Reverse Micellar Route to Nanocrystalline Titanates (SrTiO3, Sr2TiO4, and PbTiO3): Structural Aspects and Dielectric Properties

Nanoparticles of strontium titanates (SrTiO₃, Sr₂TiO₄) and lead titanate (PbTiO₃) have been obtained using reverse micelles as nanoreactors. Powder X-ray diffraction studies of the powders after calcining at 800°C show monophasic SrTiO₃, Sr₂TiO₄, and PbTiO₃. X-ray line broadening studies and transmission electron microscopic studies show spherical grains of 30–40 nm size for strontium titanates, while PbTiO₃ is obtained in the form of nanorods. The dielectric constant of SrTiO₃ and Sr₂TiO₄ is found to be 90 and 30, respectively, (at 100 kHz) for samples sintered at 1000°C. PbTiO₃ shows a dielectric constant of 160 (at 100 kHz) after sintering at 900°C. The dielectric constant of Sr₂TiO₄ (with temperature) is highly stable. The temperature variation studies of the dielectric constant of PbTiO₃ show a ferroelectric phase transition at 490°C (1 kHz). The T _c varies with frequency and is found to decrease to 470°C at 100 kHz.     

High-Dielectric-Constant and Low-Loss Microwave Dielectric in the (1−x)Nd(Zn1/2Ti1/2)O3–xSrTiO3 System with a Zero Temperature Coefficient of Resonant Frequency

High-dielectric-constant and low-loss ceramics in the (1− x )Nd(Zn_1/2Ti_1/2)O₃– x SrTiO₃ system have been prepared by the conventional mixed-oxide route and their microwave dielectric properties have been investigated. A two-phase system was confirmed by the X-ray diffraction patterns, the energy-dispersive X-ray spectrometer analysis, and the measured lattice parameters. Addition of SrTiO₃, having a much smaller grain size in comparison with that of Nd(Zn_1/2Ti_1/2)O₃, could effectively hold back abnormal grain growth in the Nd(Zn_1/2Ti_1/2)O₃ matrix. Evaporation of Zn at high temperatures caused an increase in the dielectric loss of the system. The temperature coefficient of resonant frequency increases with increasing SrTiO₃ content and tunes through zero at x =0.52. Specimens with x =0.52 possessed an excellent combination of microwave dielectric properties: ɛ_r∼54.2, Q × f ∼84 000 GHz, and τ_f∼0 ppm/°C. It is proposed as a suitable candidate material for today's 3G passive components and small-sized GPS patch antennas.     

Microstructure and Dielectric Properties of Textured SrTiO3 Thin Films

We investigate the relationship between microstructure and dielectric properties of textured SrTiO₃ thin films deposited by radio-frequency magnetron sputtering on epitaxial Pt electrodes on sapphire substrates. The microstructures of Pt electrodes and SrTiO₃ films are studied by transmission electron microscopy, atomic force microscopy, and X-ray diffraction. SrTiO₃ films grown on as-deposited and annealed Pt electrodes, respectively, consist of a mixture of (111)- and (110)-oriented grains. Temperature-dependent dielectric measurements show that differences in texture and microstructure are reflected in the Curie–Weiss behavior of the SrTiO₃ films. Phenomenological models that account for the effects of thermal mismatch strain on the dielectric behavior are developed for different film textures. The models predict that at a given temperature, paraelectric (111)-oriented films of SrTiO₃ on tensile substrates will have a higher Curie–Weiss temperature and a greater dielectric constant than (110)-oriented films or bulk SrTiO₃. The experimental dielectric behavior is compared with the predictions from theory, and different contributions, such as interfacial layers, film stress, and microstructure, to the Curie–Weiss behavior are discussed.     

Control of Microstructure and Orientation in Solution-Deposited BaTiO3 and SrTiO3 Thin Films

Columnar and highly oriented (100) BaTiO₃ and SrTiO₃ thin films were prepared by a chelate-type chemical solution deposition (CSD) process by manipulation of film deposition conditions and seeded growth techniques. Randomly oriented columnar films were prepared on platinum-coated Si substrates by a multilayering process in which nucleation of the perovskite phase was restricted to the substrate or underlying layers by control of layer thickness. The columnar films displayed improvements in dielectric constant and dielectric loss compared to the fine-grain equiaxed films that typically result from CSD methods. Highly oriented BaTiO₃ and SrTiO₃ thin films were fabricated on LaAlO₃ by a seeded growth process that appeared to follow a standard "two-step" growth mechanism that has been previously reported. The film transformation process involved the bulk nucleation of BaTiO₃ throughout the film, followed by the consumption of this matrix by an epitaxial overgrowth process originating at the seed layer. Both BaTiO₃ and PbTiO₃ seed layers were effective in promoting the growth of highly oriented (100) BaTiO₃ films. Based on the various processing factors that can influence thin film microstructure, the decomposition pathway involving the formation of BaCO₃ and TiO₂ appeared to dictate thin film microstructural evolution.     

