Structural and dielectric studies of lead-free ceramics: Na1/2Y1/2TiO3

The polycrystalline samples of Na_1/2Y_1/2TiO₃ were prepared by the mixed-oxide method. A preliminary X-ray structural analysis was shown to exhibit the formation of a single-phase compound with an orthorhombic structure. Microstructural analysis by scanning electron microscopy (SEM) exhibits well defined grains distributed uniformly through out the sample suggesting the compactness and homogeneity of the sample. Detailed studies of dielectric properties of Na_1/2Y_1/2TiO₃ in a wide frequency range (102–106 Hz) at different temperatures (31–500°C) show a dielectric anomaly at 105°C, which may be related to a ferroelectricparaelectric phase transition as suggested by hysteresis loop at room temperature. An ac conductivity (σ _ac) of the material is mainly governed by the polaron hopping mechanism, which is also influenced by both frequency and temperature. The activation energy was obtained from the plot of temperature with a.c. conductivity.      

Effect of excess Bi2O3 on the electrical properties and microstructure of (Bi1/2Na1/2)TiO3 ceramics

(Bi_1/2Na_1/2)TiO₃ ceramics (BNT) with 0–6 mol% of excess Bi₂O₃ are prepared by conventional solid-state sintering. The electrical properties of the samples are examined. The addition of excess Bi₂O₃ reduces the leakage current of BNT ceramics significantly, thus facilitating the poling process, and improves their piezoelectric properties slightly for certain amounts of added Bi₂O₃. BNT ceramics have very high dielectric constants and dissipation factors at low frequency and high temperature due to their high conductivity. Adding excess Bi₂O₃ to BNT ceramics affects their dielectric behavior and phase transition temperatures. Grain growth is suppressed by adding Bi₂O₃ and no second phase is observed for BNT ceramics with up to 6 mol% of excess Bi₂O₃ added.     

Dielectric properties and electrical conduction of La2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

La₂O₃ (2 wt%)-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (abbreviated as BNBT6) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction. X-ray diffraction (XRD) patterns indicated that La₂O₃ has diffused into the lattice of BNBT6 ceramics and formed a solid solution with a pure perovskite structure. Addition of La₂O₃ decreased the piezoelectric properties and electrical conductivity. It was used to study the electrical conductivity of the La₂O₃-doped BNBT6 lead-free piezoelectric ceramics combined with electrical modulus and impedance plots at the temperature range over 788–873 K. The values of activation energy derived from the electrical impedance and modulus were found to be 0.51 and 0.50 eV, respectively. The discrepancy between activation energy of relaxation frequency and the activation energy (0.25 eV) of dc electrical conductivity might have been due to a short-range migration or hopping of single ionized oxygen vacancy and a long-range migration or hopping of charge carriers over the whole disordered system, respectively.     

(Na1/2Bi1/2)Cu3Ti4O12陶瓷的微观结构和电学性质

利用固相反应法在不同烧结温度条件下制备了一系列(Na_1/2Bi_1/2)Cu₃Ti₄O₁₂(NBCTO)陶瓷样品,研究了它们的晶体结构、微观组织结构、介电性质和复阻抗及其随温度的变化. 实验发现NBCTO陶瓷所呈现出的电学性质与CaCu₃Ti₄O₁₂陶瓷相应的电学性质非常类似. 烧结温度为990℃至1060℃范围的NBCTO陶瓷样品室 关键词： 高介电材料 介电性质 复阻抗 内阻挡层电容     

Luminescence properties of K1/2Bi1/2TiO3:Pr3+ and Na1/2Bi1/2TiO3:Pr3+

The luminescence properties of K(1/2)Bi(1/2)TiO(3):Pr(3+) and Na(1/2)Bi(1/2)TiO(3):Pr(3+) powders are investigated in the temperature range 10-600 K. The experimental data are interpreted on the basis of metal-to-metal charge transfer processes and by considering Bi(3+)-to-Pr(3+) sensitization effects.     

Studies on structural and dielectric properties of Na1/2Dy1/2TiO3 ceramic

The polycrystalline sample of Na_1/2Dy_1/2TiO₃ ceramic was prepared by a standard high-temperature solid-state reaction technique. X-ray structural analysis confirmed the formation of single-phase (with minor secondary phase) compound in the orthorhombic (distorted tetragonal) crystal system at room temperature. Study of surface morphology by scanning electron microscope exhibits uniform distribution of rectangular/cubical grains with less voids. The elemental composition of the prepared compound was confirmed by energy dispersive X-ray spectroscopy microanalysis. Detailed studies of dielectric properties exhibit a dielectric anomaly at 94 °C suggesting a possible ferroelectric–paraelectric phase transition in the compound. The activation energy (E_a), calculated from the temperature dependence of ac conductivity plot, was found to be small (∼0.1 eV) in low temperature and large (∼0.5 eV) in high temperature region.     

