Dielectric properties of Pb(Zn<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-introduced (Ba,Pb)TiO<Subscript>3</Subscript> ceramic system

Ceramic powders of the Pb(Zn_1/3Ta_2/3)O₃-introduced BaTiO₃–PbTiO₃ system were prepared using a B-site precursor method. Perovskite formation tendencies of the system compositions were determined by X-ray diffraction. Weak-field low-frequency dielectric properties of the sintered ceramics were investigated. Dielectric constant spectra were further analyzed in terms of diffuseness. Internal microstructures of the ceramics were also examined.     

Dielectric responses in Mg<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>-replaced Pb[(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>),Ti]O<Subscript>3</Subscript> ceramics

Octahedral lattice sites of Pb[(Zn_1/3Nb_2/3),Ti]O₃ were replaced by 20 at.% Mg_1/3Ta_2/3 complex to enhance perovskite development, especially at Pb(Zn_1/3Nb_2/3)O₃-rich compositions. Resultant changes in the perovskite formation and associated dielectric responses were investigated. A perovskite structure was identified at Pb(Zn_1/3Nb_2/3)O₃-rich compositions by X-ray diffraction, although the development was rather incomplete. Phase transition modes in the dielectric constant spectra changed from diffuse to sharp ones, regardless of the introduction of Mg_1/3Ta_2/3. Dielectric maximum temperatures of the ceramics shifted linearly with the compositional change.     

Phase developments in Pb(Mg<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> and Pb(Zn<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> via B-site precursor route

Phase formation stages of MgWO₄ and ZnWO₄ (precursor compositions for following steps) were investigated by monitoring the reactions of oxide chemicals at various temperatures. Developed phases were examined by using X-ray diffraction (XRD). Successive attempts were also conducted for Pb(Mg_1/2W_1/2)O₃ (PMW) and Pb(Zn_1/2W_1/2)O₃ (PZW) by reacting PbO with the precursor compounds. Stages of phase development in the two compositions were also analyzed. The results are compared with those of another tungsten-containing perovskite Pb(Fe_2/3W_1/3)O₃ (PFW) and its B-site precursor Fe₂WO₆. After PbO addition to the precursor powders, a perovskite phase formed directly (i.e., without any intermediate phases) in the case of PMW. For PbO + ½ZnWO₄, in contrast, the decomposition of ZnWO₄ and preferential reaction with PbO resulted in Pb₂WO₅ and ZnO, instead of the perovskite PZW.     

Dielectric and magnetic properties of Ca(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>/NiZn ferrite composites

Dense Ca(Zn_1/3Nb_2/3)O₃/NiZn ferrite composites with homogeneously fine microstructures were prepared through conventional solid-state method. The powder XRD patterns confirm the coexistence of the two phases. The dielectric properties in the low frequency range (100 Hz–1 MHz) follow the rule of Maxwell–Wagner interfacial polarization. The dielectric and magnetic properties in the high frequency range (10 MHz–1 GHz) are also reported. The results show that this kind of magnetic–dielectric composites could be used in high-frequency communications for the capacitor-inductor integrating devices such as electromagnetic interference filters and antennas.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Structural and electrical properties of Ba(Fe<Subscript>1/3</Subscript>Nb<Subscript>1/3</Subscript>Ta<Subscript>1/3</Subscript>)O<Subscript>3</Subscript> perovskite

Ba(Fe_1/3Nb_1/3Ta_1/3)O₃ (BFNT) perovskite compound (phase purity>99%) was synthesized by conventional ceramic preparation method. XRD, microstructure, impedance spectroscopy and ac conductivity properties were analyzed in this study. BFNT compound has a cubic crystal structure, having grain size of 0.31 μm. This compound has shown normal ferroelectric behaviour but not obeying Curie-Weiss law. The impedance and electrical studies have been performed as a function of frequency and temperature. Impedance as a function of frequency revealed single relaxation process. The impedance spectroscopic plots exhibit the major response due to grains with partial contribution from the grain boundary and negligible electrode effect. Complex impedance plot showed data points lying on a single semicircle, implying the response originated from a single capacitive element corresponding to the bulk grains. Also, the centre of semicircle lies below the real axis indicating non-Debye type relaxation. Relaxation time was calculated from Z″_max of Cole–Cole plots. It is observed that conduction is due to hopping of charge carriers. Activation energies were computed from the Arrhenius plots of the sample.     

Microwave dielectric properties of Bi(Sc<Subscript>1/3</Subscript>Mo<Subscript>2/3</Subscript>)O<Subscript>4</Subscript> ceramics for LTCC applications

A novel microwave dielectric ceramics Bi(Sc_1/3Mo_2/3)O₄ with low firing temperature were prepared via the solid reaction method. The specimens have been characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy and DC conductivity. The Bi(Sc_1/3Mo_2/3)O₄ ceramics showed B-site ordered Scheelite-type structure with space group C2/c. Raman analysis indicated that prominent bands were attributed to the normal modes of vibration of MoO₄ ^2? tetrahedra. The dielectric loss of Bi(Sc_1/3Mo_2/3)O₄ ceramics can be depended strongly the bulk conductivity by DC measurement. The superior microwave dielectric properties are achieved in the Bi(Sc_1/3Mo_2/3)O₄ ceramic sintered at 875 °C/4 h, with dielectric constant?~?25, Q?×?f ~?51,716 GHz at 6.4522 GHz and temperature coefficient of resonance frequency ~???70.4 ppm/°C. It is a promising microwave dielectric material for low-temperature co-fired ceramics technology.     

Preparation and electrical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> solid solutions

Ceramic samples of lead magnesium niobate (PMN) and (1 ? x)Pb(Mg_1/3Nb_2/3)O₃?xPbTiO₃ (PMN-PT) solid solutions with x = 0, 0.05, 0.10, and 0.30 have been prepared by solid-state reactions, and their structural, electrical, and piezoelectric properties have been studied using x-ray diffraction, Rietveld profile analysis, impedance spectroscopy, and the resonance/antiresonance method. The results indicate that the use of nonstoichiometric columbite niobates enables the synthesis of phase-pure PMN and PMN-PT.     

Preparation and phase formation of perovskite Pb(Ni<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> by a reaction-sintering process

Pyrochlore-free Pb(Ni_1/3Nb_2/3)O₃ perovskite ceramics produced by a simple and effective reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂ and Nb₂O₅ was pressed and sintered directly into PNN ceramics. Density of 98.5% of theoretical value was obtained after sintered at 1230 °C for 2 h in air. 99.3% of theoretical density was obtained after sintered at 1,200 °C for 2 h in PbO compensated atmosphere. PNN ceramic with dielectric constant 1,680 at 25 °C and 1 kHz has been obtained.     

Synthesis and characterization of pseudo-ternary Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ferroelectric ceramics via a B-site oxide mixing route

Perovskite phase formation and dielectric/ferroelectric properties of the pseudo-ternary Pb(Fe_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ (PFN-PZ-PT) ferroelectric ceramics have been investigated as promising materials for multi-layer ceramic capacitors. Complete solid solution with pure perovskite phase can be formed in this system in the whole composition range studied using conventional solid-state reaction method via a B-site oxide mixing route. Crystal lattice of the ceramics obtained shrinkages with the increase of the concentration of Pb(Fe_1/2Nb_1/2)O₃ (PFN) and expands with the increase of the content of PbZrO₃ (PZ). With the increase of the concentration of PbTiO₃ (PT), crystal structure of PFN-PZ-PT changes from pseudo-cubic ferroelectric phase to tetragonal one while retains the fraction of PFN as constant. A morphotropic phase boundary (MPB) forms at the composition of 42 mol% PT regardless of whatever concentration of PFN, and the content of PFN affects little on the composition of MPB. The preliminary phase diagram of the PFN-PZ-PT system is determined by X-ray diffraction (XRD) measurements combining with dielectric/ferroelectric characterization. Dielectric measurements indicate that the value of dielectric maximum (ɛ_m) and the temperature where ɛ_m appears (T_m) increase with the increase of the concentration of PT. However, PFN exhibits opposite effects, i.e., ɛ_m increases with the increase of the concentration of PFN accompanied by the decrease of T_m.     

Strain-induced artificial multiferroicity in Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript>/Pb(Fe<Subscript>0.66</Subscript>W<Subscript>0.33</Subscript>)O<Subscript>3</Subscript> layered nanostructure at ambient temperature

Layered nanostructures (LNs) of the commercial ferroelectric Pb(Zr_0.53Ti_0.47)O₃ (PZT) and the natural ferroic relaxor Pb(Fe_0.66W_0.33)O₃ (PFW) were fabricated with a periodicity of PZT/PFW/PZT (~5/1/5 nm, thickness ~250 nm) on MgO substrates by pulsed laser deposition. The dielectric behavior of these LNs were investigated over a wide range of temperatures and frequencies, observing Debye-type relaxation with marked deviation at elevated temperatures (>400 K). High dielectric constant and very low dielectric loss were observed below 100 kHz and 400 K, whereas the dielectric constant decreases and loss increases with increase in frequency, similar to relaxor ferroelectrics. Asymmetric ferroelectric hysteresis loops across UP and DOWN electric field were observed with high remanent polarization (P_r) of about 33 μC/cm². High imprint (~5–7 V across 250 nm thin films) were seen in ferroelectric hysteresis that may be due to charge accumulation at the interface of layers or significant amount of strain (~3.21) across the layers. Room temperature ferromagnetic hysteresis was observed with remanent magnetization 5.32 emu/cc and a coercive field of ~550 Oe. Temperature and field dependent leakage current densities showed very low leakage ~10⁻⁷–10⁻⁵ A/cm² over 500 kV/cm. We observed imprint in hysteresis that may be due to charge accumulation at the interface of layers or active role of polar nano regions (PNRs) situated in the PFW regions.     

Effects of lanthanum modification on dielectric properties of Pb(Zr<Subscript>0.90</Subscript>,Ti<Subscript>0.10</Subscript>)O<Subscript>3</Subscript> ceramics: enhanced antiferroelectric stability

Lanthanum modified lead zirconate titanate ceramics with lanthanum content changing from 2 to 6 at% La and a Zr/Ti ratio of 90/10 (PLZT x/90/10) have been analyzed by using X-ray diffraction, dielectric response, differential scanning calorimetry, and ferroelectric hysteresis. An antiferroelectric state was found to be stabilized, whereas the long-range ferroelectric state was disrupted by lanthanum substitution on the lead sites. A ferroelectric state is shown to be stable over an antiferroelectric state for low lanthanum contents in a wide temperature range, where both phases coexist. With the increase of the lanthanum concentration, the long-range coherency of the ferroelectric state is suppressed, i.e., the temperature range of the ferroelectric state stability decreased, disappearing for x > 3 at% La.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Fabrication of thin films by sputtering deposition using (Ba<Subscript>0.3</Subscript>Sr<Subscript>0.7</Subscript>)(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramic as target

Dielectric ceramic thin films were fabricated on SiO₂ (110) substrates by the radio frequency (RF) magnetron sputtering method using (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ microwave dielectric ceramic as target. The microstructure, components, and morphology of the thin films were investigated thoroughly. The results reveal that the experimental conditions can affect the growth of the thin films significantly. The main phases of the thin films are Ba_0.5Sr_0.5Nb₂O₆ and Ba_0.27Sr_0.75Nb₂O_5.78, which are of different composition from that of the ceramic target due to Zn loss. The thin films are polycrystalline with high-quality crystalline and are made up of dense rod-like structures. The growth mechanism of the thin films is discussed in particular.     

Structural and electrical properties of Ba(Sb<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramic

Lead-free perovskite Ba(Sb_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1200 °C/5 h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were determined from the experimental results using FullProf software whereas crystallite size and lattice strain were estimated from Williamson–Hall approach. XRD analysis of the compound indicated the formation of a single-phase monoclinic structure with the space group P2/m. EDAX and SEM studies were carried out to evaluate the quality and purity of the compound. Dielectric study revealed the frequency-dependent dielectric anomaly. To find a correlation between the response of the real system and idealized model circuit composed of discrete electrical components, the model fittings were presented using the impedance data. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(Sb_1/2Nb_1/2)O₃. The ac conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy of the compound.     

Dielectric properties,microstructure and diffuse transition of Al-doped Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> ceramics

Pure and Al-doped BaZr_0.2Ti_0.8O₃ (short for BZT) ceramics are prepared via the conventional solid state reaction method. The microstructures, dielectric properties, and diffuse transition of Al-doped BaZr_0.2Ti_0.8O₃ ceramics were investigated. These results indicate that aluminum ions enter the unit cell maintaining the perovskite structure of solid solution. The addition of aluminum leads to the change of the Curie temperature. The dielectric loss of the Al-doped BZT ceramics is higher than that of pure BZT ceramics, and increases as aluminum content increases. The diffuseness of the phase transition of Al-doped BZT ceramics weakens with the increasing of aluminum content. There is no obvious frequency dispersion around the dielectric constant peaks for Al-doped BZT ceramics. The coercive electric field (E _C) increases as Al content increases, and the remanent polarization (P _r) of Al-doped BZT ceramics is lower than that of pure BZT ceramics.