Impedance spectroscopy and magneto-dielectric analysis of La3+ substituted Co2Z hexaferrite

Single phase Ba₃Co₂Fe₂₄O₄₁ (Co₂Z) and Ba_2.8La_0.2Co₂Fe₂₄O₄₁ (La-Z) were prepared by solid state ceramic method. The dielectric, impedance and electric modulus were systematically investigated as a function of temperature from 50 °C–250 °C and in the frequency range of 1 Hz–1 MHz. Frequency dependent imaginary impedance and electric modulus implies that La³⁺ substitution significantly affect hopping and relaxation mechanism of charge carriers. Cole-Cole plots (Z" vs Z') has been fitted with suitable equivalent circuit for both Co₂Z & La-Z. The obtained grain and grain boundary resistances confirmed that charge carriers experienced lower resistance in La-Z. Arrhenius plots of relaxation time (τ) vs 1/T showed parallel conduction mechanism in system. Complex electric modulus spectrum distinguished the capacitive contribution of grain, grain boundary and electric effect. A very high magnetodielectric effect at low frequencies has been observed for La-Z.     

Structural,magnetic and dielectric properties of Cr substituted yttrium iron garnets

Chromium substituted polycrystalline Yttrium Iron Garnets (Y₃Fe_5–xCr_xO₁₂ with x = 0 to 0.5) were prepared in single‐phase form with lattice constant in the range of 12.3775 Å to 12.3560 Å. All samples exhibit ferrimagnetic transition with transition temperature (T_c) in the range of 547 K for x = 0 to 494 K for x = 0.5. The saturation magnetization value at room temperature is found to increase with Cr concentration that is, from 24.8 to 26.6 emu/g and this is attributed to the preferential occupation of Cr³⁺ ions at octahedral site of Fe³⁺ ions. The frequency dependence of impedance data shows the relaxation and thermal activation of charge carriers across grains and grain boundaries. The complex impedance spectra were modeled by considering equivalent circuits having contributions from the resistance and constant phase element due to grains and grain boundaries and capacitance across grain boundaries. The dielectric constant is found to increase from 20 to 52 as the Cr concentration is increased and it is attributed to hopping of charge carriers across Fe²⁺–Fe³⁺ centers. The Arrhenius plots of relaxation time of charge carriers and conductivity show an anomaly in the vicinity of ferrimagnetic transition temperature and it highlights the presence of magneto‐electric coupling.     

Charge transport in diatomaceous earth studied by broadband dielectric spectroscopy

In the present work, broadband dielectric spectroscopy measurements in the frequency range of 10 mHz to 1 MHz and at elevated temperatures (room temperature up to 950 °C) were carried out in industrial diatomaceous earth samples, in order to study charge transport phenomena which play a key role to the transport of both organic and inorganic contaminants in this kind of minerals. Cole–Cole plots of complex impedance measurements may serve to distinguish the contributions of grain interior, grain boundaries and electrode polarization to the overall electrical behavior of diatomite. Complex electrical conductivity and electric modulus representations have been combined under the fulfillment of the BNN relationship over a wide temperature range, in order to investigate the temperature dependence of diffusion coefficients and concentration of charge carriers in thermally modified diatomite. Both diffusivity and mobility follow the same Arrhenius-type behavior at two distinct temperature regions as DC-conductivity does. The related activation energies were estimated and ascribed to proton conduction (Ea ≈ 1.00 eV) at low temperatures (T < 650 °C) and hopping conduction of small polarons (Ea ≈ 1.67 eV) at higher temperatures, due to the presence of transition metals in diatomite sample. The thermal treatment of diatomite at 950 °C enhances the available charge carriers and increases the diffusivity which might improve its adsorption capacity.     

Dielectric properties of amorphous BaTiO3 films deposited by RF magnetron sputtering

In the present paper, dielectric properties of a-BaTiO₃ films have been investigated as a function of frequency (10⁻¹ to 10⁵ Hz) and temperature (25–350 °C) using the dielectric spectroscopy technique. Relaxation and ac-conductivity processes were analyzed in order to study charge transport in the bulk and at the electrode-film interfaces. It seems that the oxygen vacancies play an essential role in both processes.     

