Microstructural Changes in Lanthanum-Doped Barium Magnesium Niobate

Observations of microstructural changes in (Ba_0.95La_0.05)-(Mg_0.35Nb_0.65)O₃ and (Ba_0.925La_0.075)(Mg_0.36Nb_0.64)O₃ (BLMN) were carried out using high-resolution transmission electron microscopy (HRTEM) and synchrotron powder X-ray diffractometry (XRD). In both samples, not only 1:1 and 1:2 ordered domains coexisted in a single grain, but also the intermediate phase, whose structure had a superlattice modulation of 1.42 nm, which was equivalent to 6 times the unit cube of disordered perovskite found on the nanoscale. The ordered 1:2 domains gradually transformed to 1:1 ordered structure through the formation of an intermediate superlattice structure that comprised 6 × 6 × 6 cubic unit cells with different chemical orderings of B-site ions in B-site lattices. Also, the features of thin plates could be detected by XRD patterns and HRTEM. When the thicknesses were very thin, about several atomic distances, stacking faults occurred on (111) planes. However, when their thicknesses were >50 nm, the thin plates existed as a transition phase with their own structure. They were coherent with the matrix and continuously decomposed into the matrix phase by the lateral migration of the interfaces.     

Interfacial Structure of Ordered Domains in Barium Lanthanum Magnesium Niobate

Microstructural studies on the interfacial boundaries of 1:1 and 1:2 ordered domains in (Ba_0.9La_0.1)(Mg_0.37Nb_0.63)O₃ were conducted using high-resolution transmission electron microscopy and X-ray diffractometry. Both 1:2 and 1:1 ordered domains coexisted in a fully ordered single grain. Each ordered domain occupied its own region, and the interfaces were atomically sharp and coherent. The wavelength of the superlattice modulation was ∼0.47 nm in the 1:1 ordered domain and ∼0.71 nm in the 1:2 ordered domain. The transition from the 1:2 ordered region to the 1:1 ordered region was clearly shown at the interface. These observations well support the structural models that have been previously presented.     

Two Types of Domain Boundaries in Lanthanum Magnesium Niobate

Microstructural studies of the domain boundaries in the complex perovskite compound lanthanum magnesium niobate (La[Mg_2/3Nb_1/3]O₃, LMN) were conducted using transmission electron microscopy. Both the 1:1 chemical ordering of B-site cations and the tilting of oxygen octahedra affected the domain boundaries. Two types of domain boundaries were observed. In addition to the presence of antiphase boundaries, which were insensitive to the crystallographic planes, ferroelastic domain boundaries that were caused by the phase transition due to the tilting of oxygen octahedra also were present. In some grains, only one type of oxygen tilting was present, which resulted in a single domain in one grain. Two or three domains were observed in a grain where the walls were parallel to the {110} plane. Many domains also were observed in a grain that had boundaries whose linear characteristics were gradually reduced.     

High-Resolution Transmission Electron Microscopy Observations on Antiphase Boundaries in Barium Lanthanum Magnesium Niobate

Atomic structural observations on the antiphase boundaries (APBs) in the complex barium lanthanum magnesium niobate perovskite compound Ba_0.7La_0.3(Mg_0.43Nb_0.57)O₃ (BLMN), which has a 1:1 chemical ordering of B-site cations, were conducted using high-resolution transmission electron microscopy. Using APB contrast, the curved APB was determined to have a ledged structure, with a terrace that was composed of the (111) plane at an atomic level. In APBs with finite widths, microfacets on the (111) planes also were observed.     

Microstructural Observations in Barium Calcium Magnesium Niobate

Microstructural studies on (1 − x )Ba(Mg_1/3Nb_2/3)O₃– x Ca(Mg_1/3Nb_2/3)O₃ (BCMN) complex perovskite compounds, which are mixtures of Ba(Mg_1/3Nb_2/3)O₃ (BMN) and Ca(Mg_1/3Nb_2/3)O₃ (CMN), were conducted using scanning electron microscopy, transmission electron microscopy, and X-ray diffractometry. Pure BMN and CMN both have a 1:2 ordered structure, via the chemical ordering of B-site cations; however, the tilting of oxygen octahedra is involved in pure CMN, whose structure has a 1:2 ordered monoclinic unit cell that is characterized by (±1/6,±1/6,±1/6)-type superlattice reflections in electron diffraction patterns along the [110] zone axis that is based on a simple cubic perovskite. Studies of the morphologic differences have indicated two types of inhomogeneities in a mixture of the BCMN system: (i) a rather large-scale segregation (i.e., grain sizes of several micrometers), where the grains are separated compositionally as being barium-rich or calcium-rich, and (ii) fine-scale lamellar-type segregations 20 nm wide and 200 nm long. The segregation that is caused by Ba and Ca ions can be identified by the difference of superlattice modulations from high-resolution transmission electron microscopy lattice images.     