Core-Shell Structure Formation in Nb2O5-Doped SrTiO3 by Oxygen Partial Pressure Change

A core-shell structure was observed in SrTiO₃ doped with 1.2 mol% of Nb₂O₅, after sintering in a reducing atmosphere (5H₂-95N₂) and then in an oxidizing atmosphere (air). In undoped and Al₂O₃-doped SrTiO₃ specimens, no core-shell structure formed after the same sintering treatments as those for SrTiO₃ doped with 1.2 mol% of Nb₂O₅. The measured chemical compositions of the core and shell regions of 1.2-mol%-Nb₂O₅-doped SrTiO₃ grains showed that the Sr/(Ti + Nb) ratio of the shell regions grown in air was ~1% less than that of core regions grown in 5H₂-95N₂, which was in good agreement with a value predicted by available defect equations. Therefore, the observed core-shell structure is thought to result from the formation of strontium vacancies in an oxidizing atmosphere.     

Microstructure and Electromagnetic Properties of SrTiO3/Ni0.8Zn0.2Fe2O4 Composites by Hybrid Process

High permittivity and low-loss SrTiO₃/Ni_0.8Zn_0.2Fe₂O₄ (STO/NZO) composites with concrete-like morphology were prepared through hybrid processing route. 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) exhibit a well integration of dielectric and magnetic properties in the composites with low dielectric and magnetic losses. The STO/NZO composites show good dielectric properties and magnetic properties with low loss in high-frequency to microwave-frequency range. The results show that this kind of magnetic–dielectric composites can be used in high-frequency communications for the capacitor–inductor integrating devices such as electromagnetic interference filters and antennas.     

Formation Mechanisms of Platelet Sr3Ti2O7 Crystals Synthesized by the Molten Salt Synthesis Method

The molten salt synthesis (MSS) method is utilized to synthesize the anisotropic platelet Sr₃Ti₂O₇ (S3T2) single-crystal particles. The aim of this study is to identify the essence of platelet Sr₃Ti₂O₇ crystal growth and guide the synthesis of anisotropic platelet SrTiO₃ crystals as well as various technologically important materials. Based on the results of X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy, the formation mechanism of platelet Sr₃Ti₂O₇ crystals conforms to a nucleation–structure rearrangement–dissolution–diffusion in situ epitaxial growth mechanism model. First, SrCO₃ reacts with TiO₂ to form submicrometer SrTiO₃ nuclei. Then, most of the nuclei surrounded by salt ions aggregate and rearrange to form a large SrTiO₃ matrix. The structural rearrangement and the subsequent in situ epitaxial growth processes control the morphology, composition, and size of the final Sr₃Ti₂O₇ crystals. In the synthesis process, the conversion between SrTiO₃ and Sr₃Ti₂O₇ is as follows: and the crystallographic orientation relationship between Sr₃Ti₂O₇ and SrTiO₃ in the interface is (100)_S3T2//{100}_ST, (010)_S3T2//{010}_ST, and (001)_S3T2//{001}_ST.     

Grain-Boundary Migration and Dielectric Properties of Semiconducting SrTiO3 in the SrTiO3-BaTiO3-CaTiO3 System

Chemically induced grain-boundary migration and its effects on the interface and dielectric properties of semiconducting SrTiO₃ have been investigated. Strontium titanate specimens that had been doped with 0.2 mol% of Nb₂O₅ were sintered in 5H₂/95N₂. The sintered specimens were diffusion annealed at 1400°C in 5H₂/95N₂ with BaTiO₃ or 0.5BaTiO₃-0.5CaTiO₃ (mole fraction) packing powder. The grain boundaries of the annealed specimens were oxidized in air. In the case of BaTiO₃ packing, grain-boundary migration occurred with the diffusion of BaTiO₃ along the grain boundary. The effective dielectric constant of the specimen decreased gradually as the temperature increased but showed two peaks, possibly because of barium enrichment at the grain boundary and an oxidized Sr(Ba)TiO₃ layer. In the case of 0.5BaTiO₃-0.5CaTiO₃ packing, although barium and calcium were present at the grain boundary of the specimen, no boundary migration occurred, as in a previous investigation. With the diffusion of barium and calcium, the resistivity of the specimen increased and the variation of the effective dielectric constant with temperature was much reduced, in comparison to those without solute diffusion. These enhanced properties were attributed to the solute enrichment and the formation of a thin diffusional Sr(Ba,Ca)TiO₃ layer at the grain boundary.     

