Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Dielectric parameters in Se70Te30 and Se70Te28Zn2 chalcogenide glasses

Temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) are studied in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈Zn₂. The measurements have been made in the frequency range (8-500 kHz) and in the temperature range 300 to 350 K. An analysis of the dielectric loss data shows that the Guintini's theory of dielectric dispersion based on two-electron hopping over a potential barrier is applicable in the present case.No dielectric loss peak is observed in glassy Se₇₀Te₃₀. However, such loss peaks exist in the glassy Se₇₀Te₂₈Zn₂ in the above frequency and temperature range. The Cole-Cole diagrams have been used to determine some parameters such as the distribution parameter (α), the macroscopic relaxation time (τ₀), the molecular relaxation time (τ) and the Gibb's free energy for relaxation (ΔF).     

Dielectric properties and conductivity in CuO and MoO3 doped borophosphate glasses

A novel set of glasses of the type (B₂O₃)_0.10-(P₂O₅)_0.40-(CuO)_0.50−x-(MoO₃)_x, 0.05≤x≥0.50, have been investigated for dielectric properties in the frequency range 100 Hz-100 kHz and temperature range 300-575 K. From the total conductivity derived from the dielectric spectrum the frequency exponent, s, and dc and ac components of the conductivity were determined. The temperature dependence of dc and ac conductivities at different frequencies was analyzed using Mott's small polaron hopping model, and the high temperature activation energies have been estimated and discussed. The observed initial decrease in conductivity (ac and dc) and increase in activation energy with the addition of MoO₃ have been understood to be due to the hindrance offered by the Mo⁺ ions to the electronic motions. The observed peak-like behavior in conductivity (dip-like behavior in activation energy) in the composition range 0.20-0.50 mol fractions of MoO₃ may be due to mixed transition effect occurring in the present glasses. The temperature dependence of frequency exponent, s, has been analyzed using different theoretical models. It is for the first time that the mixed transition metal ion (TMI) doped borophosphate glasses have been investigated for dielectric properties and conductivity over wide temperature and frequency ranges and the data have been subjected to a thorough analysis.     

Fe掺杂CaCu3Ti4O12陶瓷的介电性能与弛豫特性研究

采用固相反应法制备了CaCu₃Ti_4-xFe_xO₁₂(0≤x≤0.2)陶瓷,通过X射线衍射、扫描电子显微镜、介电频谱和阻抗谱等手段研究了Fe对CaCu₃Ti₄O₁₂陶瓷的结构和介电性能的影响.研究发现：CaCu₃Ti_4-xFe_{x关键词： 巨介电常数 双阻挡层电容模型 界面极化}     

Studies of dielectric and impedance properties of KCa2V5O15 ceramics

A polycrystalline sample, KCa₂V₅O₁₅, with tungsten bronze structure was prepared by a mixed-oxide method at low temperature (i.e., at 630 °C). A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound was studied by scanning electron microscopy (SEM). Two dielectric anomalies at 131 and 275 °C were observed in the temperature dependency of dielectric response at various frequencies, which may be attributed to the ferroelastic-ferroelectric and ferroelectric-paraelectric transitions, respectively. The nature of variation of the electrical conductivity, and value of activation energy of different temperature regions, suggest that the conduction process is of mixed-type (i.e., ionic-polaronic and space charge generated from the oxygen ion vacancies). The impedance plots showed only bulk contributions, and non-Debye type of relaxation process occurs in the material. A hopping mechanism of electrical transport processes in the system is evident from the modulus analysis. The activation energy of the compound (calculated both from loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers.     

