Formation of BaTiO3 from Barium Oxalate and TiO2

Barium titanate powder has been prepared via a semi-oxalate method that uses barium oxalate and TiO₂ precursors, instead of titanyl oxalate. Barium oxalate was precipitated from nitrate solution onto the surface of TiO₂ powders. Crystallization of BaTiO₃ from the precursors was investigated by TGA, DTA and XRD analysis. It is evident that an intermediate barium oxycarbonate along with BaCO₃, forms between 450–500°C and that decomposes to BaCO₃ again at high temperature. Decomposition of BaCO₃ occurs at much lower temperature, from 600°C onwards, due to the presence of TiO₂. The precursor completely transforms into BaTiO₃ at 900°C. Nanometer size BaTiO₃ crystallites are produced during this synthesis due to the lower calcination temperature. The crystalline morphology of BaTiO₃ is controlled mainly by the morphology of BaCO₃, which formed in the intermediate stage.     

Low-temperature sintering of BaTiO3 with Mn-Si-O glass

In order to reduce sintering temperature and prevent adverse dielectric effects, pure BaTiO₃ powder with the addition of Mn-Si-O glass was sintered in the temperature range of 1175–1300°C. Microstructural observation showed that BaTiO₃ grains of the sintered samples only grew from the initial 400 nm to an average of 430 nm between 1175–1275°C for 1 h, or sintered at 1250°C as long as 27 h. Abnormal BaTiO₃ grains are not found in the sintered samples. The microstructure and phase analysis showed that the dielectric properties, tetragonality, and grain growth of BaTiO₃ are closely controlled by the formation of the liquid phase, newly formed Ba₂TiSi₂O₈ grains, and Mn solid solution in BaTiO₃ grains.     

Growth of BaTiO3/SrTiO3 superlattices by injection MOCVD

Abstract

BaTiO₃ (BTO) and SrTiO₃ (STO) and Ba_xSr_1-xTiO₃ (x=0–1) (BST) thin films have been epitaxially grown on LaAlO₃ and SrTiO₃:Nb at a substrate temperature of 800°C using a new liquid source delivery technique called injection MOCVD. A X-ray study evidenced FWHMs of 0.16° and 0.45° for SrTiO₃ and BaTiO₃ respectively.

In a next step the feasibility of BaTiO₃/SrTiO₃ superlattices was studied. The multilayers obtained were epitaxially grown on LaAlO₃ as well as on SrTiO₃:Nb. The structural properties were studied using X-ray diffraction as well as XPS, proving the low interface roughness of 1nm. The XPS study also confirmed the absence of carbon contamination in the film.     

Low-temperature sintering of Li2O-doped BaTiO3 lead-free piezoelectric ceramics

Low-temperature sintering of BaTiO₃ ceramics using Li₂O as sintering aids was investigated with a special influences of Li₂O content (0–4?mol%) and sintering temperature (1000–1100°C) on crystalline structure and electrical properties. The sinterability of BaTiO₃ ceramics significantly improved by adding Li₂O, whose densification sintering temperature reduced from 1300°C to 1000°C. XRD pattern indicated that BaTiO₃-xLi₂O samples were single phase with a tetragonal symmetry as x?=?0–0.3?mol%, while the samples became an orthorhombic symmetry as x?=?0.5–4?mol%. The densification sintering temperature in which samples showed relative density higher than 90?% decreased with increasing Li₂O content. A maximum d ₃₃ value (200 pC/N) was obtained for the BaTiO₃-0.5?mol%Li₂O sample sintered at 1050°C, which is attributed to a vicinity of the phase transition and the high density. Adding Li₂O not only reduced the sintering temperature but also obtained the acceptable piezoelectric properties, which will make BaTiO₃ become a kind of promising and practical lead-free piezoelectric ceramics.     