Conversion of SiO2 Diatom Frustules to BaTiO3 and SrTiO3

Diatom frustules were used as bio-templates to synthesize functional ceramics via solid–gas displacement reactions. Silica-based frustules were exposed to TiF₄ at 330°C to form TiOF₂, which was later converted to TiO₂ (anatase) by heat treatment in air at 600°C. The TiO₂ frustules were then exposed to molten Ba(OH)₂ or Sr(OH)₂ to form BaTiO₃ or SrTiO₃, respectively. In both cases, near-complete conversion was achieved while retaining the morphology of the original silica frustules. BaTiO₃ and SrTiO₃ frustules exhibit nearly phase pure, nanocrystalline perovskite structure.     

Contribution of Structure to Temperature Dependence of Resonant Frequency in the (1 −x)La(Zn1/2Ti1/2)O3·xATiO3 (A = Ca, Sr) System

The crystal structure and microwave dielectric properties of the (1 − x ) La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ system were investigated. X-ray powder diffraction showed that cation ordering disappeared at x > 0.3 for both systems. However, infrared spectra demonstrated that short-range cation ordering could exist at x = 0.4. Permittivity and the temperature coefficient of the resonant frequency (τ_f) of both systems exhibited nonmonotonic variations with composition. Both systems exhibited a τ_f of zero at the same composition of x = 0.5 although the τ_f of SrTiO₃ was about two times larger than that of CaTiO₃. The behavior of the permittivity and τ_f were described by the tilting of oxygen octahedra and cation ordering. The relation between τ_f and cation ordering of La(Zn_1/2Ti_1/2)O₃ was discussed in conjunction with the experimental results on metal halides. It is suggested that cation ordering induced a negative τ_f and suppressed the increase of permittivity for compositions between x = 0 to x = 0.5 for (1 − x )La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ systems.     

Phase Equilibria in the System BaTiO3–SrTiO3

Phase equilibria in the binary system BaTiO₃–SrTiO₃ were studied above 1200°C. This system is characterized by a complete series of solid solutions with a minimum at 2.5 mole % SrTiO₃ and 1585°C. The hexagonal BaTiO₃ phase is suppressed to a region extending no farther than 0.5% SrTiO₃ at 1600°C. No immiscibility gap was found.     

Synthesis and Characterization of Sr2Ce2Ti5O16 in the System SrO-CeO2-TiO2

The ternary system SrO-CeO₂-TiO₂ was investigated using X-ray diffractometry. The formation of a new compound, Sr₂Ce₂Ti₅O₁₆, was established, and its compatibilities with SrO, SrCeO₃, and SrTiO₃ were studied. The results revealed the existence of a series of compounds Sr_6–12xCe_6xTi₅O₁₆ and solid solutions Sr_2+nCe₂Ti_5+nO_16+3n ( n ≤ 6).     

Microstructure of SrTiO3 Boundary-Layer Capacitor Material

SiTiO₃ capacitor material with indiffused Bi₂O₃ was studied using SEM, ESCA combined with Ar⁺ ion-etching, and TEM equipped with EDX. The apparent thickness of a second-phase layer observed with SEM was found to be influenced by in-depth effects. ESCA and TEM results show that only a 10- to 100-nm thick layer of second phase is present between the SrTiO₃ grains. In addition, it was found with TEM that the outer part of each grain contained Bi (at most 2 at.%), representing a diffusion layer. These results have implications for the boundary-layer model proposed to explain the dielectric properties .     

Formation of Core-Shell Structure in the BaTiO3-SrTiO3 System

When a 1-mol%-Fe₂O₃-added 0.67BaTiO₃-0.33SrTiO₃ (mole ratio) powder compact was sintered at 1380°C, a core-shell structure was developed. The core phase formed via solid-state interdiffusion of barium and strontium ions between BaTiO₃ and SrTiO₃ particles. In contrast, the shell phase formed via a solution-precipitation process in the presence of an Fe₂O₃-containing liquid phase. Energy-dispersive X-ray analysis showed that the core was a strontium-rich paraelectric phase and the shell was a barium-rich ferroelectric phase at room temperature. The core-shell structure developed in the BaTiO₃-SrTiO₃ system suggests the possibility of obtaining a variety of phase distributions with different Curie temperatures.     

Preparation of Ba2YCu3O7-δ Thin Films with Preferred Orientation through an Organometallic Route

Superconducting Ba₂YCu₃O_7-δ thin films were prepared through an organometallic route. Single-phase Ba₂YCu₃O_7-δ thin films with preferred orientation were successfully prepared on SrTiO₃ (100) single-crystal substrates at 800°C by a dip coating method using partially hydrolyzed Ba-Y-Cu organometallic solutions. Preferentially oriented Ba₂YCu₃-O_7-δ thin films were also prepared on MgO (100) substrates. By controlling the partial hydrolysis conditions, a coating solution for precursor thin films was kept accurately at the stoichiometric composition. The use of ozone gas during the pyrolysis of the precursor thin films was found to suppress the formation of BaCO₃. Ba₂YCu₃O_7-δ thin films with c -axis orientation perpendicular to a SrTiO₃ (100) substrate, which were heat-treated at 900°C for 15 min, exhibited a superconductivity transition with an onset of 90 K and an end of 75 K.     

