High-temperature impedance spectroscopy of BaFe0.5Nb0.5O3 ceramics doped with Bi0.5Na0.5TiO3

Bi_0.5Na_0.5TiO₃ (BNT)-doped BaFe_0.5Nb_0.5O₃ (BFN) ceramics were synthesized by a two-step solid-state reaction. Temperature dependence of dielectric properties measured at different frequencies was investigated over broad temperature and frequency ranges. Impedance spectroscopy and universal dielectric response were employed to study the relaxation behavior and conductivity mechanism of the ceramics in a frequency range from 40 Hz to 100 MHz and a temperature range from 300 K to 800 K. The complex plane impedance data revealed the bulk and grain boundary contributions toward conductivity processes in the form of semicircular arcs. The high-temperature conductivity of ceramics is attributable to thermally activated second ionized oxygen vacancy.     

Anisotropic electrical properties of Bi0.5(Na0.75K0.25)0.5TiO3 ceramics fabricated by reactive templated grain growth (RTGG)

We have fabricated lead-free Bi_0.5(Na_0.75K_0.25)_0.5TiO₃ (BNKT) ceramics by a conventional process (CP) and reactive templated grain growth (RTGG) methods. The effect of grain orientation on structure, dielectric, complex impedance and electrical properties was investigated. The phase formation and grain morphology of BNKT ceramics were examined by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. High dielectric constant and low dielectric loss was observed for grain oriented (textured) BNKT ceramics. Complex impedance, temperature dependent ac and dc conductivity were performed to explore the conduction behavior of the prepared BNKT ceramics.     

Structure, ferroelectric and piezoelectric properties of (Bi1−x−yNa0.925−x−yLi0.075)0.5BaxSryTiO3 lead-free piezoelectric ceramics

Lead-free multi-component ceramics (Bi_1−x−yNa_{0.925−x−y}Li_0.075)_0.5Ba_xSr_yTiO₃ have been prepared by an ordinary sintering technique and their structure and electrical properties have been studied. All the ceramics can be well-sintered at 1100 °C. X-ray diffraction patterns shows that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) is formed at 0.04 < x < 0.08. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the coercive field E_C of the ceramics decreases greatly and the remanent polarization P_r of the ceramics increases significantly after the formation of the multi-component solid solution. Due to the MPB, lower E_C and higher P_r, the piezoelectricity of the ceramics is greatly improved. For the ceramics with the compositions near the MPB (x = 0.04–0.08 and y = 0.02–0.04), piezoelectric coefficient d₃₃ = 133–193 pC/N and planar electromechanical coupling factor k_P = 16.2–32.1%. The depolarization temperature T_d reaches a minimum value near the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T_d.     

Synthesis, phase and microstructure characteristics of Pb(Zr0.52Ti0.48)O3–(Bi3.25La0.75)Ti3O12 ceramics

Ceramics with formula (1 − x)Pb(Zr_0.52Ti_0.48)O₃–x(Bi_3.25La_0.75)Ti₃O₁₂ (when x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were prepared by a solid-state mixed-oxide method and sintered at temperatures between 950 °C and 1250 °C. It was found that the optimum sintering temperature was 1150 °C at which all the samples had densities at least 95% of theoretical values. Phase analysis using X-ray diffraction indicated the existence of BLT- as well as PZT-based solid solutions with corresponding lattice distortion. Scanning electron micrographs of ceramic surfaces showed a plate-like structure in BLT-rich phase while the typical grain structure was observed for PZT-rich phase. The grain sizes of both pure BLT and PZT ceramics were found to decrease as the relative amount of the other phase increased. This study suggested that tailoring of properties of this PZT–BLT system was possible especially on the BLT-rich side due to its large solubility limit.     

Structure and electrical properties of Bi0.5(Na, K)0.5TiO3−BiGaO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃− yBiGaO₃ have been fabricated by an ordinary sintering technique, and their structure and electrical properties and depolarization temperature have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ and BiGaO₃ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure. An obvious change in microstructure with increasing concentration of Bi_0.5K_0.5TiO₃ and BiGaO₃ was observed. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p of the ceramics attain maximum values of 165 pC/N and 0.346 at y = 0.01(x = 0.18) and x = 0.21(y = 0.01), respectively. The temperature dependence of dielectric constant indicates an obvious relaxor characteristic with strong frequency dependence of dielectric constant. The depolarization temperature decreased with increasing content of BiGaO₃ and first decreases and then increases with increasing amount of Bi_0.5K_0.5TiO₃.     

Pyroelectric properties in three phases coexistence Pb[(Mn0.33Nb0.67)0.5(Mn0.33Sb0.67)0.5]0.08(ZrxTi1−x)0.92O3 lead ceramics

The bulk dense Pb[(Mn_0.33Nb_0.67)_0.5(Mn_0.33Sb_0.67)_0.5]_0.08(Zr_xTi_1−x)_0.92O₃ pyroelectric ceramics have been successfully prepared by the conventional solid method. The effect of three phases coexistence in the ceramics is studied. When x = 0.95 and 0.85 in the ceramics, the maximum pyroelectric coefficient peaks appear at 23 °C and 45 °C, and the maximum values are 26.5 × 10⁻⁴ C/m² °C and 25.5 × 10⁻⁴ C/m² °C, respectively. The maximum pyroelectric coefficient appears large while the peaks widths are small. When the two kinds of ceramic powders mixed with the mol ratio of 2:1, the pyroelectric coefficient of the ceramics is above 10.0 × 10⁻⁴ C/m² °C in a broad temperature range from 20 °C to 55 °C. The possible physical mechanism of the temperature broadened phenomenon is briefly discussed.     