Fabrication and operation limit of lead-free PTCR ceramics using BaTiO3–(Bi1/2Na1/2)TiO3 system

The electric properties of BaTiO₃–(Bi_1/2Na_1/2)TiO₃ (BT–BNT) solid solution ceramics were studied as a lead-free PTCR (positive temperature coefficient of resistivity) thermistor material usable over 130°C. For determining the maximum switching temperature T _s, the phase diagram of BT–BNT binary system was clarified. Two semiconductorization processes and their electric properties are described. The lanthanum(La)-doped BBNT ceramics sintered in air still showed dielectric behaviors, but the niobium(Nb)-doped ones had a low resistivity at room temperature, ρ _RT, on the order of 10³ Ωcm and showed a PTC behavior. Sintering under a low O₂ atmosphere produces BT–BNT ceramics with less than 10² Ωcm compared to those prepared in air. Our current research produced the BBNT ceramics with T _s values around 210°C by increasing the (Bi_1/2Na_1/2) content in the ceramics.     

PREPARATION OF BaTiO3 FILMS FOR MLCCS BY DIRECT VAPOR DEPOSITION

ABSTRACT

BaTiO₃ films were deposited by the direct vapor deposition (DVD) technique to prepare thin dielectric layers for multilayer ceramic chip capacitors (MLCCs). The BaTiO₃ films were successfully prepared by co-evaporation of the BaTiO₃ ceramic and Ti metal source. The films deposited at room temperature and 600°C were amorphous and crystalline phases, respectively. The intensity of (110) and (111) peaks increased as Ba/Ti ratios were close to stoichiometric composition. BaTiO₃ films deposited with e-beam power of 700 W showed the deposition rate of 33 nm/min. The dielectric constant and dissipation factor of BaTiO₃ films measured at 1 kHz were 150～ 180 and 2～ 5%, respectively. The capacitance decreased with increasing the temperature and varied only between 787pF and 752pF in the temperature range 15～ 125°C.     

Effect of reoxidation on positive temperature coefficient of resistance behavior for BaTiO3-K0.5Bi0.5TiO3 ceramics

As a positive temperature coefficient of resistivity (PTCR) material, (1-x)BaTiO₃-xK_0.5Bi_0.5TiO₃ (BT-KBT, 0.05≦ x ≦0.15) ceramics without any donor doping were prepared by a conventional oxide mixing method. All samples were sintered in an Ar atmosphere at 1280?~?1350°C, subsequently, reoxidized at 800?~?1100°C in a gas mixture (99 %Ar–1 %O₂). The PTCR behavior of BT-KBT ceramics were investigated in terms of KBT content, reoxidation temperature and time. The results showed that the BT-KBT ceramics exhibited an abrupt increase in their resistivity near the Curie temperature (Tc) after annealing in gas mixture, Tc of 0.9BT-0.1KBT ceramic was shifted to a higher temperature (~150°C). Furthermore, the room-temperature resistivity (ρ_RT) of ceramic samples sintered in Ar and reoxidized in a gas mixture decreased to 10² Ω·cm. The jump in resistivity (maximum resistivity [ρ_max]/minimum resistivity [ρ_min]) was enhanced by three orders of magnitude through a suitable reduction–reoxidation method without sacrificing the ρ_RT.     

Microwave dielectric properties of B2O3-added Li2MgTiO4 ceramics for LTCC applications

Li₂MgTiO₄ (LMT) ceramics which are synthesized using a conventional solid-state reaction route. The LMT ceramic sintered at 1250°C for 4 h had good microwave dielectric properties. However, this sintering temperature is too high to meet the requirement of low-temperature co-fired ceramics (LTCC). In this study, the effects of B₂O₃ additives and sintering temperature on the microstructure and microwave dielectric properties of LMT ceramics were investigated. The B₂O₃ additive forms a liquid phase during sintering, which decreases the sintering temperature from 1250°C to 925°C. The LMT ceramic with 8 wt% B₂O₃ sintered at 925°C for 4 h was found to exhibit optimum microwave dielectric properties: dielectric constant 15.16, quality factor 64,164 GHz, and temperature coefficient of resonant frequency -28.07 ppm/°C. Moreover, co-firing of the LMT ceramic with 8 wt% B₂O₃ and 20 wt% Ag powder demonstrated good chemical compatibility. Therefore, the LMT ceramics with 8 wt% B₂O₃ sintered at 925°C for 4 h is suitable for LTCC applications.     