Electrical studies on bulk Se96Sn4 semiconducting glass before and after gamma irradiation

Bulk Se₉₆Sn₄ chalcogenide glass was prepared by melt quenching technique and irradiated by different doses of 4, 8, 12, 24 and 33 kGy using ⁶⁰Co gamma emitter. I-V characteristics were obtained for this glass, before and after gamma irradiation, in the temperature range 200-300 K. Ohmic behavior was observed at low electric fields (≤1×10⁴ V/m), while at higher fields, a deviation from ohmic towards non-ohmic behavior was observed. The plots of ln(I/V) vs. V were found to be straight lines and the slopes of these lines decrease linearly with temperature indicating the presence of SCLC. In the temperature range of measurements, the dependence of DC conductivity on temperature at low electric field shows two types of conduction channels, one in high temperature range 270-300 K and the other at low temperature range 200-270 K. Analysis of the experimental data shows that the conductivity at room temperature decreases with increase in irradiation dose. This is attributed to rupturing of SnSe_4/2 structural units, upon irradiation, and rebuilt of Se atoms between Se chains. This redistribution of bonds, induced by gamma irradiation, is responsible for the corresponding increase in the activation energy. The obtained values of the activation energy indicate that the conduction occurs due to thermally assisted charge carriers movement in the band tail of localized states. However, in the low temperature range, results obtained from Mott’s variable range hopping (VRH) model reveal that the density of localized states has its maximum value at a gamma dose of 12 kGy, while the disorder parameter T_o, hopping distance R_hop and hopping energy W have their minimum value at this particular dose.     

Giant dielectric relaxation in SrTiO3-SrMg1/3Nb2/3O3 and SrTiO3-SrSc1/2Ta1/2O3 solid solutions

Ceramic samples of (1−x)SrTiO₃-xSrMg_1/3Nb_2/3O₃ and (1−x)SrTiO₃-xSrSc_1/2Ta_1/2O₃ were prepared, and their dielectric properties were studied at x=0.005–0.15 and 0.01–0.1, respectively, at frequencies 10 Hz–1 MHz and at temperatures 4.2–350 K. A giant dielectric relaxation was observed in the temperature range 150–300 K, and not so strong but well-developed relaxation was found in the temperature range 20–90 K. The activation energy U and the relaxation time τ₀ were determined to be 0.21–0.3 eV and from 10⁻¹¹ to 10⁻¹² s for the high-temperature relaxation and 0.01–0.02 eV and 10⁻⁸–10⁻¹⁰ s for the low-temperature relaxation, respectively. The additional local charge compensation of the heterovalent impurities Mg²⁺ and Nb⁵⁺ (or Sc³⁺ and Ta⁵⁺) by free charge carriers or the host ion vacancies is suggested to be the underlying physical mechanism of the relaxation phenomena. On the basis of this mechanism, the Maxwell-Wagner model and the model of reorienting dipole centers Mg²⁺ (or Sc³⁺) associated with the oxygen vacancy are proposed to explain the high-temperature relaxation with some arguments in favor of the latter model. The polaron-like model with the Nb⁵⁺-Ti³⁺ center is suggested as the origin of the low-temperature relaxation. The reasons for the absence of ferroelectric phase transitions in the solid solutions under study are also discussed. From Fizika Tverdogo Tela, Vol. 44, No. 11, 2002, pp. 1948–1957. Original English Text Copyright ? 2002 by Lemanov, Sotnikov, Smirnova, Weihnacht. This article was submitted by the authors in English.     

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250 K, in addition to the well-investigated dielectric relaxation close to 100 K. The effect of sintering and doping (La³⁺) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La_2/3Cu₃Ti₄O₁₂, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers.     

Semiconduction in xFe2O3.(1-x) [3B2O3.PbO] glasses

The electrical resistivity of iron lead borate glasses was measured over the temperature range 300–700 K. The resistivity increases with the iron content and is a function of the Fe²⁺/Fe_tot ratio, but the minimum does not appear for 0.28 ≤ c ≤ 0.50. The samples with x > 15 mol % Fe₂O₃ show the presence of two activation energies for conduction. A change in the activation energy can be explained by charge transfer between iron ions in similar positions at low temperatures, and between iron ions in different positions at higher temperatures. In order to analyse the conductivity data, we have considered in all the glasses a polaronic model for conduction.     