弛豫铁电陶瓷Ba(Mg,Nb)O_3的制备及性能研究

采用传统陶瓷烧结方法,在空气气氛下烧结制得Ba(Mg,Nb)O3(BMN)陶瓷,并分析了烧结温度对体系相组成及相结构的影响。X射线衍射(XRD)研究表明,随着烧结时间的增加,体系中钙钛矿相也相应增加。红外(FTIR)研究研究表明结构无序的BMN钙钛矿相中部分的区域出现了结构有序现象。通过X射线光电子能谱(XPS)可以发现,随着烧结温度的增加,体系中Nb2O5进入Ba(Mg1/3,Nb2/3)O3晶格。微波介电性能表明,随着烧结温度的增加,Ba(Mg,Nb)O3的rε和Qf值有逐渐增加的趋势。     

Defect Structure and Phase Relations of Highly Lanthanum-Doped Barium Titanate

Incorporation of La³⁺ into the BaTiO₃ lattice was studied on samples of various composition, using quantitative WDS microanalysis (EPMA) in combination with scanning electron microscopy (SEM) and X-ray powder diffractometry (XRPD). Direct determination of solid-solution formulas by microanalysis supports the structure model of a solid solution with La³⁺ on Ba²⁺ sites and a deficient Ti⁴⁺ sublattice, independent of the starting composition. Solid solution extends on the tie line, which points from BaTiO₃ to La₄Ti₃O₁₂, to the composition of approximately Ba_0.70- La_0.38Ti_0.925( V "")_0.075O₃. On the basis of these results, the BaTiO₃-rich part of the BaO-La₂O₃-TiO₂ phase diagram was constructed.     

Infrared Spectroscopic Investigations in Ordered Barium Magnesium Niobate Ceramics

Highly ordered Ba(Mg_1/3Nb_2/3)O₃ ceramics from hydrothermal powders were investigated for the first time using infrared spectroscopy. The experimental data were analyzed in view of the 16 predicted modes of the trigonal structure and adjusted by a four–parameter semiquantum model. The obtained phonon parameters allowed us to calculate the real part of the dielectric permittivity and losses in all infrared regions, and also to estimate the quality factor ( Q ) for this material in the microwave region. The values obtained for the dielectric permittivity (ɛ'= 19) and Q (12 800 at 10 GHz) showed that hydrothermal Ba(Mg_1/3Nb_2/3)O₃ ceramics are good materials for passive components in microwave circuits.     

Dielectric and Structural Characteristics in Barium Lanthanum Magnesium Niobate

The dielectric properties and their related microstructural characteristics in solid solutions of (1 — x )Ba(Mg_1/3Nb_2/3)O₃ (BMN)— x La(Mg_2/3Nb_1/3)O₃ (LMN) (BLMN) were investigated by measuring the relative permittivity (ɛ_r), Q value, and temperature coefficient of resonator frequency (τ_f), and by observing the microstructure using transmission electron microscopy. The trend of variation of the temperature coefficient of the dielectric permittivity (τ_ɛ) was the same for our solid solutions as that reported by Reaney et al . When the tolerance factor ( t ) was >1.01 in BLMN with composition x = 0 to 1.0, where the tilting of oxygen octahedra was not involved, the components of the microstructure included a disordered and transition phase as well 1:1 and 1:2 ordered phases. In the region where 1.01 < t < 0.96 with x = 0.2 to 0.7, the 1:1 order, the disorder, and the phase due to the antiphase tilting of oxygen octahedra were present. Finally, in the region where t < 0.96 with x = 0.7 to 1.0, the microstructure of BLMN was the same as that of the pure LMN, including the 1:1 order and the antiphase, inphase tilting of oxygen octahedra, and the antiparallel shift of A-site cations.     

Microstructure and Dielectric Properties of Barium Strontium Magnesium Niobate

Dielectric properties and their related microstructural characteristics in solid solutions of (1 – x )Ba(Mg_1/3Nb_2/3)O₃– x Sr(Mg_1/3Nb_2/3)O₃ (BMN–SMN, or BSMN) were investigated by measuring the relative permittivity (ɛ_r), Q values, and temperature coefficient of resonator frequency (τ_f), and by observing microstructure using transmission electron microscopy. When the tolerance factor ( t ) was >0.99 in BSMN with composition 0 < x < 0.5, where the tilting of oxygen octahedra was not involved, the microstructure included only 1:2 ordered phase. In the region where 0.99 > t > 0.97 with 0.7 < x < 1.0, the phase due to the antiphase tilting of oxygen octahedral, the disordered phase, and the 1:2 ordered phase were also present. In a few of the grains, core–shell-type structures, whose main components were dislocations and stacking faults, were found in the solid solution of BSMN.     

