Enhancement in electrical and magnetodielectric properties of Ca‐ and Ba‐doped BiFeO3 polycrystalline ceramics

We carried out a comparative study on the electrical and magnetodielectric properties of polycrystalline BiFeO₃, Bi_0.9Ca_0.1FeO_2.95, Bi_0.9Ba_0.05Ca_0.05FeO_2.95, and Bi_0.9Ba_0.1FeO_2.95 ceramics. The two dielectric anomalies, near 25 K and 281 K, are observed for BiFeO₃. Interestingly, the anomaly near 25 K shifts towards a higher temperature above 60 K with Ca and/or Ba doping, attributed to the doping induced chemical pressure. In addition, the room temperature switchable magnetodielectric effect is witnessed for the doped BiFeO₃ compounds, due to the quadratic magnetoelectric coupling. This indicates the improved magnetoelectric coupling in BiFeO₃ with the Ca and Ba doping. This is essentially due to the enhanced magnetic ordering and reduced leakage current in BiFeO₃ after the doping.     

Defect structure‐electrical property relationship in Mn‐doped calcium strontium titanate dielectric ceramics

Ca_0.6Sr_0.4TiO₃ (CST) ceramics with different amounts of Mn dopant (0‐2.0 mol%) were prepared by solid‐state reaction method. The electric field and temperature stability of energy storage performance was found to be greatly enhanced with moderate doped level of 0.5 mol%. The dielectric loss‐frequency spectra revealed the existence and evolution of defect dipoles at elevated temperature, which was confirmed directly by electron paramagnetic resonance (EPR) spectra. The response of defect dipoles was characterized by thermally stimulated depolarization current (TSDC), where the activation energy and the concentration evolution of defect dipoles were calculated, with the highest values observed for 0.5% doped samples. The dissociation of defect dipoles and the movement of free were analyzed by high‐temperature impedance spectra analysis, with the activation energy of 1.04‐1.60 eV, and 0.5% doped samples also demonstrated the highest E_a. The relationship between microscopic defect structure and macroscopic electrical behavior was established in this work.     

Preparation, Characterization, and Microwave Properties of RETiNbO6 (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, and Yb) Dielectric Ceramics

Microwave ceramic dielectric resonators (DRs) based on RETiNbO₆ (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, and Yb) have been prepared using the conventional solid-state ceramic route. The DR samples are characterized using XRD and SEM methods. The microwave dielectric properties are measured using resonant methods and a net work analyzer. The ceramics based on Ce, Pr, Nd, and Sm have dielectric constants in the range 32–54 and positive coefficient of thermal variation of resonant frequency (τ_f). The ceramics based on Gd, Tb, Dy, Y, and Yb have dielectric constants in the range 19–22 and negative τ_f.     

Inversion domain boundaries in Mn and Al dual‐doped ZnO: Atomic structure and electronic properties

The atomic and electronic structures of inversion domain boundaries in Mn‐Al dual‐doped ZnO (Zn_0.89Mn_0.1Al_0.01O) have been investigated. Using atomic‐resolution scanning transmission electron microscopy, a head‐to‐head c‐axis configuration and cation stacking sequence of αβαβ|γ|αβαβ along the c‐axis were observed at the basal‐plane inversion domain boundary. Energy‐dispersive X‐ray spectroscopy and electron energy‐loss spectroscopy revealed significant localization of Mn and minor localization of Al at the basal‐plane inversion domain boundary. Based on experimental findings, a Mn‐doped basal‐plane inversion domain boundary slab model was constructed and refined by first principles calculations. The model is in agreement with atomic‐resolution images. The local electronic density of states of the slab model basal‐plane inversion domain boundary shows a hybridization of the Mn d and O p states within the valence band and localized Mn d states in the conduction band. The thermoelectric properties of Zn_0.99?xMn_xAl_0.01O ceramics have been reported in a previous work. In this work, the effects of inversion domain boundaries on the thermoelectric properties are discussed. In comparison to Zn_0.99?xMn_xAl_0.01O ceramics with x≤0.05, inversion domain boundaries in Zn_0.89Mn_0.1Al_0.01O caused thermal and electrical conductivity reduction due to interface scattering of phonons and electrons. The Seebeck coefficient increased, suggesting electron filtering at inversion domain boundaries.     

Immobilization of metal nanoparticles on polyurethane membranes: synthesis and electrical properties

Ag and Cu nanoparticles were immobilized into crosslinked polyurethane (PU) membranes by taking advantage of the swelling characteristics of the membranes. The formation, shape and size of the nanoparticles inside the post‐swollen PU membranes were observed by transmission electron microscopy and atomic force microscopy. X‐ray diffraction indicated the presence of the pure Ag and Cu embedded in the amorphous PU matrix. Because of their compatibility, the nanoparticles improved the thermal stability and increased the glass transition temperature of PU. The membranes exhibited interesting conducting behavior with increasing temperature. The metal immobilization increased the ionic conductivity which further increased with temperature, with an activation energy of 0.15 eV indicating a thermally activated conduction mechanism. The optical and electrical properties of these starch‐based membranes can be utilized in the development of novel sensors for biomedical applications. Copyright © 2012 Society of Chemical Industry     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Frequency independent‐dependent conductivity and dielectric properties of some ionomers

The preparation and physical properties of some ionomers have been investigated. The addition of CH₃I significantly improved the conductivity of the ionomers. At room temperature, the highest ionic conductivity value was found to be 4.93 10⁻⁸ S cm⁻¹ in the I4 ionomer. The conductivity data do not obey the Arrhenius law and the non‐linearity indicates ionic transport. The alternating current conductivity parameters and dielectric constants of the ionomers were determined. Copyright © 2005 Society of Chemical Industry     

Room‐temperature‐densified Li2MoO4 ceramic patch antenna and the effect of humidity

A patch antenna was realized utilizing a Li₂MoO₄ disk fabricated by a room‐temperature densification method, where the densification takes place during pressing. Therefore, the size of the ceramic can easily be managed by controlling the mold dimensions, making this method advantageous for patch antenna design. The antenna showed reasonably good performance. A relative humidity of 80% lowered the resonant frequency and reduced the efficiency of the antenna. Use of a conformal coating reduced the changes and speeded up their reversibility. The results show that the room‐temperature densified Li₂MoO₄ ceramics are feasible for use under high humidity with a silicone coating.     

Remarkable piezoelectricity and stable high‐temperature dielectric properties of quenched BiFeO3–BaTiO3 ceramics

Effects of quenching process on dielectric, ferroelectric, and piezoelectric properties of 0.71BiFeO₃?0.29BaTiO₃ ceramics with Mn modification (BF–BT?xmol%Mn) were investigated. The dielectric, ferroelectric, and piezoelectric properties of BF–BT?xmol%Mn were improved by quenching, especially to the BF–BT?0.3 mol%Mn ceramics. The dielectric loss tanδ of quenched BF–BT?0.3 mol%Mn ceramics was only 0.28 at 500°C, which was half of the slow cooling one. Meanwhile, the remnant polarization P_r of quenched BF–BT?0.3 mol%Mn ceramics increased to 21 μC/cm². It was notable that the piezoelectric constant d₃₃ of quenched BF–BT?0.3 mol%Mn ceramics reached up to 191 pC/N, while the T_C was 530°C, showing excellent compatible properties. The BF–BT?xmol%Mn system ceramics showed to obey the Rayleigh law within suitable field regions. The Rayleigh law results indicated that the extrinsic contributions to the dielectric and piezoelectric responses of quenched BF–BT?xmol%Mn ceramics were larger than the unquenched ceramics. These results presented that the quenched BF–BT?xmol%Mn ceramics were promising candidates for high‐temperature piezoelectric devices.     

YCrO3/Al2O3 Core‐Shell Design: The Effect of the Nanometric Al2O3‐Shell on Dielectric Properties

We report a novel strategy to improve the dielectric properties of the biferroic YCrO₃ ceramic compound through interface conduction control by means of an insulating Al₂O₃ using a core‐shell design. The YCrO₃ particles were covered with several layers of insulating Al₂O₃ using the atomic layer deposition technique to produce the core‐shell structure. TEM images reveal homogeneous and well‐defined Al₂O₃ coatings of ~8, ~60, and ~130 nm thickness. XRD shows the Al₂O₃‐shell to be amorphous. The dielectric characteristics of the sintered nano‐composite were investigated in the 100 Hz–1 MHz frequency range and temperature between 300 and 580 K. As the Al₂O₃‐shell thickness covering the YCrO₃ particles is increased, a decrease of the dielectric permittivity, loss tangent and AC conductivity values was found in the whole range of temperatures and frequencies. Furthermore, the rounded hysteresis loop, typical of conductive ceramic is restored as the insulating Al₂O₃ layer becomes thicker. This behavior is explained because the insulating Al₂O₃‐shell acts as internal barrier layer localizing the surface charges on the sintered grain boundaries. This fact was confirmed by Electron Beam Induced Current technique where a clear contrast at the grain boundaries confirms the charge localization at the YCrO₃/Al₂O₃ interface. These results also reveal that the Al₂O₃‐shell induces another conductive mechanism when the insulating Al₂O₃ layer becomes thicker. Nonetheless, this new strategy is an effective approach to suppress the parasitic conductivity in polycrystalline multiferroic ceramics and increasing thus the multifuncionality.     

Decisive role of mixed‐valence structure in colossal dielectric constant of LaFeO3

The role of mixed‐valence structure in colossal dielectric constant (CDC) behavior has been investigated in LaFeO₃ ceramics by tuning the ratio of Fe²⁺/Fe³⁺ through substituting Al for Fe. The ratio of Fe²⁺/Fe³⁺ is decreased gradually from 1.0 to 0.0 by increasing the concentration of Al³⁺. Two clear‐cut correlations have been found: (i) the relationship between the CDC behavior and the ratio of Fe²⁺/Fe³⁺ follows an exponential function and (ii) the activation energy of the polaron relaxation is proportional to , where is the intrinsic dielectric constant. These findings underscore the role of the mixed‐valence structure in CDC behavior and suggest that adjusting the mixed‐valence structure through doping/alloying can be a promising strategy to achieve superior CDC behavior in transition‐metal oxides.     

Porosity‐dependent properties of Nb‐doped Pb(Zr,Ti)O3 ceramics

In the present work, it is shown how the controlled porosity can be exploited to obtain a compromise between a reduced permittivity down to a few hundreds and maintaining a high tunability level as in the dense material, to fulfill requirements for tunable applications. Nb‐doped Pb(Zr,Ti)O₃ ceramics with porosity in the range 5%‐30% have been prepared by direct sintering method. X‐ray diffraction analysis and Rietveld refinement indicated a co‐existence of tetragonal and monoclinic phases in the porous ceramics. Dielectric properties revealed a gradual reduction in permittivity when increasing the porosity level, while maintaining low dielectric losses below 3%. The ferroelectric switching behavior is also influenced by the porosity level: a continuous reduction in the saturation and remnant polarization is observed with increasing porosity. The nonlinear dielectric properties of all the investigated ceramics preserve a high level of tunability in comparison with one of the dense material, irrespective of the porosity level, while zero field permittivity was decreased below 1000. An optimum behavior is found for the ceramic sample with 25% porosity, which shows a high tunability, smaller losses, and moderate dielectric constant (ε ~600).     

Improved dielectric properties in A′‐site nickel‐doped CaCu3Ti4O12 ceramics

The improved dielectric properties and voltage‐current nonlinearity of nickel‐doped CaCu₃Ti₄O₁₂ (CCNTO) ceramics prepared by solid‐state reaction were investigated. The approach of A′‐site Ni doping resulted in improved dielectric properties in the CaCu₃Ti₄O₁₂ (CCTO) system, with a dielectric constant ε′≈1.51×10⁵ and dielectric loss tanδ≈0.051 found for the sample with a Ni doping of 20% (CCNTO20) at room temperature and 1 kHz. The X‐ray photoelectron spectroscopy (XPS) analysis of the CCTO and the specimen with a Ni doping of 25% (CCNTO25) verified the co‐existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺. A steady increase in ε′(f) and a slight increase in α observed upon initial Ni doping were ascribed to a more Cu‐rich phase in the intergranular phase caused by the Ni substitution in the grains. The low‐frequency relaxation leading to a distinct enhancement in ε′(f) beginning with CCNTO25 was confirmed to be a Maxwell‐Wagner‐type relaxation strongly affected by the Ni‐related phase with the formation of a core‐shell structure. The decrease of the dielectric loss was associated with the promoted densification of CCNTO and the increase of Cu vacancies, due to Ni doping on the Cu sites. In addition, the Ni dopant had a certain effect on tuning the current‐voltage characteristics of the CCTO ceramics. The present A′‐site Ni doping experiments demonstrate the extrinsic effect underlying the giant dielectric constant and provides a promising approach for developing practical applications.     

Influence of B‐Site Disorder on the Properties of Unpoled Bi1/2Na1/2TiO3‐0.06Ba(ZrxTi1‐x)O3 Piezoceramics

The influence of B‐site disorder on the dielectric, microstructural, and structural characteristics of unpoled, lead‐free (Bi_1/2Na_1/2)TiO₃‐0.06Ba(Zr_xTi_1‐x)O₃ piezoelectric ceramics with x = 0.02, 0.10, and 0.15 was investigated. The low and medium doping level introduced a stabilization of polar nanoregions reflected in the shift of the dispersive permittivity anomalies to higher temperatures and the development of lamellar rhombohedral domains embedded in the prevalent tetragonal nanodomain matrix. For higher Zr level, the regions of lamellar domains remain, but the dielectric characteristics indicate a reduction in the previous stabilization effect. This behavior is rationalized by a reduction in the correlation length due to the increasing amount of nonpolar sample volume with increasing Zr addition.     

Enhanced magnetic and dielectric properties of Ti‐doped YFeO3 ceramics

Polycrystalline YFeO₃ (YFO) and YFe_1?(4/3)xTi_xO₃(YFTO) ceramics were prepared using the powder synthesized from the sol‐gel route. X‐ray diffraction analyses of the polycrystalline ceramics revealed the crystallization of the phase in orthorhombic crystal structure associated with the space group Pnma. The magnetization versus magnetic field hysteresis loops were obtained at room temperature for YFO and YFTO ceramics. The magnetic property changes from weak ferromagnetic in YFO to ferromagnetic in YFTO ceramics. The dielectric constant recorded at room temperature for YFTO ceramics was six times higher than that of YFO, whereas the dielectric loss gets reduced to 0.06 from 0.3 for YFO at 1 kHz. Impedance spectroscopy study carried out on YFO and YFTO ceramics confirmed the existence of non‐Debye‐type relaxation. Observed single semicircle in Z′ vs ?Z′′ plot established the incidence of intrinsic (bulk) effect and ruled out any grain boundary or electrode effects. The mechanism for the dielectric relaxation and electrical conduction process observed in YFO and YFTO ceramics was discussed by invoking electric modulus formalisms. Activation energy obtained by ac conductivity study suggested that the conduction process in YFO was linked up with the existence of the polaron and oxygen vacancies, whereas only oxygen vacancies contribute to the conduction process in YFTO ceramics.     

Li2MoO4‐based composite ceramics fabricated from temperature‐ and atmosphere‐sensitive MnZn ferrite at room temperature

The first magnetic ceramic composites manufactured, using the room‐temperature densification method are reported. The samples were prepared at room temperature using Li₂MoO₄ as a matrix and MnZn ferrite with loading levels of 10‐30 vol‐% followed by postprocessing at 120°C. The method utilizes the water solubility of the dielectric Li₂MoO₄ and compression pressure instead of high temperatures typical of conventional solid‐state sintering. Hence, composite manufacturing using temperature‐ and atmosphere‐sensitive materials is possible without special conditions. This was demonstrated with MnZn ferrite, which is prone to oxidation when heat treated in air. Samples manufactured with room‐temperature densification showed no signs of reactivity during processing, whereas reference samples sintered at 685°C suffered from oxidation and formation of an additional reaction phase. The densities achieved with different loading levels of MnZn ferrite with both methods were very similar. Measurements up to 1 GHz showed relatively high values of relative permittivity (21.7 at 1 GHz) and permeability (2.6 at 1 GHz) with 30 vol‐% loading of MnZn ferrite in the samples manufactured by room‐temperature densification. In addition, pre‐granulation is proposed to improve the processability of the composite powders in room‐temperature densification.     