Electrical properties of KTiOPO4 single crystal in the temperature range from −100 °C to 100 °C

The electrical property of a KTiOPO₄ single crystal was studied by means of a dielectric spectroscopy method in the temperature range from −100 to 100 °C. Dielectric dispersion began at a temperature, T_S=−80 °C. It is believed that this dielectric dispersion is related to the ionic hopping conduction, which arises mainly from the jumping of K⁺ ions. The activation energy concerned with hopping conduction is E_a∼0.20 eV above T_S. T_S=−80 °C can be the minimum temperature for the hopping K⁺ ion.     

Impact of annealing atmosphere on the multiferroic and dielectric properties of BiFeO3/Bi3.25La0.75Ti3O12 thin films

Multiferroic BiFeO₃/Bi_3.25La_0.75Ti₃O₁₂ films annealed in different atmospheres (N₂ or O₂) were prepared on Pt/Ti/SiO₂/Si substrates via a metal organic decomposition method. Based on our experimental results, it is considered that, in the films annealed in N₂, fewer Fe²⁺ ions while more oxygen vacancies are involved. As a result, at room temperature, predominated by the reduced Fe²⁺ fraction, lower leakage current and dielectric loss, better ferroelectric property while reduced magnetization are observed. However, the oxygen vacancies might be thermally activated at elevated temperature; thus, more strongly temperature-dependent leakage current and a higher dielectric relaxation peak are observed for the films annealed in N₂.     

Transport behavior and mechanism of conduction of simultaneously substituted Y and Fe in La0.7Ba0.3MnO3 perovskite

The electrical properties and the mechanism of conduction of the simultaneously substituted La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ perovskite (0≤x≤0.30) have been studied. The insertion of Y³⁺ and Fe³⁺ ions in the parent compound La_0.7Ba_0.3MnO₃ leads to an increase of the resistivity. The undoped sample (x=0) shows a metallic behavior, which can be fitted by the relation ρ(T)=ρ₀+ρ₂T²+ρ_4.5T^4.5, indicating the importance of electron-magnon scattering effects in this material. All the other samples (x≥0.10) are semiconductors throughout the studied temperature range (80-290 K). Several models have been used to fit their temperature-dependent resistivity: thermal activation, adiabatic nearest-neighbor hopping of small polarons (Holstein theory) and variable range hopping (VRH) models. The fits show that the electronic transport in semiconducting La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ is well described and dominated by the VRH mechanism, for which the hopping distance (a) grows with increasing Fe³⁺ doping, thus increasing the average hopping energy W.     

Synthesis,structural and complex impedance spectroscopy studies of Ni0.4Co0.4Mg0.2Fe2O4 spinel ferrite

Spinel ferrite having composition Ni_0.4Co_0.4Mg_0.2Fe₂O₄ was prepared by sol-gel method. X-ray diffraction result indicates that the ferrite sample has a cubic spinel type structure. FT-IR showed two absorption bands (ν₁ and ν₂) that are attributed to the stretching vibration of tetrahedral and octahedral sites. Complex impedance properties have been investigated in 200–420 K temperature range with varying frequency between 40 and 10⁷ Hz. Frequency and temperature dependency of imaginary part of permittivity (?″) and dielectric loss (tanδ) has been discussed in terms of hopping of charge carriers between Fe²⁺ and Fe³⁺ ions. Activation energy has been estimated from both temperature dependency of dc conductivity and relaxation time data, which indicates that the relaxation process and conductivity have the same origin. Nyquist plots of impedance show semicircle arcs for sample and an electrical equivalent circuit has been proposed to explain the impedance results.     