铌酸锶钡的结构和制备工艺研究进展

铌酸锶钡(Sr1-xBaxNb2O6,简称SBN)是一种重要的滤波压电陶瓷,具有重要的实际应用价值。本文综述了铌酸锶钡的结构,从烧结温度、制备方法、掺杂等方面分析了铌酸锶钡的研究进展,评述了制备工艺和掺杂等对铌酸锶钡的结构和性能的影响,并指出了铌酸锶钡研究领域内尚待解决的问题。     

Characterization of Lanthanum-Doped Barium Titanate Ceramics Using Impedance Spectroscopy

The electrical properties of two single-phase, lanthanum-doped BaTiO₃ compositions, x = 0.03 and x = 0.20, in Ba_{1– x} La _x Ti_{1– x /4}O₃ were investigated by impedance spectroscopy after heat treatment in oxygen, argon, and air at 1350°C. Samples heated in oxygen were electrically insulating, whereas those heated in argon lost oxygen and were semiconducting at room temperature, irrespective of x . Samples heated in air showed intermediate electrical properties and also were electrically inhomogeneous; the two compositions showed different electrical behaviors, and a model for each, based on oxygen nonstoichiometry within the ceramics, is proposed. Oxygen deficiency in samples sintered in air was avoided by heating at 1200°C, instead of 1350°C. Alternatively, oxygen lost from ceramics heated in air at 1350°C was regained by postannealing in oxygen at 1350°C.     

Effect of Barium Titanate on Microstructural Evolution and Properties of Lead Zinc Magnesium Niobate Ceramics

BaTiO₃ (BT) addition vastly alters the dielectric behavior of lead zinc magnesium niobate (PZMN) relaxor ferroelectrics. Heat treatment, including the sintering process, influences the dielectric properties through changes in the distribution of heterogeneous compositions and in the extent of diffused phase transition. With more than 15 mol% BaTiO₃ addition, two cubic phases composed of Ba-rich and Ti-rich PZMN substances exist. The destruction of the BaTiO₃ phase and reconstruction of Ba-rich and Ti-rich regions are initiated during heat treatment, and the extent of destruction and reconstruction determines the dielectric properties of the PZMN ceramics. The BT-rich PZMN phase, which occurs with higher BaTiO₃ addition, plays a less important role in the present investigation.     

铌镁酸钡缓冲层对锆钛酸铅薄膜漏电流的抑制

将铌镁酸钡(Ba(Mg1/3Nb2/3)O3,BMN)作为缓冲层,通过溶胶-凝胶法制备了锆钛酸铅(Pb(Zr0.52Ti0.48)O3,PZT)铁电薄膜.探究BMN缓冲层对PZT铁电薄膜介电、铁电性能影响.研究发现:BMN缓冲层不仅可以改善PZT薄膜晶化生长,同时阻碍了PZT与Pt的互扩散而降低了漏电流.由于对漏电流的抑制作用,适当厚度BMN缓冲层的引入可改善PZT的铁电性能,但随着缓冲层厚度的增加,由于其分压作用,复合膜铁电性减弱.当厚度为10 nm时,薄膜的综合性能最好:介电常数εr=1612.03,介电损耗tanδ=0.024,剩余极化值Pr=31.65 μC/cm2,矫顽场Ec=71.5 kV/cm,漏电流密度J=4.4×10-6 A/cm2.     

Formation of Lead Magnesium Niobate Perovskite from Niobate Precursors Having Varying Magnesium Content

Formation of lead magnesium niobate (PMN) perovskite phase using a columbite type of precursor together with the addition of excess MgO has been investigated. When MgO and Nb₂O₅ are reacted with 1:1 stoichiometry, a minor amount (}2%) of Mg₄Nb₂O₉ is formed along with the columbite-type phase which in turn could lead to the formation of a minor amount of "free Nb₂O₅" in the precursor. This may be the reason for the formation of small amounts of pyrochlore phase during the synthesis of PMN perovskite from the stoichiometric 1:1 precursor. However, it has been found that the perovskite phase can easily be stabilized by the addition of a large excess of MgO in the precursor, although this leads to additional Mg-Nb-O phase Mg₄Nb₂O₉, besides the columbite-type phase MgNb₂O₆. It has been shown that, after this precursor reacts with PbO to form the PMN perovskite, the excess Mg present in the Mg-rich niobate precursor separates out as MgO, as evidenced by X-ray diffraction, which can be removed by leaching with dilute nitric acid, thus forming pure PMN.     