Synergistically optimizing electrical and thermal transport properties of Bi2O2Se ceramics by Te‐substitution

Bi₂O₂Se oxyselenides, characterized with intrinsically low lattice thermal conductivity and large Seebeck coefficient, are potential n‐type thermoelectric material in the mediate temperature range. Given the low carrier concentration of ~10¹⁵ cm^?3 at 300 K, the intrinsically low electrical conductivity actually hinders further enhancement of their thermoelectric performance. In this work, the isovalent Te‐substitution of Se plays an effective role in narrowing the band gap, which notably increases the carrier concentration to ~10¹⁸ cm^?3 at 300 K and the electron conduction activation energy has been lowered significantly from 0.33 to 0.14 eV. As a consequence, the power factor has been improved from 104 μW·K^?2·m^?1 for pristine Bi₂O₂Se to 297 μW·K^?2·m^?1 for Bi₂O₂Se_0.96Te_0.04 at 823 K. Meanwhile, the suppressed lattice thermal conductivity derives from the introduced point defects by heavier Te atoms. The gradually decreased phonon mean free path reflects the increasingly intense phonon scattering. Ultimately, the ZT value attains 0.28 for Bi₂O₂Se_0.96Te_0.04 at 823 K, an enhancement by a factor of ~2 as compared to that of pristine Bi₂O₂Se. This study has demonstrated that Te‐substitution of Se could synergistically optimize the electrical and thermal properties thus effectively enhancing the thermoelectric performance of Bi₂O₂Se.     

The illumination intensity and applied bias voltage on dielectric properties of au/polyvinyl alcohol (Co,Zn‐doped)/n‐Si Schottky barrier diodes

The Au/polyvinyl alcohol (PVA) (Co, Zn‐doped)/n‐Si Schottky barrier diodes (SBDs) were exposed to various illumination intensities. Illumination effect on the dielectric properties has been investigated by using capacitance–voltage (C–V) and conductance–voltage (G/ω–V) characteristics at 1 MHz and room temperature. The values of dielectric constant (ε′), dielectric loss (ε″), loss tangent (tanδ), electric modulus (M′ and M″), and AC electrical conductivity (σ_AC) were found strongly intensity dependent on both the illumination levels and applied bias voltage especially in depletion and accumulation regions. Such bias and illumination dependency of these parameters can be explained on the basis of Maxwell–Wagner interfacial polarization and restructuring and reordering of charges at interface states. In addition, the ε′–V plots also show an intersection feature at ～ 2.8 V and such behavior of the ε′–V plots appears as an abnormality compared with the conventional behavior of an ideal SBD. The obtained results revealed that illumination intensity enhances the conductivity of Au/PVA(Co, Zn‐doped)/n‐Si SBD. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sintering behavior,structural phase transition,and microwave dielectric properties of La1‐xZnxTiNbO6‐x/2 ceramics

La_1‐xZn_xTiNbO_6‐x/2 (LZTN‐x) ceramics were prepared via a conventional solid‐state reaction route. The phase, microstructure, sintering behavior, and microwave dielectric properties have been systematically studied. The substitution of a small amount of Zn²⁺ for La³⁺ was found to effectively promote the sintering process of LTN ceramics. The corresponding sintering mechanism was believed to result from the formation of the lattice distortion and oxygen vacancies by means of comparative studies on La‐deficient LTN ceramics and 0.5 mol% ZnO added LTN ceramics (LTN+0.005ZnO). The resultant microwave dielectric properties of LTN ceramics were closely correlated with the sample density, compositions, and especially with the phase structure at room temperature which depended on the orthorhombic‐monoclinic phase transition temperature and the sintering temperature. A single orthorhombic LZTN‐0.03 ceramic sintered at 1200°C was achieved with good microwave dielectric properties of ε_r~63, Q×f~9600 GHz (@4.77 GHz) and τ_f ~105 ppm/°C. By comparison, a relatively high Q × f~80995 GHz (@7.40 GHz) together with ε_r~23, and τ_f ~?56 ppm/°C was obtained in monoclinic LTN+0.005ZnO ceramics sintered at 1350°C.