Temperature-dependent Mössbauer and dielectric studies of Mg0.95Mn0.05Fe1.0Ti1.0O4

The effect of tetravalent Ti⁺⁴ substitution in Mg_0.95Mn_0.05Fe₂O₄ on its magnetic and electrical properties has been studied using X-ray diffraction, Mössbauer spectroscopy, isothermal dc magnetization and dielectric measurements. X-ray diffraction studies have shown the structural transformation from cubic to tetragonal with the Ti⁺⁴ substitution. The Mössbauer spectra of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ recorded in the temperature range 20-300 K shows the presence of the magnetic as well as quadrupole interactions. The isothermal hysteresis loop infers that the system exhibits a ferrimagnetic ordering at room temperature. The Zero-field-cooled (ZFC) and field-cooled (FC) magnetization studies support ferrimagnetic ordering of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ at room temperature. Signatures of ferroelectric transition have been observed in the temperature range 200-300 K from dielectric measurements. The observed magnetic and dielectric behaviour indicate that this material exhibits multiferroic behaviour.     

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Hopping type of conduction in (Na0.5Bi0.5)ZrO3 ceramic

Polycrystalline sample with (Na_0.5Bi_0.5)ZrO₃ (NBZ) stoichiometry was prepared using a high-temperature solid-state reaction technique. X-ray diffraction (XRD) analyses indicate the formation of a single-phase perovskite-type orthorhombic structure. AC impedance plot is used as tool to analyse the electrical behaviour of the sample as a function of temperature at different frequency. The AC impedance studies revealed the presence of grain boundary effect and evidence of a negative temperature coefficient of resistance (NTCR) character. Pseudo Cole-Cole and complex electric modulus analyses indicated non-Debye-type dielectric relaxation. The AC conductivity obeys the universal power law. The pair approximation type correlated barrier hopping (CBH) model explains the universal behaviour of the s exponent. The apparent activation energy to the conduction process and minimum hopping distance are discussed.     

Oxygen-vacancy-related dielectric relaxation and conduction mechanisms in Bi5TiNbWO15 ceramics

This paper reports that the intergrowth ceramics Bi5TiNbWO15 （BW-BTN） have been prepared with the conventional solid-state reaction method. The dielectric and conductivity properties of samples were studied by using the dielectric relaxation and AC impedance spectroscopy in detail. Two distinct relaxation mechanisms were detected both in the plots of dielectric loss （tanδ） and the imaginary part （Z″） versus frequency in the frequency range of 10 Hz-13 MHz. We attribute the higher frequency relaxation process to the hopping process of the oxygen vacancies inside the grains, while the other seems to be associated with the space charges bound at the grain boundary layers. The AC impedance spectroscopy indicates that the conductivities at 625 K for bulk and grain boundary are about 1.12 × 10^-2 S/m and 1.43 × 10^-3 S/m respectively. The accumulation of the space charges in the grain boundary layers induces a space charge potential of 0.52 eV.     

Mössbauer spectroscopy as a probe of magnetic states in La0.5Ca0.5FeO3−δ perovskite

Charge disproportionation in La_0.5Ca_0.5FeO_3−δ perovskite has been detected by zero-field Mössbauer spectra from 20 K to room temperature. On the basis of the parameters of center shifts and hyperfine fields, Mössbauer spectra identified that the iron ionic states are Fe³⁺ and Fe⁵⁺ below 150 K, Fe³⁺, Fe⁴⁺ and Fe⁵⁺ in the intermediate temperature region, as well as Fe³⁺ and Fe⁴⁺ above 220 K. At low temperatures, the system exhibits a cluster-glass-like state resulting from competition between antiferromagnetic interaction of Fe³⁺–Fe³⁺ and ferromagnetic interaction of Fe³⁺–Fe⁵⁺.     

Crystal structure,NMR study,dielectric relaxation and AC conductivity of a new compound [Cd3(SCN)2Br6(C2H9N2)2]n

The crystal structure, the ¹³C NMR spectroscopy and the complex impedance have been carried out on [Cd₃(SCN)₂Br₆(C₂H₉N₂)₂]_n. Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355±2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of ¹³C CP/MAS line shapes shows indirect spin–spin coupling (¹⁴N and ¹³C) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325–376 K and the frequency range from 10⁻² Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of σ(ω,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism.