Preparation and properties of strontium barium niobate based glass-ceramics for energy storage capacitors

Na₂O–BaO–SrO–Nb₂O₅–B₂O₃–SiO₂ glass-ceramics were prepared by melt-casting followed by controlled crystallization. X-ray diffraction results show that Ba_0.27Sr_0.75Nb₂O_5.78 with tungsten bronze structure formed as the dielectric phases from the glass matrix at 800°C. However, a secondary phase NaSr_1.2Ba_0.8Nb₅O₁₅ occurs when crystallization temperature exceeds 850°C. The glass-ceramics exhibit excellent stability in permittivity values from room temperature to 200°C and low dielectric losses below 0.05. Electrical testing demonstrates that the breakdown strength increases with crystallization temperature. The P–E characteristics at room temperature do not show any clear ferroelectric behavior. The glass-ceramic material heated at 800°C/3 h + 950°C/3 h shows a breakdown strength of 1400 kV/cm and its energy storage density can reach up to 4.0 J/cm³, which may be a strong candidate for high energy density storage capacitors for portable or pulsed power applications.     

Dielectric, thermal and sintering behavior of BaO-B2O3-SiO2 glasses with the addition of Al2O3

In the Pb-free low temperature sinterable glass of the (55)BaO-(35)B₂O₃-(10)SiO₂ system, different amounts of Al₂O₃ were added and the crystallization behavior, sintering behavior and physical characteristics of the glass were examined. It was found that Al₂O₃ suppressed crystallization of the glasses because it played the role of a network former. The glass transition temperatures, crystallization temperatures, and optimum sintering temperatures increased as the amount of Al₂O₃ increased. In the case of a specimen with a large amount of Al₂O₃, which was not easily crystallized, an over-firing phenomenon was observed when the sintering temperature was higher than the optimum sintering temperature. While the over-firing phenomenon was not observed due to the crystallization in the sample with a little amount of Al₂O₃. The dielectric constant and thermal expansion coefficient of the glasses were also examined and explained in correlation with the crystallization and densification.     

The effect of TiO<Subscript>2</Subscript> and P<Subscript>2</Subscript>O<Subscript>5</Subscript> on densification behavior and properties of Anortite-Diopside glass-ceramic substrates

In this work the synthesis of anorthite-diopside glass-ceramics (GCs) was carried out via sintering and crystallization of glass powder compacts in the temperature interval 800°C and 950°C. Glass powder compacts with mean particle size of 2 μm were prepared. The effects of adding TiO₂ and P₂O₅ on the sintering behavior of glass powder compacts and on the properties of resultant glass-ceramics were studied. Mechanical, thermal, chemical and dielectric properties of sintered GCs were investigated with the aim to evaluate the potential of the GCs as substrate materials for microelectronics applications.     

Crystallization behavior and microwave dielectric characteristics of ZnO-(La, Nd)2O3-B2O3-based dielectrics

Crystallizable zinc borate glasses modified with different contents of La₂O₃ or Nd₂O₃ were investigated as a potential low loss dielectric with respect to their crystallization behavior and microwave dielectric characteristics. The glasses were admixed with Al₂O₃ filler and fired at 850°C for 30 min in air to prepare low temperature dielectrics. Crystallization behavior and microwave dielectric properties of the resulting samples strongly depended on the relative content of La₂O₃ or Nd₂O₃ in the glass. As a promising result, the composition of 0.15ZnO-0.25Nd₂O₃-0.6B₂O₃ exhibited k?～?6.5 and Q?～?1194 at the resonant frequency of 18.9 GHz. Near zero temperature coefficient of frequency (TCF) was obtained by additional modification of the composition with ～10 wt.% of TiO₂ filler. Crystallization kinetics of the samples was studied based on the differential thermal analysis (DTA) curves obtained with different heating rates. Correlation of the observed dielectric properties to the crystallization behavior is the main subject of this work.     

Thermal and dielectric properties of glass-ceramics sintered based on diopside and anorthite composition

To develop a low dielectric constant of LTCC substrate, we studied the effect of the sintering and crystallization behavior on the dielectric properties of a sintered body by mixing a CaO–Al₂O₃–SiO₂ frit and a CaO–MgO–SiO₂ frit for a low dielectric constant of LTCC substrates. In this work, the two glass frits were mixed at different proportions and sintered at 860~920°C. After sintering at 900^oC for 1h, the glass frits crystallized into diopside and anorthite. The sintered bodies exhibited dielectric properties, ? _r?=?6~8.6 at 1 GHz, which is an essential condition for a substrate in microwave devices. The results suggest that the glass-ceramic can be applied to low dielectric LTCC materials in the electronics packaging industry.     

Influence of fillers on the re-crystallization and dielectric properties of 60ZnO-30B<Subscript>2</Subscript>O<Subscript>3</Subscript>-10SiO<Subscript>2</Subscript> glass

This paper reports re-crystallization behaviour of 60ZnO-30B₂O₃-10SiO₂ pure glass. Influence of different fillers on the re-crystallization is also highlighted. Irrespective of the nature of the filler, glass transition temperature (T_g) remains the same as that of the pure glass at 570 °C. The onset crystallization temperature is enhanced by 15 to 25 °C owing to filler addition. The peak crystallization temperature corresponding to Zn₃B₂O₆, ZnB₂O₄ and willemite occurs at 735, 810 and 851 °C for the pure glass. In the presence of alumina, gahnite emerges first at 700 °C followed by ZnB₂O₄ phase. With mullite as filler, initially ZnB₂O₄ and willemite formed at 700 °C and gahnite phase emerged only at 750 °C and peaks at 787 °C. In the presence of fused silica only ZnB₂O₄ and willemite phases were observed. The dielectric properties of the pure glass and that of the glass + fillers are also reported. Re-crystallization of various low K phases ensures good dielectric porpertis with reduced glass content after sintenring.     

Low-temperature sintering of ferroelectric Pb(Zr,Ti)O3 thick films derived from stable sol-gel solutions

Abstract

We have studied sintering and densification of PbZr_0.52Ti_0.48O₃ (PZT) films derived from diol-based sol-gel solutions. We found that densification by sintering began at below 750°C and completed at 850°C in 5 min. Initially, 0.83- μm-thick PZT single-coated films were prepared on Pt/Ti/SiO₂/Si substrates from stable propylene-glycol (l,2-propanediol)-based solutions by crystallization at 700°C. The crystallized films consisted of fine perovskite grains and voids. We studied the firing temperature dependence of various properties such as microstructure, crystallinity, and ferroelectric properties for the single-coated films. Finally, 0.54- μm-thick PZT single-coated dense films were prepared by firing at 850°C for 5 min. In order to prepare thicker PZT dense films, we studied low-temperature sintering of PZT multicoated thick films. Using this approach, 1.7- μm-thick PZT dense films were prepared by firing at 850°C for 5 min.     

Microwave dielectric properties of Ca[(Li1/3Nb2/3)1−x Tix]O3−δ ceramics with glass

The effect of the addition of glass on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−x Ti_x]O_3−δ(CLNT) was investigated. Addition of glass (B₂O₃-ZnO-SiO₂-PbO system) improved the densification and reduced the sintering temperature from 1150^∘C to 900^∘C of Ca[(Li_1/3Nb_2/3)_1−x -Ti_x]O_3−δ microwave dielectric ceramics. As increasing glass contents from 10 wt% to 15 wt%, the dielectric constants (ε_r) and bulk density were increased. The quality factor (Q⋅f₀), however, was decreased slightly. The temperature coefficients of the resonant frequency (τ_f) shifted positive value as increasing glass contents over Ti content is 0.2 mol. The dielectric properties of Ca[(Li_1/3Nb_2/3)_0.75Ti_0.25]O_3−δ with 10 wt% glass sintered at 900^∘C for 3 h were ε_r = 40 Q·f₀ = 11500 GHz, τ_f = 8, ppm/°C. The relationship between the microstructure and dielectric properties of ceramics was studied by X-ray diffraction (XRD), and scanning electron microscope (SEM).     

Crystallization,microstructures and properties of low temperature co-fired CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass-ceramic

CaO-Al₂O₃-SiO₂ glass-ceramic were prepared by melt quenching technique. The crystallization behavior and properties were studied by means of a non-isothermal, thermal analysis technique, X-ray diffraction and scanning electron microscopy. The influence of sintering temperature on phase formation, microstructure, bending strength, dielectric and thermal properties were determined. The activation energy of crystallization and the Avrami parameter were also discussed. The X-ray diffraction results show that SiO₂ phase could be found in all samples and CaSiO₃ and anorthite phases could only be observed in the samples sintered at above 875°C. The densification of glass-ceramic starts at 730°C after the liquid glass is formed and stops at 803°C. Complete densification was achieved at 875°C and the highest mechanical strength was obtained at 850°C, but density significantly decreased at higher temperatures. The coefficient of thermal expansion and the dielectric constant increase with the increasing sintering temperature. The value of the Avrami parameter (n) is ~1.6 and the apparent activation energy (E) is 298 kJ/mol.     

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.     