Structural and optical properties of In0.5Ga0.5As/GaAs quantum dots in an In0.1Ga0.9As well using repeated depositions of InAs/GaAs short-period superlattices for the application of optical communication

We report structural and optical properties of In_0.5Ga_0.5As/GaAs quantum dots (QDs) in a 100 Å-thick In_0.1Ga_0.9As well grown by repeated depositions of InAs/GaAs short-period superlattices with atomic force microscope, transmission electron microscope (TEM) and photoluminescence (PL) measurement. The QDs in an InGaAs well grown at 510 °C were studied as a function of n repeated deposition of 1 monolayer thick InAs and 1 monolayer thick GaAs for n=5–10. The heights, widths and densities of dots are in the range of 6–22.0 nm, 40–85 nm, and 1.6–1.1×10¹⁰/cm², respectively, as n changes from 5 to 10 with strong alignment along [1 −1 0] direction. Flat and pan-cake-like shape of the QDs in a well is found in TEM images. The bottoms of the QDs are located lower than the center of the InGaAs well. This reveals that there was intermixing—interdiffusion—of group III materials between the InGaAs QD and the InGaAs well during growth. All reported dots show strong 300 K-PL spectrum, and 1.276 μm (FWHM: 32.3 meV) of 300 K-PL peak was obtained in case of 7 periods of the QDs in a well, which is useful for the application to optical communications.     

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.     

Characterization of lead free (K0.5Na0.5)NbO3-LiSbO3 piezoceramic

(K_0.5Na_0.5)NbO₃ (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO₃ (LS) modified KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefficients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a “softening” behavior. However, a high coercive field (∼17 kV/cm) was found for the LS modified KNN material. The properties as a function of temperature were determined in the range of −50-250 ^°C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Improving microwave dielectric properties of La2.98/3Sr0.01(Mg0.5Sn0.5)O3 ceramics with CuO additive

The microwave dielectric properties of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were investigated with a view to their application in microwave devices. CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method. The X-ray diffraction patterns of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics exhibited no significant variation of phase with sintering temperature. By adding 0.75 wt.% CuO, a dielectric constant of 20.07, a quality factor (Q × f) of 63,000 GHz, and a temperature coefficient of resonant frequency τ_f (−77.0 ppm/°C) were obtained when La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were sintered at 1500 °C for 4 h.     

Effect of the solid-state synthesis parameters on the physical and electronic properties of perovskite-type Ba(Fe,Nb)0.5O3 ceramics

Single-phase cubic Ba(Fe,Nb)_0.5O₃ (BFN) powder was synthesized by solid-state reaction at 900, 1000, 1100, 1200 °C for 4 h in air. X-ray diffraction indicated that the BFN oxide mixture calcined at 1200 °C crystallizes to the pure cubic perovskite phase. The crystallite size of the BFN increases slightly with increasing temperature, while the lattice strain progressively decreases. BFN ceramics were produced from this powder by sintering at 1350–1400 °C for 4 h in air. Samples prepared under these conditions achieved up to 97.4% of the theoretical density. The temperature dependence of their dielectric constant and loss tangent, measured at difference frequencies, shows an increase in the dielectric constant with sintering temperature and measurement frequency which is probably due to disorder on the B site ion of the perovskite. The Mössbauer spectra of these sintered BFN ceramics suggests the presence of a superstructure on the B-cation sublattice.     

Li mobility in Li0.5 − xNaxLa0.5TiO3 perovskites (0 ≤ x ≤ 0.5): Influence of structural and compositional parameters

The dependence of Li mobility on structure and composition of Li_0.5 − xNa_xLa_0.5TiO₃ perovskites (0 ≤ x ≤  0.5) has been investigated by means of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. At 300 K, all samples display a rhombohedral superstructure (R-3c S.G.), where octahedra are out of phase tilted along [111] direction of the ideal cubic cell. The elimination of the octahedral tilting is responsible for the rhombohedral–cubic transformation, detected near 1000 K. In these perovskites, La and Na cations are randomly distributed in A sites, but Li ions are fourfold coordinated at unit cell faces of the cubic perovskite. Lithium conductivity, σ_300 K, decreases with the sodium content, decreasing from values typical of fast ionic conductors, 10^− 3 S/cm, to those of good insulators, 10^− 10 S/cm, when the interconnectivity between vacant A sites is lost (x > 0.3). In samples with x < 0.3, dc conductivity displays a non-Arrhenius behaviour, decreasing activation energy from ~ 0.37 to 0.25 eV when the sample is heated between 77 and 500 K. The temperature dependence of B_Li factors shows the existence of two regimes for Li motion. Below 373 K, Li ions remain partially located near square oxygen windows that connect contiguous A sites, but above 400 K, extended Li motions become dominant. The additional decrease of activation energy from 0.25 to 0.16 eV (low-temperature ⁷Li NMR value), should require the full elimination of octahedral tilting which is only produced above 1000 °C.     

