Low-Temperature Sintering of (Ba0.6Sr0.4)TiO3

An addition of just 0.4 wt% Li₂O to (Ba_0.6Sr_0.4)TiO₃ powder was able to reduce the sintering temperature to ≤900°C and produce ceramics with a relative density of 97%. Small amounts of two secondary phases were formed during this process: Li₂TiO₃ and Ba₂TiO₄. The addition of Li₂O depresses the ferroelectric character of the (Ba_0.6Sr_0.4)TiO₃ and, as a result, reduces the permittivity, improves the temperature coefficient of permittivity, and reduces the dielectric losses. The tunability shows no significant variation with Li₂O concentration and remains between 16.5% and 13.5%. A low-temperature sintering mechanism was proposed. The mechanism involves the intermediate formation of BaCO₃, its melting and the incorporation of Li⁺ into the BST. The sintering mechanism can be characterized as reactive liquid-phase sintering.     

The Structure and Dielectric Tunable Properties of Fine-Grained Ba0.6Sr0.4TiO3 Ceramics Prepared by Spark Plasma Sintering

Barium strontium titanate is a promising material for microwave-phased array applications. ^1,2 In this study, highly dense and fine-grained Ba_0.6Sr_0.4TiO₃ ceramics were prepared using the spark plasma sintering (SPS) technique. The structure and dielectric tunable properties of the samples were investigated. The "distorted nano-region" emerged in the interior of the grains of SPS samples, and resulted in the deterioration of the dielectric tunable properties of Ba _x Sr_{1− x} TiO₃. This phenomenon indirectly testified to the assumption of the "polar nano-region" mechanism. After the SPS samples were annealed, the "distorted nano-region" disappeared and better dielectric tunable properties were obtained. The dielectric constant was decreased to 1048, and the K value (Commutation Quality Factor) reached 7089.     

Construction of PbZr0.4Ti0.6O3- and Ba0.9Sr0.1TiO3-Based Optical Microcavities by Chemical Solution Deposition

Herein we report on a simple, low cost, and feasible route for the construction of PbZr_0.4Ti_0.6O₃ (PZT)- or Ba_0.9Sr_0.1TiO₃ (BST)-based optical microcavities using a single chemical solution containing polymer polyvinylpyrrolidone. The obtained multilayer systems not only exhibit good ferroelectric performance, but also display well-defined resonant modes with a quality factor of no <66. Compared with PZT microcavities, the optical properties of the BST microcavities appear to be superior.     

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.     

Fabrication and Characterization of Pyroelectric Ba0.8Sr0.2TiO3 Thin Films by a Sol-Gel Process

A sol-gel process was used to prepare pyroelectric Ba_0.8Sr_0.2TiO₃ thin films with large columnar grains (100–200 nm in diameter) on Pt/Ti/SiO₂/Si substrates, via using a 0.05 M solution precursor. The relationship between dielectric constant and temperature (ɛ_r- T ) showed two distinctive phase transitions in the Ba_0.8Sr_0.2TiO₃ thin films. Both the remnant polarization and the coercive field decreased as the temperature increased from −73°C to 40°C. Its low dissipation factor (tan δ= 2.6%) and high pyroelectric coefficient ( p = 4.6 × 10⁻⁴ C·(m²·K)⁻¹ at 33°C), together with its good insulating properties, made the prepared Ba_0.8Sr_0.2TiO₃ thin films promising for use in uncooled infrared detectors and thermal imaging applications.     

Effects of Heating Rate on the Sintering Behavior and the Dielectric Properties of Ba0.7Sr0.3TiO3 Ceramics Prepared by Boron-Containing Liquid-Phase Sintering

The effects of heating rate on the sintering behavior and the dielectric properties of Ba_0.7Sr_0.3TiO₃ ceramics prepared by boron-containing liquid-phase sintering were investigated. When 0.5 wt% B₂O₃ was added to Ba_0.7Sr_0.3TiO₃, sintering was achieved at ∼1150°C, and the overdoped B₂O₃ did not form an adequate amount of liquid phase or volatilize; it remained in the samples and formed a secondary phase. A transition broadening was observed as the heating rate increased. As the heating rate increased, the Curie temperature increased and the maximum dielectric constant ( k _max) at the Curie temperature decreased. This result is attributable to a decrease in the diffuseness parameter (δ) and the tetragonality ( c / a ).     

Effect of Donor, Acceptor, and Donor–Acceptor Codoping on the Electrical Properties of Ba0.6Sr0.4TiO3 Thin Films for Tunable Device Applications

We have investigated the effects of donor, acceptor, and donor–acceptor codoping on both the dielectric properties and the leakage current behavior of Ba_0.6Sr_0.4TiO₃ thin films prepared by the metalorganic solution deposition technique. La and Co were selected as donor and acceptor dopants, respectively. The electrical properties depend strongly on the type of dopants. Compared with others, codoped BST films have a much lower loss tangent, higher figure of merit, and lower leakage current. The electronic conduction mechanisms of the three types of dopants are reported.     

Structural and Electric Properties of Sol–Gel-Derived Ba0.9Sr0.1TiO3 Multilayers

Crack-free Ba_0.9Sr_0.1TiO₃ (BST) and Mn-doped Ba_0.9Sr_0.1TiO₃ (BSTM) multilayers with thickness over 2 μm have been prepared by chemical solution deposition based on one single precursor. Both multilayers exhibit good performance as Bragg reflectors. Mn doping tends to suppress the leakage current in BST multilayers effectively by smoothing the layers and the reduction of the charge carries. The Mn-doped BST multilayer displays an excellent ferroelectric property, with an average remnant polarization ( P _r⁺– P _r⁻)/2 of 12.69 μC/cm² and an average coercive field ( E ⁺ – E ⁻ )/2 of about 72.95 kV/cm under an applied field of 440 kV/cm.     

Direct-Current Field Dependence of Dielectric Properties in Alumina-Doped Barium Strontium Titanate

The dielectric properties of (Ba_0.6Sr_0.4)TiO₃ and Al₂O₃-doped (Ba_0.6Sr_0.4)TiO₃ have been characterized. The grain size of the specimen is maximum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃. The density and the real part of the relative dielectric constant each decrease as the Al₂O₃ content increases. The loss factor is minimum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 2 wt% Al₂O₃. The dielectric constant of the specimens decreases as the applied dc field increases. The influence of the dc field on the loss factor is much less than that on the dielectric constant. The tunability is ∼24% for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃.     

Effects of B2O3 Addition on the Dielectric and Ferroelectric Properties of Ba0.7Sr0.3TiO3 Ceramics

The effects of B₂O₃ addition on the sintering behavior and the dielectric and ferroelectric properties of Ba_0.7Sr_0.3TiO₃ (BST) ceramics were investigated. The dielectric and ferroelectric properties of a BST sample with 0.5 wt% B₂O₃ sintered at <1150°C were as good as those of undoped BST sintered at 1350°C, and the dielectric loss was better. When >1.0 wt% B₂O₃ was added to BST, the overdoped B₂O₃ did not form a liquid phase or volatilize; it remained in the samples and formed a secondary phase that lowered the sintering behavior and the dielectric and ferroelectric properties of the BST.     

Formation of BaTiO3 from BaCO3 and TiO2 in Air and in CO2

The formation of BaTiO₃ from equimolar BaCO₃ and TiO₂ (rutile) mixtures was studied in air and in CO₂. A small amount of BaTiO₃ is formed first directly from BaCO₃ and TiO₂ at the surface of contact. From then on it is a diffusion-controlled reaction, and both BaTiO₃ and Ba₂TiO₄ are produced, with Ba₂TiO₄ being formed in much larger amounts. In 1 atmosphere of CO₂, the intermediate Ba₂TiO₄ was suppressed up to a temperature of about 1100°C. in agreement with thermodynamic calculations. Ba₂TiO₄ reacts fast with 1 atmosphere of CO₂ below about 1100°C. to produce BaTiO₃and BaCO₃     

The Optical Properties and Band Gap Energy of Nanocrystalline La0.4Sr0.6TiO3 Thin Films

The effects of microstructure on the optical properties of La_0.4Sr_0.6TiO₃ thin films were investigated. Dense films with the thickness of ∼200 nm and grain size 14–30 nm were produced on monocrystalline sapphire substrates by using a polymeric precursor spin coating technique at annealing temperatures under 800°C. X-ray data showed the formation of a single-phase cubic perovskite-type structure similar to undoped SrTiO₃ for annealing temperatures >500°C. The results of optical measurements showed that the optical spectra varied with the change of the grain size. From these data, the absorption coefficients were calculated and the band gap energy determined. In agreement with the quantum confinement model, it was shown that the band gap energy increased as the grain size decreased.     