Dielectric Tunability,Dielectric Relaxation,and Impedance Spectroscopic Studies on (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 Lead‐Free Ceramics

Dielectric and impedance spectroscopies were employed to study the electrical behavior of (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ (abbr. BCTZ) lead‐free ceramic. The dielectric properties versus dc bias electric field experiment revealed high dielectric tunability (> 65%) as well as figure of merit (> 27) at 10 kHz and room temperature. At elevated temperature range, a dielectric loss peak was observed and verified to be correlate of oxygen vacancy relaxation. The impedance spectra studies indicate that the ceramic is a mixed ionic conductor of p‐type nature at the paraelectric phase and, the grain and total conductivity at 600°C reaches 6.0 × 10^?5 and 2.0 × 10^?5 S/cm, respectively.     

Structural,thermal and dielectric properties of 2D layered Ti3C2Tx (MXene) filled poly (ethylene-co-methyl acrylate) (EMA) nanocomposites

Light-weight and flexible 2D MXene-based polymer materials with low dielectric loss and high dielectric constant have drawn great attention in the power systems and modern electronic field. A series of Ti₃C₂T_x/EMA composites were fabricated via simple solution casting followed by a compression molding method with various mass concentrations of Ti₃C₂T_x (0, 1, 3, 5, 8, 10, 12, and 15 wt%). Morphological and micro structural properties of the prepared composites were studied via X-ray diffraction (XRD) and field-emission scanning electron microscope (FESEM), where the distribution of Ti₃C₂T_x in the Ti₃C₂T_x/EMA composites was confirmed. Thermal behaviors were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) investigations. The DSC analysis reveals that the % of crystallinity decreases from 11.06 with 1 wt% to 5.68 with 15 wt%, where Ti₃C₂T_x acts as an efficient nucleating agent. TGA data confirm the enhancement of the thermal stability of the composites upon increasing in Ti₃C₂T_x loading. The room temperature electrical and dielectric behavior of the studied composites were examined in the frequency range of 100 Hz–5 MHz. In this work, the 10 wt% of Ti₃C₂T_x loaded poly (ethylene-co-methyl acrylate) composite (EMA) showed higher dielectric permittivity (ε′ = 124.22) with lower dissipation loss (tan δ = 0.051) at 100 Hz among all weight percentages. The behavior of charge carriers in the prepared composites was studied by utilizing the impedance spectroscopy technique. The electrical parameters were calculated from the fitted Nyquist plots with a corresponding circuit model. I–V curves confirmed the conduction mechanisms of the composites. This beneficial enhancement in electrical properties recommends the composite can be utilized in flexible electronic storage devices.     

Structural and dielectric properties of CuO nanoparticles

The DC conduction and dielectric behaviour of copper oxide nanoparticles prepared by sol-gel method and sintered at 950 °C were studied in the temperature range of 200–526 K. The formation of single phase monoclinic CuO was confirmed by x-ray diffraction. Chemical composition of the CuO ceramic was investigated with X-ray photoelectron spectroscopy (XPS) technique. Although XRD analysis shows the formation of single phase CuO, XPS spectra revealed the presence of Cu³⁺ and Cu²⁺. Deviation from linearity ln (σ_DC) vs. 1/T plot at ~390 K was observed, which indicates that DC conduction in the CuO pellet is dominated by two different conduction mechanisms. The results obtained on AC conductivity indicate that AC conduction mechanism could be well explained by the multihopping model at low frequencies, while high frequency AC conductivity data can be described by small polaron tunnelling model. The dielectric relaxation mechanism in the CuO pellet was studied by impedance spectroscopy. It was found that while dielectric constant is an increasing function of temperature, it decreases with increasing frequency. The obtained impedance spectra indicated that the grain boundary effects and intergranular activities play a crucial role on the dielectric relaxation processes.     

Dielectric and Magnetodielectric Properties of R2NiMnO6 (R = Nd,Eu, Gd,Dy, and Y)

We have prepared polycrystalline R₂NiMnO₆ (R = Nd, Eu, Gd, Dy, and Y) samples by conventional solid‐state reaction and all the samples have shown monoclinic structure with P2₁/n space group. With the decrease in rare‐earth ionic size (<r_R>), the <Ni–O–Mn> bond angle decreases, correspondingly a decrease in ferromagnetic (FM) Curie temperature is noticed. In the dielectric measurement, the dielectric anomaly shifts to high temperature with the decrease in the <r_R> and shows no correlation with the FM Curie temperature and hints the absence of apparent magnetodielectric (MD) coupling. Appearance of multiple relaxations in the dielectric study suggests the electrical heterogeneity of the system. The dielectric/impedance analysis has revealed a close correlation between dc conductivity and the dielectrics; in fact, both dc resistivity and the grain relaxations follow the variable range hopping mechanism. The thermal activation of charge carriers at the grain boundary led to Maxwell–Wagner interfacial polarization. Finally, dielectric study under magnetic field showed no effect, it implies that not only the intrinsic MD is absent, but also the extrinsic MD due to the lack of magnetoresistance.     

