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.     

(1-x)(K0.5Na0.5)NbO3-xSrTiO3陶瓷的弛豫铁电性能

通过对(1-x)(K0.5Na0.5)NbO3-xSrTiO3(0≤x≤0.15)陶瓷的相组成、晶体结构和介电性能的研究发现,该陶瓷为单一的钙钛矿结构相.当x含量较小(x＜0.1)时为正交相结构,x≥0.1时转变为四方相结构.随着SrTiO3掺杂量的增加,样品的致密度增加,样品由正常铁电相逐渐向弥散铁电相转变,且相变温度明显下降,其相变峰的半高宽D和临界指数γ,随 x 的增加而增加.样品损耗ε″r(复介电常数虚部)随温度T的变化表明低温时弛豫极化损耗起主要作用,高温时漏导损耗起主要作用.同时介电常数实部ε′r随频率的变化显示(1-x)(K0.5Na0.5)NbO3-xSrTiO3弛豫为德拜弛豫.     

The effect of some transition metal oxides on the physical properties of K0.5Na0.5Nb0.95Ta0.05O3 ceramics

Abstract

Both K_0.5Na_0.5Nb_0.95Ta_0.05O₃ (KNNTO) and (K_0.5Na_0.5Nb_0.95Ta_0.05O₃)_0.99-M_0.01, M = Co₃O₄ and Mn₂O₃ (M/KNNTO) Ferromagnetic behaviour was observed for some M/KNNTO compounds. The hardness and compressive strength of all investigated samples are given. Comparisons with similar materials are discussed. Ceramics were synthesised using a solid-state reaction method. X-ray diffraction patterns of all samples revealed that the crystal structure is orthorhombic. Field-emission scanning electron microscopy was performed. Polarisation hysteresis curves indicated a disruption of ferroelectric order with the addition of M into KNNTO ceramics. The dielectric properties of the investigated ceramics have been studied as a function of frequency and temperature.     

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.     

New crystallographic dielectric phase boundary in K0.5Na0.5NbO3‐based lead‐free ceramics

0.979K_0.5Na_0.5Nb_1‐xSb_x O₃‐0.021Bi_0.5Na_0.5TiO₃ (KNNSx ‐BNT) lead‐free piezoelectric ceramics were fabricated by conventional solid state reaction technique, and their phase transition and electrical properties were studied. With the increase of x, the rhombohedral‐orthorhombic phase transition temperature of the ceramics increases. Finally, both the rhombohedral‐orthorhombic and orthorhombic‐tetragonal phase transitions of the ceramics were modified to be around room tempera‐ ture when about 6% Sb were substituted for the Nb site, resulting in the formation of a new phase boundary separating rhombohedral and tetragonal phases. The formation of the new phase boundary results in excellent properties for the ceramics, that is, the KNNS0.05‐BNT ceramic shows an enhancement in piezoelectric properties: d₃₃ = 380 pC/N and k_P = 0.438. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and physical properties of Ca- and Ta-modified (K,Na)NbO3 lead-free piezoelectric ceramics

Polycrystalline samples of lead-free Ca and Ta co-substituted potassium sodium niobate (K_0.5Na_0.5NbO_3, KNN) ceramics have been prepared by solid state reaction technique. X-ray diffraction showed formation of a single-phase perovskite structure with orthorhombic symmetry. Substitution inhibits the grain growth, improves densification and decreases the ferro-paraelectric phase transition temperature. Temperature dependent dielectric permittivity studies demonstrate significant decrease in peak-permittivity values in the substituted samples. Bulk longitudinal piezoelectric coefficient is significantly enhanced, up to ～155 pC/N for (K_0.48Na_0.48Ca_0.02)(Nb_0.85Ta_0.15O₃) as compared to 95 pC/N for pristine KNN ceramic. Local piezoelectric properties have been observed by piezoresponse force microscopy (PFM) technique. Distinct piezocontrast was studied in both vertical and in-plane modes of PFM for all samples. The samples exhibit self-polarization effect in the unpoled state and effective local vertical piezoelectric coefficient was the largest in Ca and Ta co-substituted sample whereas the in-plane piezoelectric coefficient was maximum for Ca-substituted KNN sample. These studies are important for using substituted lead free KNN materials in various piezoelectric applications.     