Chemical Control of the Grain-Boundary Migration of SrTiO3 in the SrTiO3─BaTiO3─CaTiO3 System

The grain-boundary migration induced by chemical instability has been studied in SrTiO₃. Sintered SrTiO₃ has been packed with various BaTiO₃/CaTiO₃ powder mixtures and annealed at 1400°C for various times. At the surface region of most SrTiO₃ specimens, the grain boundary has migrated with the diffusion of Ba and Ca ions. The ratio of Ba and Ca ions present in the migrated region varies with the depth from the surface and the packing-powder composition, and is not equal to the cation ratio of packing powder. When the Ba/Ca ratio of packing powder is 1, cessation of migration has been observed. The composition of the area without migration is estimated to be approximately equal to the composition for the matching of crystal lattices between the original grain (SrTiO₃) and the layer formed by diffusion of Ba and Ca ions. The coherency strain energy induced by diffusion of solute atoms is believed to be the major driving force for the grain-boundary migration of SrTO₃ under the chemical instability. The grain-boundary migration can be accordingly controlled by lattice parameter change and matching.     

Synthesis of High Aspect Ratio Platelet SrTiO3

A method for synthesis of high aspect ratio platelet seeds by growth of SrTiO₃ on Sr₃Ti₂O₇ core particles is reported. The aim of this study was to identify and control the morphology and size of SrTiO₃ particles via molten salt synthesis. Platelet and tabular morphologies with rectangular faces were obtained using rutile and anatase, respectively. Platelet SrTiO₃ particles with an edge length of 10–40 μm and a thickness of 1–4 μm were obtained. High aspect ratios (edge length to thickness) of 7–10 were measured for platelet particles as opposed to lower aspect ratios of 2–4 for tabular particles. Highly anisotropic platelets are suitable template candidates to achieve textured ceramics.     

Microstructure–Dielectric Properties Relationship in Ba0.6Sr0.4TiO3–Mg2SiO4–Al2O3 Composite Ceramics

0.60Ba_0.6Sr_0.4TiO₃(BST)–(0.40− x )Mg₂SiO₄(MS)– x Al₂O₃ ( x =0, 0.5, 3, 5wt%) composite ceramics exhibit excellent characteristics suitable for tunable device applications. With increasing amount of Al, the dielectric peak can be quantitatively broadened and suppressed; the "phase transition temperature" T _c or ( T _m) shifts to a lower temperature. Meanwhile, the tunability is still high in a wider temperature range. Far from T _c, pyroelectric effects are observed by using the Byer and Roundy technology and Slim polarization hysteresis loops are observed under high ac dielectric field at 10Hz. These proved the existence of spontaneous polarization in certain possible orientations in a broad temperature range above T _c in the paraelectric medium and reveal why 0.60BST–(0.40− x )MS– x Al₂O₃ have such remarkable dielectric nonlinearity.     

Atomic Resolution Imaging of Au Nanocluster Dispersed in TiO2, SrTiO3, and MgO

Gold nanoclusters dispersed in single crystal TiO₂, MgO, and SrTiO₃ have been prepared by ion implantation at 300–975 K and subsequent annealing at 1275 K for 10 h. High-resolution transmission electron microscopy and high-angle annular dark field (HAADF) imaging in aberration corrected scanning transmission electron microscope (STEM) have been used to characterize the microstructure of the gold nanoclusters dispersed materials. STEM-HAADF imaging with atomic resolution has directly revealed for all three materials that Au atoms partially occupy cation lattice positions. Cavities up to several tens of nanometers were observed in MgO and SrTiO₃. The cavities and gold clusters are spatially associated in MgO and SrTiO₃, indicating a strong interaction between the Au cluster and cavities. For MgO and SrTiO₃, the faceting planes appear to be the same for both nanometer-sized cavity and the Au cluster, demonstrating that both the surface energy and the interfacial energy between Au cluster and the matrix are lowest on these planes.     

Oxygen Partial Pressure and Grain Growth in Donor-Doped BaTiO3

The grain growth of donor-doped BaTiO₃ at different oxygen partial pressures was studied. Results showed that the oxygen pressure had a pronounced influence on the grain growth and related effects. A model for the grain size anomaly during sintering of donor-doped BaTiO₃ in the presence of a TiO₂-rich liquid phase is proposed.