Microstructure Characterizations in Calcium Magnesium Niobate

Microstructural studies on the domain boundaries in Ca(Mg_1/3CNb_2/3)O₃ (CMN) complex perovskite compound were conducted using X-ray diffractometry and transmission electron microscopy. The 1:2 chemical ordering of B-site cations and the tilting of oxygen octahedra were involved in the CMN microstructure, as inferred from the presence of two types of domain boundaries. One type was the antiphase boundaries (APBs), which did not lie on a specific set of crystallographic planes. These boundaries were caused by the chemical 1:2 ordering of B-site cations, magnesium and niobium. The other type was the ferroelastic domain boundaries, which were parallel to a certain crystallographic plane. Therefore, CMN had the 1:2 ordered monoclinic unit cell distorted by the antiphase or in-phase tilting of oxygen octahedra. CMN had the mixed phases rather than the homogeneous phase.     

铌酸锶钡/钛酸锶钡复相陶瓷形成过程研究

应用粉末-溶胶工艺合成出铌酸锶钡/钛酸锶钡复相陶瓷(SBN/SBT)。采用X射线衍射技术研究了不同预烧温度的原始粉料、不同烧结温度和不同保温时间得到的铌酸锶钡/钛酸锶钡复相陶瓷。研究表明:钨青铜相和钙钛矿相共存于体系之中。复相陶瓷形成过程中形成了TiO2、BaNb2O6(BN)、SrNb2O6(SN)等中间相,增加烧结温度至1250℃,形成了铌酸锶钡/钛酸锶钡复相陶瓷。     

Creation of Periodical Antiparallel Domain Structure in Lithium Niobate Crystals During Growth Process

The advantages of producing a periodically poled lithium niobate (PPLN) structure during crystal growth process are the possibility of obtaining thicker and wider structures that leads to greater useful surfaces in addition to the elimination of the subsequent poling process. We report in this paper a new technology of creating bulk periodically poled LiNbO 3 single crystals with antiparallel ferroelectric domains, by direct electric field poling during growth processes. Growth system configuration, crystal composition and geometry selection are explored to allow successful control of the direction of spontaneous polarization using external electric field. PPLN crystal samples with periodicity 20-100μm were grown using this electric field modulated growth technique.     

Microstructural Characteristics of Strontium Magnesium Niobate

Microstructural studies were conducted on the domain boundaries in Sr(Mg_1/3Nb_2/3)O₃ (SMN) complex perovskite compound using X-ray diffractometry and transmission electron microscopy. Both the 1:2 chemical ordering of B-site cations and the tilting of oxygen octahedra were involved in SMN. SMN had a 1:2 ordered monoclinic unit cell, which was distorted by the antiphase tilting of oxygen octahedra. Two types of domain boundaries were found: the antiphase boundaries (APBs), which are not confined crystallographically, and the ferroelastic domain boundaries, which were parallel to the crystallographic planes. SMN had the superlattice reflections of type ±⅙[111] and ±½[111] in the electron diffraction patterns, which cannot be indexed in terms of the 1:2 ordered trigonal phase with only a hexagonal unit cell. The presence of the ferroelastic domains that contained both the 1:2 ordered and the antiphase tilting had been verified by a high-resolution transmission electron microscopy lattice image. The structure of SMN was well explained by a model proposed by other researchers. The formation of the 1:2 ordered domains preceded the ferroelastic domains. Normally, the growth of the ferroelastic domain is not affected by APBs, but it is interrupted by them when the driving force for growth is insufficient, resulting in the stoppage of the domains at APBs.     

Diffuse Phase Transition of Tantalum-Bearing Strontium Barium Niobate

The dielectric constants, ε' and ε", of tantalum-bearing strontium barium niobate (SBNT) ceramics were measured as functions of temperature and frequency. The phase transition of SBNT became ambiguous by adding Ta and the apparent Curie temperature determined from the maximum of ε' had a linear relation with the axial ratio c/a. A dielectric loss peak was observed in the phase transition region of SBNT, and its peak frequency increased with temperature. The loss peak was attributed to dielectric relaxation by the jump between two states with different polarizing directions as a preliminary phenomenon of the phase transition. A model based on the local variation from one unit cell to the next rather than the macroscopic compositional fluctuation in the crystal was proposed for the mechanism of diffuse phase transition.