Piezoelectric and ferroelectric properties of [(K0.4725Na0.4725)Li0.055]NbO3–(Ag0.5Li0.5)TaO3 lead‐free ceramics

New lead‐free piezoelectric (1 – x)[(K_0.4725Na_0.4725)Li_0.055]NbO₃– x (Ag_0.5Li_0.5)TaO₃ [(1 – x)KNNL–x ALT] ceramics were prepared by conventional sintering. Piezoelectric and ferroelectric properties and Curie temperature of the ceramics were studied. The (1 – x)KNNL–x ALT (x = 0.04) ceramics exhibit good properties (d₃₃ ～ 252 pC/N, k_p ～ 41%, T_C ～ 471 °C, T_o–t = 47 °C, P_r = 33.1 μC/cm², E_c = 10.6 kV/cm). These results show that (1 – x)KNNL–x ALT (x = 0.04) ceramic is a promising lead‐free piezoelectric material for high temperature application. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

四方和正交以及单斜相K0.5Na0.5NbO3的结构稳定性和电子结构的第一性原理研究

采用基于密度泛函理论框架下的第一性原理超原胞方法和虚晶近似方法, 在局域密度近似和广义梯度近似下, 对四方和正交以及单斜相K_0.5Na_0.5NbO₃的能量和原子结 构以及电子结构进行了系统的研究. 计算结果表明三种K_0.5Na_0.5NbO₃相的能量差别较小, 这与实验上它们之间容易发生相转化是一致的. 进一步发现单斜相的能量比四方相和正交相低, 说明单斜相结构更加稳定, 并且理论计算的结构参数与实验值符合得很好. 电子结构结果也表明单斜相的键合作用比四方相和正交相键合作用更强, 进一步说明单斜相结构更加稳定. 关键词： 铌酸钾钠 四方相 单斜相 密度泛函理论     

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.     

Raman tensor analysis of (K0.5Na0.5)NbO3–LiSbO3 lead‐free ceramics and its application to study grain/domain orientation

A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO₃ (LS‐modified) (K_0.5Na_0.5)NbO₃ (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman‐active modes. Complete sets of Raman tensor elements of A_g, and E_g phonon modes for orthorhombic/tetragonal structures of KNN have been determined. Through this spectroscopic algorithm, quantitative information could be extracted in terms of three Euler angles in space for KNN samples consisting of mixed phases, thus enabling quantitative visualization of the local distribution of grains/domains in the solid angle. As an application of the method, we quantitatively examined the unknown crystallographic grain orientation patterns on the surfaces of pure KNN and of KNN‐0.05LS ceramics. These two samples were useful to clarify a polymorphic phase transition from the orthorhombic to the tetragonal phase taking place in the LS‐modified KNN system. Thus, we demonstrated that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three‐dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures. We believe that the data shown here represent a typical scenario encountered in grain/domain orientation assessments of piezoelectric perovskites. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Photoluminescence and electrical properties of Eu-doped (Na0.5Bi0.5)TiO3 ferroelectric single crystals

Eu³⁺-doped Na_0.5Bi_0.5TiO₃ (Eu:NBT) single crystals were grown by a top-seeded solution growth method. Photoluminescence emission and excitation spectra of Eu:NBT were investigated. The two transitions in ⁷F₀ → ⁵D₀ excitation spectra reveal that Eu³⁺ ions were incorporated into two adjacent crystallographic sites in NBT, i.e., Bi³⁺ and Na⁺ sites. The former has a symmetrical surrounding, while the later has a disordered environment, which was confirmed by decay curve measurements. The dielectric dispersion behavior was depressed and the piezoelectric and ferroelectric properties were improved after Eu doping.     

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.     

Bi-fluctuation in Na0.5Bi0.5TiO3 ferroelectric ceramics with abnormal relaxor behaviour

ABSTRACT

The existence of Bi-fluctuation dispersing in Na_0.5Bi_0.5TiO₃ (NBT) relaxor ferroelectric is hinted in other recent studies. However, this fluctuation has not been directly observed yet. We introduce the Bi-rich nano-regions with different sizes in a series of NBT ceramics by the slight excess of Bi³⁺ content. The crystal symmetries of the Bi-rich nano-regions and the NBT matrix are rhombohedral. The lattice parameters of the nano-regions are larger than those of the matrix in NBT ceramics, which were confirmed by the X-ray diffraction Rietveld refinement, TEM techniques and first-principles calculation. Also, the disorder-induced nano-regions appearing as Bi-fluctuation are associated with the complex phase transitions and the high-frequency relaxor behaviour of NBT suggested by the dielectric measurements and Raman spectra.     

Growth and properties of Li,Ta modified (K,Na)NbO3 lead‐free piezoelectric single crystals

Li, Ta modified (K,Na)NbO₃ single crystals with the size of 18 mm × 18 mm × 10 mm were successfully grown by top‐seeded solution growth method, with orthorhombic–tetra‐gonal phase transition temperature ～79 °C and Curie temperature ～276 °C. The electromechanical coupling factors k₃₃ and k_t were found to be ～88% and ～65%, respectively. The piezoelectric coefficient d₃₃ for the [001]_c poled crystals reached 255 pC/N. In addition, the electromechanical coupling factor exhibited high stability over the temperature range of –50 °C to 70 °C, making these lead free crystals good candidates for electromechanical applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.