Low-Temperature Sintering (Ba0.6Sr0.4)TiO3 Thick Film Prepared by Screen Printing

(Ba_0.6Sr_0.4) TiO₃ thick films doped with glass slurry were fabricated by the screen-printing technique. The dielectric properties and the sintering mechanism were investigated. The films can be sintered at 600°C. The dielectric constant is 88 and the dielectric loss is 0.002 with a tunability of 23.86% under 100 kV/cm. Higher dielectric constant and tunability were obtained in the samples sintered at higher temperatures. The highest tunability is 61.12% under 150 kV/cm in the sample sintered at 800°C. The low sintering temperature and dielectric loss of the glass-doped thick films make them potential candidates for LTCC and microwave tunable devices.     

Molten-Salt Synthesis of Ba1–xPbxTiO3 in the System BaTiO3–PbCl2

Ba_{1– x} Pb _x TiO₃ powder with a fixed composition was prepared by the reaction of BaTiO₃ powders with molten PbCl₂at various PbCl₂/BaTiO₃ molar ratios at 600° and 800°C in a nitrogen atmosphere. When 0.1 μm powder was used, the reaction was finished when x = 0.9. Two phases of BaTiO₃and a solid solution of Ba_{1– x} Pb _x TiO₃ coexisted, but the final phase gave a solid solution of Ba_{1– x} Pb _x TiO₃ at 800°C. When 0.5 μm powder was used, the two phases coexisted in the products at 600°C at PbCl₂/BaTiO₃= 1.0. A sintered compact of Ba_{1– x} Pb _x TiO₃ powders solid solution was prepared by hot isostatic pressing, and its dielectric constant was measured in the temperature range 20°–550°C.     

Effect of Orientation on the Ferroelectric Behavior of (Pb,Sr)TiO3 Thin Films

Pb_0.6Sr_0.4TiO₃ (PST) ferroelectric thin films were prepared on two different substrates by sol–gel methods. Films derived on the LaNiO(LNO)/Pt/Ti/SiO₂/Si substrates showed a strong (100) preferred orientation. The PST thin films grown on the LNO/Pt/Ti/SiO₂/Si(100) substrate showed a non-uniform rounded grain size distribution and have a larger polarization and lower coercive field E _c. The dependence of electrical properties derived on the Pt/Ti/SiO₂/Si and LNO/Pt/Ti/SiO₂/Si substrates has been studied, with a focus on the change of dielectric constant versus direct current (DC) bias field. The dielectric and ferroelectric properties of the Pb_0.6Sr_0.4TiO₃ thin films deposition on two kinds of substrates were investigated as a function of temperature, frequency and DC bias field.     

Chemical Solution Deposition of Transparent and Metallic La0.5Sr0.5TiO3+x/2 Films Using Topotactic Reduction

Metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films were prepared by the chemical solution deposition (CSD) method using topotactic reduction processing. The use of Si powder as the reducing agent was facile and allowed easy manipulation. It was observed that metallic (resistivity at 300 K ∼2.43 mΩ cm) and transparent (∼80% transmittance at visible light) La_0.5Sr_0.5TiO_{3+ x /2} films could be obtained with an annealing temperature of 900°C, which was significantly lower than the hydrogen reduction temperature (∼1400°C). The successful preparation of metallic and transparent La_0.5Sr_0.5TiO_{3+ x /2} films using CSD has provided a feasible route for depositing other perovskite-structured functional layers on La_0.5Sr_0.5TiO_{3+ x /2} films using this low-cost all CSD method.     