Dielectric and impedance spectroscopic study of lithium doped potassium tantalum niobium oxide

The (K_0.90Li_0.10) (Nb_0.80Ta_0.20)_0.99Mn_0.01O₃ (KLTN) ceramic has been synthesized by the conventional solid-state reaction route. The Rietveld refinement X-Ray diffraction (XRD) patterns confirmed the single-phase orthorhombic crystal structure with space group Amm2. The frequency dependent electrical properties were examined by the complex dielectric and impedance spectroscopy in the temperature range 30 °C–500 °C where multiple structural phase transition was observed with high dielectric constant, low tangent loss and well saturated electric polarization. The shifting of the ferroelectric phase transition temperature by 30 °C in heating and cooling mode suggests the irreversible motion of the domains and domain walls and significant effects on grain boundaries on structural phase transition temperature. A series of phase transitions from orthorhombic to tetragonal (∼190 °C) and tetragonal to Cubic (∼390 °C in cooling and 420 °C in heating) have been obtained in the wide range of temperature. The different type of analogy such as Modulus formalism, complex impedance spectra, frequency dependent conductivity, the activation energy of charge carriers has been used to understand the microstructure-electrical properties relation.     

High Temperature Structural,Dielectric, and Ion Conduction Properties of Orthorhombic InVO4

Orthorhombic InVO₄ was prepared by solid‐state reaction method and characterized by powder X‐ray diffraction and scanning electron microscopy. The frequency‐dependent dielectric and conductivity properties were studied from 300 to 973 K by impedance spectroscopy. A significantly enhanced conductivity was observed at higher temperature whereas almost no conduction was observed below 723 K. Appreciable grain boundary conductivity was observed at higher temperature. The activation energies for grain and grain boundary conductivities are 0.87 and 1.28 eV, respectively. The relative permittivity of ~35 was observed in a wider range of frequencies and temperatures. The frequency dispersion dielectric studies indicated thermally activated hopping conduction process. The high temperature structural studies revealed no significant change in structural parameters except a gradual increasing trend in the unit cell parameters and amplitude of isotropic thermal parameters with increasing temperature.     

Dielectric properties of Sr0.5Ca0.5TiO3: x Pr3+ ceramics

The frequency dependent dielectric and AC conductivity properties of different concentrations of Pr³⁺ doped Sr_0.5Ca_0.5TiO₃ ceramics were investigated for the frequency range 100 Hz to 2 MHz at different temperatures. The morphology of the prepared samples was analyzed by using Field-Emission Scanning Electron Microscope images. The value of dielectric constant and dielectric loss decreases with increase in the frequency of the applied signal in all the samples. Also, the value of dielectric constant and dielectric loss decreased with doping of different concentrations of Pr³⁺ ions. The conductivity of the samples obeys Jonscher's power-law and shows a decrease with increasing doping concentration of Pr³⁺ ions. The higher value of real and imaginary part of impedance at lower frequency indicates the space charge polarization of the material and its absence at higher frequencies was confirmed from the low value of impedance at higher frequency region. The Cole- Cole parameters of the samples were calculated and the semi-circle observed indicates a single relaxation process and can be modeled by an equivalent parallel RC circuit. At lower frequency region, the value of dielectric constant and dissipation factor increases with increase in the temperature. Also the value of conductivity increases with temperature at high frequency region, due to the enhanced mobility of charge carriers.     

Phase evolution,dielectric and impedance spectroscopic study of SrNb2O6 columbite phase

Strontium niobate SrNb₂O₆ has been synthesized by columbite solid-state reaction method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and temperature as well as frequency dependence of dielectric and impedance study. XRD analysis indicates single phase formation of the compound with ∼180 nm crystallite size. Study of SEM micrographs pointed out that prepared material has good sinterability and enough density with homogeneous grain distribution. It was found that the magnitude of relative dielectric constant (?_r) was relatively high with low dielectric loss compared with reported columbite compounds. Impedance spectroscopy was used to characterize the electrical behavior of the compound. AC impedance spectrum results indicate that the relaxation mechanism of the material is temperature dependent and has bulk and grain boundary contribution in different temperature ranges.     