Structural,thermal, electrical and magnetic properties of pure and 50% La doped BiFeO3 ceramics

Polycrystalline ceramic samples of pure and 50% La substituted BiFeO₃ have been prepared by standard solid state reaction method using high purity oxides and carbonates. The formation of the single phase compound as well as its chemical analysis has been checked by X-ray diffraction and energy dispersive X-ray microanalysis (EDAX) techniques. A better agreement between observed and calculated X-ray powder diffraction patterns was obtained by performing the Rietveld refinement with a structural model using the non-centrosymmetric space group R3c. The lattice parameters in both the cases have been refined but the over-all structure remains the same. The microstructural studies have been carried out using scanning electron microscopy (SEM). Modulated differential scanning calorimetry (MDSC) has been used to detect the Neel/transition temperature in the compounds. The activation energies calculated from log σ vs 1/T curve are 0.81 eV and 1.13 eV respectively. Vibrating sample magnetometer (VSM) has been used to study the magnetic behaviour of the compounds. It has been observed that by 50% La substitution the insulating behaviour of the material has been improved and showing the antiferromagnetic to weak ferromagnetic behaviour.     

Ferroelectric (Na1/2Bi1/2)TiO3 thin films showing photoluminescence properties

Polycrystalline lead-free (Na_1/2Bi_1/2)TiO₃ (NBT) ferroelectric thin films doped with 1 mol% of rare earth (RE) elements are processed on Pt-terminated silicon substrates using a solution deposition method. The thin films that exhibit single-phase perovskite structure show photoluminescence properties with highest intensities in the wavelength range between 700 and 850 nm, depending on RE element. The ferroelectric properties of the pure NBT film (P _r: 20.5 µC cm^?2, E _c: 150 kV cm^?1) are somewhat decreased for the doped films, which is ascribed to decreasing of the number of Bi lone pairs through the substitution of Bi with RE elements in the perovskite lattice.     

23Na NMR in the relaxor ferroelectric Na1/2Bi1/2TiO3

The ²³Na NMR spectra of a Na_1/2Bi_1/2TiO₃ crystal are studied at frequencies of 79.4 and 15.7 MHz in the temperature range 150–720 K. It is revealed that, at all temperatures, the crystal contains regions with a nearly cubic matrix and polar clusters. The temperature dependence of the local distortion of the Na environment in the clusters is determined. The dynamics of the reorientation of the local cluster polarization in the tetragonal and trigonal NBT phases is analyzed.     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na0.25K0.25Bi0.5TiO3(NKBT50)陶瓷,研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰,而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示,陶瓷的去极化温度为225℃,与此相对应的介电、损耗峰也与氧空位有关.     

(Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics with simultaneous addition of CeO2 and La2O3

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT-6) with simultaneous addition of 0.5 mol% CeO₂ and 0.25, 0.5 and 0.75 mol% La₂O₃, respectively, was prepared by a conventional ceramic fabrication technique. An addition of 0.5 mol% CeO₂ together with 0.5 mol% La₂O₃ enhanced the piezoelectric and dielectric constant of BNBT-6 ceramics significantly. At room temperature, this composition exhibits a high piezoelectric constant (d₃₃=162×10^-12 C/N) and relatively low dielectric loss (cos=2.0%) at 1 kHz. X-ray diffraction pattern shows that the coexistence of tetragonal and rhombohedral phases in the BNBT-6 composition was not changed by adding CeO₂+La₂O₃, and they diffused into the BNBT lattice during sintering. SEM observation indicates that a small amount of CeO₂+La₂O₃ almost does not affect the microstructure. PACS 77.65.Bn; 77.84.Dy; 77.22.-d     

Na1/2 Bi1/2 TiO3体系的电子结构与极化特性

采用自洽场离散变分X_α计算方法,研究了ABO₃型钙钛矿结构无铅压电陶瓷Na_1/2Bi_1/2TiO₃体系的电子结构,分析了A,B位元素取代对Na_1/2Bi_1/2TiO₃压电陶瓷极化性能的影响.结果表明:NBT体系压电陶瓷材料存在自发极化,B位离子位移使铁电性增强,Ba,Sr与Mn离子A,B位复合取代可降低矫顽场、提高自发极化强度,从而提高材料的铁电性能,并通过实验对此结论进行了验证.     

Structural and electrical properties of lanthanum-substituted lead titanate ceramics

The effect of lanthanum substitution on the structural, dielectric and piezoelectric properties of lead calcium titanate (PCT) ceramics is studied. Samples with compositional formula Pb_{0.76? x} La _x Ca_0.24Ti_0.98Mn_0.02O₃ (PLCT) (x?=?0–0.08, in steps of 0.02) were prepared by the conventional dry ceramic technique. Phase and structural analysis was carried out using XRD and SEM respectively. X-ray analysis confirmed the formation of single-phase compound with tetragonal crystal structure. Dielectric properties were studied in detail as a function of frequency and temperature. The Curie temperature (T _C) and tetragonality (c/a) was found to decrease with increase in lanthanum content. The Curie temperature was also confirmed from the thermal-expansion behaviour of the sintered samples. Piezoelectric coefficients (d ₃₃, d ₃₁, g ₃₃, g ₃₁, g _h, d _h, k _t and k _p) were measured at room temperature. From this study it is found that La³⁺ substitution helps in the improvement of electro-mechanical anisotropy.     

Ferropiezoelectric properties and microstructure of PbFe1/2Nb1/2O3 ceramics

Ceramic samples of lead ferroniobate (PFN) having a rhombohedral symmetry at room temperature are obtained. Their ferroelectric and magnetic properties in the vicinity of the antiferromagnetic and ferroelectric phase transition temperatures are investigated. The electrophysical parameters of the polarized ceramic are presented. By means of electron-probe microanalysis, the number of inclusions of Fe-containing impurity phases (??0.2 vol %) is revealed to be several times higher than that in grains of the PFN ceramics. It is suggested that the above could be caused by the magnetic properties of PFN at room temperature.     

Improved electrical properties of La2/3Ba1/3MnO3:Ag0.04 thin films by thermal annealing

La_2/3Ba_1/3MnO₃:Ag_0.04 (LBMO:Ag_0.04) thin films were prepared on single crystalline (001)-orientated LaAlO₃ substrates by pulsed laser deposition technique. Thermal annealing with temperatures of 780, 800 and 820 °C has been investigated to improve electrical properties of the films. All the samples are shown along the (00l) orientation in rhombohedral structure with \( R\overline{3} c \) space group. With thermal annealing temperature increasing, insulator–metal transition temperature (T _p) and resistivity at T _p ( \( \rho_{{T_{\text{p}} }} \) ) of the epilayer reach optimal value of 288 K and 0.03 Ω·cm, respectively. The electrical properties improvement of the LBMO:Ag_0.04 films is due to an improved film crystallization, oxygen balance and photon scattering suppression. The fitting curves show that the region of ferro-magnetic metallic (FM, T < T _p) is fitted with grain/domain boundary, electron–electron and magnon scattering mechanism, as well as the region of para-magnetic insulating (PI, T > T _p) is fitted with adiabatic small polaron hopping mechanism.     

Grain size effect on the giant dielectric and nonlinear electrical behaviors of Bi1/2Na1/2Cu3Ti4O12 ceramics

Single phase Bi_1/2Na_1/2Cu₃Ti₄O₁₂ (BNCTO) ceramics with different grain sizes (1.4–4.3 μm) are prepared by a modified Pechini method to investigate their giant dielectric and nonlinear electrical behaviors. The results show that the giant dielectric and nonlinear electrical behaviors are strongly dependent on grain size. With the increment of grain size, the dielectric constant increases monotonically from 14110 (for 1.4 μm sample) to 36183 (for 4.3 μm sample) at 1 kHz, in accompaniment with the breakdown voltage reducing from 112.5 to 43.2 V/mm and the nonlinear coefficient reducing from 4.9 to 3.4. On the basis of the internal barrier layer capacitor (IBLC) model and the IBLC model of Schottky-type potential barrier, an interpretation of the grain size effect on the giant dielectric and nonlinear electrical behaviors is presented.     

Structural and dielectric properties of La- and Ti-modified K0.5Na0.5NbO3 ceramics

We report the results of studies of rectifying behavior, positive magneoresistance (MR), the charge-transport mechanism and the effect of an electric field on a ZnO (n)/La_0.5Pr_0.2Sr_0.3MnO₃ (LPSMO) (p)/SrNb_0.002Ti_0.998O₃ (SNTO) (n) heterostructure comprising two p–n junctions fabricated using the pulsed laser deposition technique. The heterostructure exhibits rectifying behavior over a wide temperature and field range having hysteresis in I–V behavior (forward bias) due to the tunneling of charge carriers. It is also observed that, depending on the nature of the electric field bias to n-type ZnO and SNTO, the junction resistance becomes modified, which has been explained on the basis of spin injection in the heterostructure. The observation of unconventional positive MR at room temperature has been justified on the basis of interface effects and the reduction in barrier height obtained using fitting of the I–V data by a thermionic emission model.     

Synthesis and properties of La1-xSrxNiO3 and La1-xSrxNiO2

Superconductivity has been realized in films of La_1-xSr_xNiO₂. Here we report synthesis and characterization of polycrystalline samples of La_1-xSr_xNiO₃ and La_1-xSr_xNiO₂ (0 ≤ x ≤ 0.2). Magnetization and resistivity measurements reveal that La_1-xSr_xNiO₃ are paramagnetic metal and La_1-xSr_xNiO₂ exhibit an insulating behavior. Superconductivity is not detected in bulk samples of La_1-xSr_xNiO₂. The absence of superconductivity in bulk La_1-xSr_xNiO₂ may be due to the generation of hydroxide during reduction, a small amount of nickel impurity, or incomplete reduction of apical oxygen. The effect of interface in films of La_1-xSr_xNiO₂ may also play a role for superconductivity.