Spark Plasma Sintering Behavior of Nano-Sized (Ba, Sr)TiO3 Powders: Determination of Sintering Parameters Yielding Nanostructured Ceramics

Nano-powders of BaTiO₃, SrTiO₃, Ba_0.6Sr_0.4TiO₃ (BST64), and a mixture of the composition (BaTiO₃)_0.6(SrTiO₃)₀₄ with particle sizes in the range of 60–80 nm were consolidated by spark plasma sintering (SPS). An experimental procedure is outlined that allows the determination of a "kinetic window," defined as the temperature interval within which the densification process can be kinetically separated from the grain growth one, enabling preparation of dense nanostructured ceramics. The width of this window varied from almost zero for BST64 to 125°C for the (BaTiO₃)_0.6(SrTiO₃)_0.4 mixture. During the densification (sintering) of the (BaTiO₃)_0.6(SrTiO₃)₀₄ mixture, BST64 is formed. The main part of this reaction occurs in a fully densified body through which suggesting that the constitutional phase(s) have a self-pinning effect on the grain growth.     

Microwave Dielectric Properties of A6B5O18-Type Perovskites

Cation-deficient perovskites with the general formula A₆B₅O₁₈ (A=Ba, Sr, La; B=Nb, Ta, Ti, Zr, Mg, and Zn) have been synthesized and their microwave dielectric properties have been investigated. X-ray diffraction studies indicate the formation of monophase materials. The structures of Ba₆Ta₄TiO₁₈ and Ba₅SrTa₄TiO₁₈ are different from that of Sr₆Ta₄TiO₁₈. The A₆B₅O₁₈ have Q × f in the range 5600–51 000 GHz, dielectric constants 26–48, and the temperature coefficient of resonant frequency varies from −39 to +83 ppm/°C, depending on the composition. Scanning electron microscopy studies show that the grain size decreases with an increase in the Sr content.     

Improvement of Microwave Loss Tangent and Tunability of Ba0.55Sr0.45TiO3/MgO Composites Using the Heterogeneous Precipitation Method

Ba_0.55Sr_0.45TiO₃/MgO composites were successfully prepared by the heterogeneous precipitation method and their structural, surface morphological, tunable properties, and dielectric properties at microwave frequency were systemically investigated. Compared with the sample prepared by the traditional solid-state method, the sample prepared by the heterogeneous precipitation method exhibits a smaller grain size, more uniform microstructure, higher tunability, and lower microwave loss, and these properties are very beneficial to the development of the microwave tunable devices application. Moreover, the effects of La₂O₃ doping on the dielectric and tunable properties of BST/MgO composites are investigated. The result shows that the La³⁺-doped sample has higher tunability and lower microwave loss than the undoped one.     

Effects of CuO Doping on the Microstructural and Dielectric Properties of Ba0.6Sr0.4TiO3 Ceramics

This study investigates the effect of CuO on the sintering behavior, dielectric properties, and microstructures of Ba_0.6Sr_0.4TiO₃ (BST) ceramics. The ceramics were sintered in air at temperatures ranging from 1000° to 1230°C. It is found that a small amount of added CuO (0.6 mol%) can significantly increase the density and improve the dielectric properties of BST ceramics. Doped BST ceramics can be sintered to a density >95% of the theoretical density at 1150°C. scanning electron microscopic observations show that the BST grain sizes increase with increasing amounts of CuO. No secondary phases in the BST ceramics are observed using X-ray diffraction pattern for CuO additions up to 0.9 mol%. However, compositional analysis using transmission electron microscopy-EDX for the BST ceramics with 0.9 mol% CuO sintered at 1150°C showed that a small level of secondary phase formation is present. On the other hand, large dislocations are observed for BST with 0.6 mol% CuO addition as a result of lattice distortion, which creates the vacancy condensation because of the atomic mismatch in the solid solutions. Optimal CuO doping concentrations can reduce the loss tangents of BST that can also ensure a high dielectric constant. When the doping concentration of CuO is 0.6 mol% and the ceramic is sintered at 1150°C, the BST ceramic has the following properties at 1 MHz: dielectric constant=4094, tan δ=0.55%.