Nanocomposite ceramics based on La-doped BaTi2O5 and BaTiO3 with high temperature-independent permittivity and low dielectric loss

Nanocomposite ceramics containing a mixture of two ferroelectric phases, La-doped BaTi₂O₅ and BaTiO₃, with carefully-controlled phase amounts and ceramic microstructure have temperature-independent permittivity and low dielectric loss over very wide temperature ranges: ɛ = 95 ± 10 from 25 to 600 °C; tan δ = 0.02(2) from 25 to 400 °C, measured at 100 kHz. Further optimisation of properties should be possible.     

Microstructure and electrical properties of the rare-earth doped 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 piezoelectric ceramics

Phase structure, microstructure, piezoelectric and dielectric properties of the 0.4 wt% Ce doped 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ (Ce-BNT6BT) ceramics sintered at different temperatures have been investigated. The powder X-ray diffraction patterns showed that all of the Ce-BNT6BT ceramics exhibited a single perovskite structure with the co-existence of the rhombohedral and tetragonal phase. The morphologies of inside and outside of the bulk indicated that the different sintering temperatures did not cause the second phase on the inside of bulk. However, the TiO₂ existed on the outside of the bulk due to the Bi₂O₃ and Na₂O volatilizing at higher temperature. The ceramics sintered at 1,200 °C showed a relatively large remnant polarization (P _r) of about 34.2 μC/cm², and a coercive field (E _c) of about 22.6 kV/cm at room temperature. The permittivity ? _r of the ceramics increased with the increasing of sintering temperature in antiferroelectric region, the depolarization temperature (T _d) increased below 1,160 °C then decreased at higher sintering temperature. The resistivity (ρ) of the Ce-BNT6BT ceramics increased linearly as the sintering temperature increased below 1,180 °C, but reduced as the sintering temperature increased further. A maximum value of the ρ was 3.125?×?10¹⁰ ohm m for the Ce-BNT6BT ceramics sintered at 1,180 °C at room temperature.     

Hydrothermal Preparation and Characterization of Ultra-Fine BaTiO3 Powders from Amorphous Peroxo-Hydroxide Precursor

Ultra-fine BaTiO₃ powders were hydrothermally prepared by using Ba Ti-peroxo-hydroxide precursor. Amorphous Ba Ti-peroxo-hydroxide precursor were prepared by coprecipitation of Ba(NO₃)₂ and TiCl₄ aqueous solution adding in NH₄OH aqueous solution. The phase-pure BaTiO₃ powders with a cubic perovskite structure were synthesized at temperature as low as 110_C and in the pH range of 10–12. This processing method provides a simple low temperature route for producing BaTiO₃ nanoparticles. Under a TEM image and a SAD pattern analysis, it is evident that BaTiO₃ powders had spherical shape and single crystal nature. The BaTiO₃ ceramic sintered at 1200_C for 1 h had 97% of theoretical density and a relatively high dielectric constant ( _r = 3500).     

Analysis on the temperature dependent structural properties of Li2CO3 doped (Ba,Sr)TiO3 ceramics

We have fabricated various amount of Li₂CO₃ doped (Ba,Sr)TiO₃ (BST) ceramics for LTCCs (Low Temperature Co-fired Ceramics) applications through the conventional sintering method. By introducing Li₂CO₃ into BST ceramics, the sintering temperature was decreased from 1350°C to 900°C. In this study, we discussed the crystalline and structural properties of Li₂CO₃ doped BST ceramics. By scanning X-ray diffraction analysis, we found that 1, 3, and 5 wt% Li₂CO₃ doped (Ba,Sr)TiO₃ ceramics have perovskite structure without any pyrochlore phases. Frequency dependent dielectric properties were analyzed and discussed. Scanning Electron Microscopy (SEM) images depending on the sintering temperature and dopants were prepared and discussed. The crystalline and dielectric properties of Li₂CO₃ doped (Ba,Sr)TiO₃ were discussed.     

Effect of attrition milling on the piezoelectric properties of Bi0.5Na0.5TiO3-based ceramics

Bismith sodium titanate (BNT)-based powders were prepared by conventionally mixed-oxide method using Bi₂O₃, Na₂CO₃ and TiO₂. The La₂O₃ was added as the modifier to the BNT composition for easily poling and reducing an abnormal dielectric loss at high temperatures. In this study, the investigated compositions were Bi_0.5Na_0.5TiO₃ and Bi_0.5Na_0.485La_0.005TiO₃. The powders were calcined at 900 °C for 2 h by slow heating rate at 100 °C/h. The calcined BNT-based powders were then attrition-milled for 3 h with a high speed at 350 rpm. After drying, the fine powders were uniaxially pressed and then cold-isostatically pressed (CIP) at 240 MPa for 10 min. All pressed pellets were sintered at 1000–1100 °C for 2 h in air atmosphere. The microstructure of sintered pellets was investigated by SEM. Results of dielectric and piezoelectric property measurement were also reported.     

Ab initio calculations of the BaTiO3 (100) and (110) surfaces

We present and discuss the results of calculations of BaTiO₃ (100) surface relaxation and surface rumpling with two different terminations (BaO and TiO₂) and BaTiO₃ (110) surface relaxation with three different terminations (Ba, TiO and O). These are based on a hybrid B3PW exchange-correlation technique. The O-terminated A-type BaTiO₃ (110) surface has a surface energy close to that for the (100), which indicates that both (110) and (100) BaTiO₃ surfaces can exist simultaneously in perovskite ceramics.     

Sintering and dielectric properties of Al2O3 ceramics doped by TiO2 and CuO

The effects of CuO and TiO₂ additives on the microstructure and microwave dielectric properties of Al₂O₃ ceramics were investigated. Al₂O₃ ceramics with CuO and TiO₂ additions can be well sintered to achieve 93∼98% theoretical densities below 1,360 °C due to Ti₄Cu₂O liquid phase sintering effect. The Qf values decreased with increasing CuO and TiO₂ content, due to the formation of the second phase Ti₄Cu₂O. However, the varying behaviors of the dielectric constant (ɛ _r ) and temperature coefficients (τ _f ) were associated with phase constitutions, as a result of the change of CuO and TiO₂content. The τ _f can be shifted close to 0 ppm/°C by controlling the content of CuO and TiO₂. The specimens with 0.5 wt.% CuO and 7 wt.% TiO₂ sintered at 1,360 °C for 4 h showed ɛ _r of 11.8, Qf value of 30,000 GHz, and τ _f of −7 ppm/°C.     

Pulsed Laser Deposited Ba(Mg1/3Ta2/3)O3 Microwave Dielectric Thin Films

Ba(Mg_1/3Ta_2/3)O₃ (BMT) microwave dielectric thin films were successfully synthesized by a modified pulsed laser deposition (PLD) process, which includes low temperature (200°C) deposition and high temperature (>500°C) annealing. Crystalline structured BMT thin films were obtained when the PLD-deposited films were post-annealed at a temperature higher than 500°C in oxygen atmosphere. The characteristics of BMT thin film, including crystallinity, grain size, film roughness, and dielectric properties were improved with annealing temperature, achieving dielectric constant K = 23.5 and dissipation factor tan δ = 0.015 (at 1 MHz) for the 800°C-annealed films.     