Microstructures and microwave dielectric properties of La1-xBx(Mg0.5Sn0.5)O3 ceramics

The microwave dielectric properties of La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A maximum apparent density of 6.58 g/cm³, a dielectric constant (ε_r) of 19.8, a quality factor (Q × f) of 41,800 GHz, and a temperature coefficient of resonant frequency (τ_f) of −86 ppm/°C were obtained for La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.     

Electrical properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

Dielectric and piezoelectric properties of non-stoichiometric (K0.5Na0.5)(Nb0.9+xTa0.1)O3 ceramics

In the study, in order to develop the lead-free piezoelectric ceramics for actuator, transformer and other electronic-devices application, (K_0.5Na_0.5)(Nb_0.9+xTa_0.1)O₃ + 0.5 mol% CuO + 0.2 mol% MnO₂ ceramics were prepared by conventional mixed oxide method. The effects of B-site non-stoichiometry in [(K_0.5Na_0.5)] [(Nb_0.9+xTa_0.1)O₃] ceramics on microstructure and piezoelectric properties were investigated. The density, electromechanical coupling factor (k_p), mechanical quality factor (Q_m), piezoelectric constant (d₃₃), T_C and T_O-T of NKNT ceramics with x = 0.0065 showed the optimum values of 4.58 g/cm³, 0.427, 1554, 109 pC/N, 373 °C and 226 °C, respectively, suitable for piezoelectric motor, and transformer applications.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

Dielectric and piezoelectric properties of Fe2O3-doped (Na0.5K0.5)0.96Li0.04Nb0.86Ta0.1Sb0.04O3 lead-free ceramics

The effect of a small amount Fe₂O₃ (0.1-2 mol%) doping on the electrical properties of (Na_0.5K_0.5)_0.96Li_0.04Nb_0.86Ta_0.1Sb_0.04O₃ (NKLNTS) ceramics was investigated. It was found that the B-site substitution of Fe³⁺ does not change the crystal structure within the studied doping level and all modified ceramics have a pure tetragonal perovskite structure at room temperature. The addition of Fe₂O₃ can promote the sintering of NKLNTS ceramics, and simultaneously cause the grain growth so that Fe³⁺-doped NKLNTS compositions show degraded densification at higher doping level. Furthermore, the dielectric properties of the NKLNTS ceramics do not show a significant change by Fe₂O₃ doping. However, the addition of Fe₂O₃ was found to have a significant influence on the electric fatigue resistance and the durability against water. The presence of oxygen vacancies caused by the replacement of Fe³⁺ for B-site ions makes the NKLNTS ceramics harder.     

Study of dielectric and ac impedance properties of Ti doped Mn ferrites

We have reported dielectric and ac impedance properties of Ti doped Mn_1+xFe_2−2xO₄ (0x0.5) ferrites prepared by solid-state reaction method, using dielectric and impedance spectroscopy in the frequency range of 42 Hz–5 MHz, between the temperatures (300K–473K). The dielectric constant and dielectric loss (tan δ) decreases with increasing frequency but these parameters increase with increasing temperature. The dielectric loss tangent curves exhibit dielectric relaxation peaks at high frequencies (3.6 kHz–5 MHz), which are attributed to the coincidence of the frequency of charge hopping between the localized charge states and the external field. The dielectric properties have been explained on the basis of space charge polarization according to Maxwell–Wagner’s two-layer model and the hopping of charge between Fe²⁺ and Fe³⁺ as well as between Mn³⁺ and Mn²⁺ ions at B-sites. The complex impedance analysis has been used to separate grain and grain boundary in studied samples. Two semicircles corresponding to grain and grain boundary have been observed at low temperature, while only one semicircle has been seen at high temperatures. The resistance of grain and grain boundary both increase with Ti⁴⁺ doping.     

Crystal structure and ferroelectric properties of Mn-doped ((Ka0.5Na0.5)0.935Li0.065)NbO3 lead-free ceramics

In this study, ceramics in Mn-doped ((Ka_0.5Na_0.5)_0.935Li_0.065)NbO₃ ceramics (Mn content = 0.25, 0.50, 1.00 and 1.50 mol%) were successfully prepared by the conventional mixed-oxide technique. The crystal structure was identified by XRD as a single-phase perovskite structure with tetragonal symmetry. The valence of Mn ions, characterized by the synchrotron XAS technique, was seen to change from Mn⁴⁺ to Mn³⁺ during the formation of the crystal. The valence state of Mn strongly affected the crystal structure and ferroelectric properties of the ceramics. The ferroelectric parameters show the decrease of remnant polarization and the increase of the coercive field with increasing MnO₂ content. The results confirm the Mn³⁺ in KNNL perovskite lattices, leading to the formation of oxygen vacancies and hardening effects.