Origin of giant dielectric response in LiCuNb3O9 distorted perovskite ceramics

LiCuNb₃O₉ ceramics with the distorted cubic perovskite structure were prepared by a solid-state reaction method. The ceramic exhibited a very large value of permittivity (∼4.4 × 10⁴ at 100 kHz) at room temperature (∼300 K) and a low-temperature dielectric relaxation behaviour following the Arrhenius law. The origin of the giant dielectric response of the LiCuNb₃O₉ ceramics was correlated with the structure of the ceramics. The barrier layers in the grain boundaries and the mixed-valent structure of Cu⁺/Cu²⁺ were found to contribute to the giant permittivity of the ceramics and confirmed by X-ray spectroscopy and complex impedance spectroscopy analyses.     

Improved Energy Storage Properties Accompanied by Enhanced Interface Polarization in Annealed Microwave‐Sintered BST

Microwave‐sintering (MWS) technique was employed to fabricate dense (Ba_0.4Sr_0.6)TiO₃ (BST) ceramics. With respect to the high dielectric loss at room temperature, induced by the formation of oxygen defects during the MWS under vacuum atmosphere (?60 kPa), the as‐sintered samples were thermally annealed in air to reduce tanδ and recover the insulating performance. Accompanied by the decreased tanδ, the energy storage properties for annealed MWS BST were optimized, with increasing energy density (γ) from 0.77 to 1.15 J/cm³ and energy efficiency (η) from 60% to 82%. The lower oxygen vacancy concentrations were believed to account for the enhanced insulating characteristics of grain boundaries and contribute to the improved properties after annealing. Electrical characterization of grain and grain boundary by impedance spectroscopy demonstrated that the annealing preferentially modified the grain boundary. In addition, resistances extracted from the high temperature impedance analysis were found to be inadequate for evaluating the electrical characteristics of materials affected by extrinsic mechanisms, such as the interfacial polarization. For comparison, annealing effect on energy storage properties were also discussed for conventionally sintered BST.     

Colossal Permittivity in Microwave‐Sintered Barium Titanate and Effect of Annealing on Dielectric Properties

Colossal permittivity (ε′ = 301,484 at room temperature and 1 kHz) of barium titanate was induced in ceramics synthesized using the microwave sintering method. Three different sintering processes (conventional, spark plasma, and microwave) were performed to better understand colossal permittivity in sintered barium titanate. The dielectric permittivity measurements revealed that the appearance of colossal permittivity has strong dependence on the sintering temperature and atmosphere, and less on the grain size of the sintered ceramics. However, the as‐sintered barium titanate samples produced by microwave sintering show high dielectric loss (tanδ > 1) consistent with oxygen reduction during the microwave sintering process and consequent accumulation of oxygen vacancies and associated charge carriers at the grain boundary. Since the highly conductive state of as‐sintered ceramics precludes their use in dielectric applications, thermal annealing at different conditions was performed to recover insulating characteristics. Microwave‐sintered barium titanate with post annealing process (950°C for 12 h in air) showed low dielectric loss (tanδ = 0.045) at room temperature and 1 kHz, while still showing a much higher permittivity (ε′ = 36,055) than conventionally sintered barium titanate (ε′ = 3500).     

Influence of micro- and nanoparticles of zirconium oxides on the dielectric properties of CaCu3Ti4O12

This work presents the results of Zr oxide doping of a CaCu₃Ti₄O₁₂ (CCTO) ceramic prepared by a solid-state reaction. Different stoichiometries (ZrO and ZrO₂) and grain sizes (micro- and nanoparticles) were added as dopants at concentrations of 0.5 and 1.0 wt%. Zr-doping controls the grain size growth, leading to a reduction of the grain size as observed by scanning electron microscopy. For both dopant concentrations, all of the samples exhibited lower dielectric loss and a smaller dielectric constant than those of undoped CCTO. The sample doped with 0.5% of the non-stoichiometric ZrO exhibits a dielectric constant over 3200 and a dissipation factor of 0.02 at 1 kHz. The impedance spectroscopy analysis confirms that the decrease of dielectric loss is mainly due to an increase in resistivity at grain boundaries, which is attributed to the suppression of oxygen-loss promoted by dopants.     