Synthesis of BaTiO3 by soft chemistry routes

In this paper we report a comparison concerning the properties of BaTiO₃ (BTO) ceramics obtained by two soft chemical routes, modified Pechini method and thermal decomposition of oxalate-based precursor. XRD data show the formation of single phase BaTiO₃ with tetragonal symmetry when the polymeric citrate-based precursor was annealed at 850 °C, 2 h. In the case of oxalate based-precursor, longer thermal treatment is required to obtain BaTiO₃ free of any secondary phases. For BaTiO₃ powders prepared by modified Pechini method, TEM and SEM investigations revealed the obtaining of uniformly sized particles forming spherical agglomerates inside large, non-uniform and partially sintered aggregates. The powders synthesized via oxalate route show particles of various sizes, with the same tendency of spherical agglomerates formation, but unlike the modified Pechini synthesis, more uniform and smaller aggregates with well-defined hexagonal-like shape were noticed. The relative permittivity values of 6,478 and 5,088 at Curie temperatures of 127 and 130 °C and low dielectric losses (tan δ?=?0.012) at room temperature were obtained for ceramic samples synthesized via Pechini method and oxalate route, respectively.     

Fabrication and electrical properties of textured Na1/2Bi1/2TiO3-BaTiO3 ceramics by reactive-templated grain growth

The <001> fiber-textured Na_1/2 Bi_1/2TiO₃-BaTiO₃ (6 mol% BaTiO₃) ceramics were fabricated by reactive-templated grain growth (RTGG), using plate-like Bi₄Ti₃O₁₄ (BiT) particles prepared by a molten salt method as templates. The effects of sintering conditions on texture development and microstructure evolvement were both studied, and the mechanisms of grain orientation and densification were discussed. High Lotgering factor (≥96%) and high density (≥96% theoretic density) textured Na_1/2 Bi_1/2TiO₃-6BaTiO₃ ceramics were prepared by using the max templates concentration supplying 100% Bi in the final product, and sintering at 1200 °C for 10 h. The NBT-6BT obtained exhibited good piezoelectric performance with piezoelectric coefficient d ₃₃ ?=?241pC/N, and electromechanical coupling factor k _p ?=?41.2%, k _t ?=?66.5% at room temperature.     

Gas-phase driven nano-machined TiO2 ceramics

A simple, inexpensive gas phase reaction termed as “nanocarving process” converts TiO₂ grains into arrays of single crystal nanofibers by selective and anisotropic etching. This process is conducted by exposing dense polycrystalline TiO₂ to a H₂/N₂ environment at 700 °C. The dimensions of nanofibers are around 20 nm in diameter and 1 μm in length. The preferred crystallographic orientation for the nanocarving process is the <001> direction. Nanoparticles composed of Fe and Ni were observed on the surface of TiO₂ that formed nanofiber tips. Sintering parameters before the nanocarving treatment play a critical role in the formation of nanofibers. As sintering temperature and time increased, the rate of nanofiber generation decreased. Moreover, it was observed that by varying the heat treatment conditions, it is possible to create other structures like nanowhiskers and nanofilaments. Nanowhiskers were formed by reoxidation of nanofiber-formed TiO₂ over 600 °C. Nano-filaments were generated by heat treating sintered TiO₂ in N₂-carrying water vapor at 700 °C.     

La2O3–B2O3–TiO2 Glass/BaO–Nd2O3–TiO2 ceramic for high quality factor low temperature co-fired ceramic dielectric

A conventional BaO–Nd₂O₃–TiO₂ ceramic of microwave dielectric material was added to rare-earth derived borate glasses (La₂O₃–B₂O₃–TiO₂) for use as LTCC (low temperature co-fired ceramic) materials. The sintering behavior, phase evaluation, and microwave dielectric properties were investigated. It was found that increasing the sintering temperature from 750 to 850 °C led to increases in shrinkage and microwave dielectric properties (≈15 for ?_r , >10,000 GHz for Q*f₀ and >94 ppm/ °C for τ _f at 7–8 GHz for resonant frequency). The results suggest that a composite with suitable additives for τ _f could feasibly be developed as a material for LTCC applications.