–iron amorphous–nanocrystalline pulsed laser deposited thin films

We prepared pulsed laser deposited planar and cylindrical amorphous–nanocrystalline Co–Fe thin films using the corresponding target with composition Co_1−xFe_x, x = 0, 0.02, …, 1.0. Their room temperature spontaneous magnetization, M_s (film), was always a fraction of the M_s of the corresponding crystalline alloy, M_s (film) = γ M_s (crystal): γ ≈ 0.8 for pure Co, γ ≈ 0.88 for the Co₃₅Fe₆₅ film and γ ≈ 0.94 for pure Fe. Their isotropic magnetostriction coefficient, λ_s, was also determined. From pure Co to 30 at.% Fe λ_s values were similar to those corresponding to the crystalline alloys: from pure Co to 4 at.% Fe was negative and of the order of 10⁻⁶; λ_s increased to 10⁻⁵ up to 25 at.% Fe and achieved 10⁻⁴ from 30 at.% Fe to 90 at.% Fe; λ_s decreased to 10⁻⁵ for pure Fe. A chemical short-range order between the Co atoms surrounded by the Fe ones, increasing the magnetic moment of Fe atoms, was used to explain the observed behavior.     

Transport behavior of yttrium substituted polycrystalline La0.7Pb0.3MnO3

The transport properties in La_0.7?xY_xPb_0.3MnO₃ (0.0 ? x ? 0.2) is investigated. The substitution of La³⁺ ions by smaller nonmagnetic Y³⁺ leads to greater spin disorder and induces variations in the magnetotransport behavior. From resistivity versus temperature curves a metal–insulator transition phenomenon is observed at the transition temperature, T_P, decreases as the Y content increases. The resistivity is well fitted using the equation ρ(T) = ρ_nexp[(T¹/T)ⁿ] with n = 1/4 and n = 1/2 at high and intermediate temperatures, respectively. The characteristic temperature T¹ varies with Y content in a manner consistent with the localization model of variable range hopping. Below T_P, resistivity varies as a function of power law contributions, ρ = ρ₀ + ρ₂T² + ρ_5/2T^5/2, corresponding to the electron scattering processes in the ferromagnetic phase.     

Experimental determination of the solid–liquid equilibrium,metastable zone,and nucleation parameters of the flunixin meglumine–ethanol system

Measurements of the metastable zone and solubility for flunixin meglumine–ethanol system were obtained. The solubility was measured within the temperature range from 288.15 to 328.15 K. The mole fraction solubility was correlated satisfactorily with the temperature by the equation: x_eq=2.35×10^?12e^0.07121T. The value of enthalpy of dissolution, enthalpy of fusion and enthalpy of mixing were determined to be 49.04, 64.03 and ?14.99 kJ mol^?1 respectively. The metastable zone width of flunixin meglumine was measured by an electric conductivity method. A comparison of the nucleation temperatures from electric conductivity measurement and from focused beam reflectance measurement (FBRM) shows that both detection techniques give almost the same results for flunixin meglumine. The nucleation parameters of flunixin meglumine in ethanol were determined from the metastable zone data. Over the equilibrium temperature range from 312.28 to 325.55 K, the nucleation rate constant was varied from 0.00001 to 0.00120 #/m² min, whereas the nucleation order was varied from 2.23022 to 3.39299. The obtained high values of nucleation order indicated a high rate of nucleation.