Structural,capacitive and resistive characteristics of (Pb0.6Bi0.2Sm0.2)(Fe0.4Ti0.6)O3

Samarium substituted BiFeO₃–PbTiO₃ ceramic compound of (Pb_0.6 Sm_0.2 Bi_0.2)(Fe_0.4Ti_0.6)O₃ has been fabricated by mixed oxide solid state reaction method. The crystallographic structure from XRD study, distribution of grains from SEM micrograph, dielectric behavior, conductivity spectrum, impedance along with electric modulus spectroscopy have been illustrated. The experimental results corroborate the impact of samarium substitution in BiFeO₃–PbTiO₃ entailing reduced grain size, higher dielectric response with reasonably dielectric loss and enrichment in capacitive behavior with negative temperature coefficient of resistance. The temperature dependent conductivity spectra exhibit Arrhenius behavior, whereas the frequency dependent conductivity spectra follow the Jonscher universal power law. The basic correlated barrier hopping (CBH) model governs the charge transport mechanism in the fabricated compound. The exploration reveals the enriched dielectric and electrical behavior that endorse the samarium substituted material as a potential ceramic entity for designing electronic devices such as capacitors and ferroelectric accessories.     

Defect structure evolution and electrical properties of BaTiO3-based ferroelectric ceramics

Relaxor perovskite ferroelectric 0.1Bi(Zn_1/2Zr_1/2)O₃-0.9BaTiO₃(0.1BZZ-0.9BT) ceramics were successfully prepared, whose powders synthesized by the sol-gel process, with average grain size about 1.29 μm. 1.75 J/cm³ discharge energy density and good dielectric stability were obtained over a wide temperature range from 25°C to 140°C. The pulse discharge capability of 0.1BZZ-0.9BT ceramics was tested under different electric fields. The discharge time was 2.13 μs, which proved its ability to charge and discharge quickly. Complex impedance analysis and thermally stimulated depolarization current tests were applied to investigate the defect types and activation of 0.1BZZ-0.9BT ceramics. The evolution process of composite defects and oxygen vacancies profoundly affects the dielectric temperature stability of 0.1BZZ-0.9BT ceramics’ energy storage property.     

Effect of sintering temperature on structural and dielectric properties of Bi and Li co-substituted barium titanate ceramic

Bi and Li co-substituted barium titanate, Ba_0.98(Bi,Li)_0.02TiO₃ ceramic samples were sintered at different temperatures using conventional solid state sintering technique. X-Ray Diffraction patterns confirm tetragonal phase in all the sintered samples. Microstructure analysis using Scanning Electron Microscopy (SEM) reveals increasing grain sizes with an increase in sintering temperature. Dielectric spectroscopy performed in the range of 40 Hz to 2 MHz at room temperature shows that the dielectric constant increases with increasing sintering temperature, reaching a maximum of value of 1200 at 40 Hz where the dielectric loss observed was less than 0.02 for samples sintered at 1300 °C. Temperature dependant impedance spectroscopy data in the range of 30–300 °C was used to measure AC conductivity. The activation energy of grains was deduced through Arrhenius plots. Loss tangent at different frequencies for 1300 °C sintered samples was less than 0.1 over the entire temperature range. The high dielectric constant with a low dielectric loss at elevated temperatures make Ba_0.98(Bi,Li)_0.02TiO₃ samples suitable for Multi-Layer Ceramic Capacitors (MLCC)s used in high-temperature applications.     

Influence of Sr ions on the structure and dielectric properties of Cu/Nb Co-doped BaTiO3 ceramics

Sr-modified Cu/Nb co-doped BaTiO₃ ceramics were prepared using solid-state reactions and the structures and dielectric properties were studied. All the samples had single-phase perovskite structures with no detectable secondary phases. In the low-temperature range, the dielectric constant decreased as the Sr content increased in the high- and low-frequency ranges. Two dielectric constant plateaus accompanied by dielectric relaxation peaks were present in the loss curves, and the relaxation process deviated from the Arrhenius law at low temperatures. The dielectric constants of different plateaus were related to inhomogeneous structures such as grain interiors and grain boundaries. The polarization strength of the grain boundaries in the low-frequency range increased with the temperature and that of the grain interiors demonstrated paraelectric behaviour in high-temperature ranges. An analysis of the electric modulus spectra indicated a close relationship between the relaxation process and resistivity of the grains for high-frequency relaxation. The impedance spectra at high temperatures consist of three electrical responses, corresponding to the effects of grains, grain boundaries, and electrodes. The dielectric relaxation appeared in high temperature range was related to the electrical properties of the grain boundaries.