The High Frequency Properties and Crystallization of PbTiO3 Glass-Ceramics by Sol-Gel Process

PbTiO₃ glass-ceramics were produced by a sol-gel process. DTA and X-ray diffraction analysis provided information about the structural transformations and crystallization temperature. The range of crystallization temperature of PbTiO₃ is larger than that of PbTiO₃ glass-ceramics. By increasing the glass composition, the crystallization temperature was increased. The phase transformation of PbTiO₃ from the cubic to the tetragonal phase depends on the crystal size caused by the different heat treatment temperatures. The dielectric measurements in high frequency range (> 10⁷Hz) exhibited evidence of a relaxation phenomena near 850 MHz. With increasing glass composition, the position of the relaxation frequency was increased. The temperature dependence of the dielectric constant of PbTiO₃ and PbTiO₃ glass-ceramics has an obvious discrepancy. The dielectric constant of PbTiO₃ glass-ceramics shows the characteristic dispersion at the Curie point. It indicated that the glass ceramic sample has a stronger tendency for a diffuse phase transition.     

Effects of various oxide fillers on physical and dielectric properties of calcium aluminoborosilicate-based dielectrics

Physical and dielectric properties of LTCC (low temperature co-fired ceramics) materials based on a typical calcium aluminoborosilicate glass and various fillers such as Al₂O₃, BaTiO₃, CaTiO₃, TiO₂, ZrO₂, MgO and SiO₂ were investigated. Densification, crystallization and thermal and dielectric properties were found to strongly depend on the type of filler. The XRD patterns of Al₂O₃, BaTiO₃, CaTiO₃ and MgO samples demonstrated crystalline phases, CaAl₂Si₂O₈, BaAl₂Si₂O₈, CaTiSiO₅ and CaMgSi₂O₆, respectively, as a result of firing at 850 °C. For the sample containing CaTiO₃ filler, specifically, dielectric constant increased drastically to approximately 19.9. A high quality factor of >210 and a high TCE (temperature coefficient of expansion) of >8.5 ppm/°C were obtained for the composition containing MgO or SiO₂. Near zero TCF (temperature coefficient of frequency) was obtained for the samples containing TiO₂. The purpose of this work is to investigate the effects of various ceramic fillers on physical and dielectric properties and ultimately to provide the technical guidelines for the proper choice of filler in various LTCC systems.     

The effect of heat treatment temperature on phase formation and luminescence properties of calcium magnesium silicate glass-ceramics doped with Sm2O3

Abstract

The transparent glasses of CaO-MgO-Al₂O₃-SiO₂-ZnO system doped with Sm₂O₃ was prepared by conventional melt-quenching method. The obtained glasses were heat treated at a suitable temperature (875?°C–920?°C for 2?h) identified by differential thermal analysis (DTA). Phase formation and microstructure of glass-ceramics were characterized by X-ray diffraction and scanning electron microscopy, respectively. The optical transmission spectra were recorded by UV-Vis spectrophotometer in the wavelength range between 350 and 1000?nm. It was found that the increase in heat treatment temperature reduced the transparency of the glass-ceramics. The luminescence properties were identified by fluorescence spectroscopy. The excitation spectra of Sm₂O₃ doped CaO-MgO-Al₂O₃-SiO₂-ZnO glass-ceramic samples are in wavelength range of 550–750?nm and the emission spectra exhibited a strong orange-red luminescence composed of 562, 599 and 654?nm under excited at 402?nm. The results of XRD studies revealed the occurrence of diopside (CaMgSi₂O₆) and akermanite (Ca₂MgSi₂O₇) phases. The increasing of heat treatment temperature has no effect on the shift of emission spectra.     

Phase formation and dielectric properties of ferroelectric glass-ceramics in Na2O-BaO-Nb2O5-SiO2 system doped with Nd3+

Ferroelectric Glass-ceramics of the Na₂O–BaO–Nb₂O₅–SiO₂ system were obtained from controlled crystallization process performed on the parent glass of composition (24-x)Na₂O-xBaO-26Nb₂O₅-50SiO₂ where x?=?4 was selected. Nd₂O₃ doping was applied in the range 0–3 mol%. X-ray diffraction analysis indicated that NaNbO₃ and NaBa₂Nb₅O₁₅ crystals formed as two main crystalline phases. Their relative intensities varied with treatment temperature. Crystalline sizes of both NaNbO₃ and NaBa₂Nb₅O₁₅ calculated from XRD peak broadening were in nanoscale range. Increasing of doping content also gave a parent glass with higher bulk density. The dielectric constant measured at room temperature for glass-ceramic samples was found to be sensitive to the presence of NaBa₂Nb₅O₁₅ phase. The results of the present work suggest that introduction of Nd³⁺ into Na₂O-BaO-Nb₂O₅-SiO₂ system not only alters the dielectric response but also changes the phase transition behaviors of the co-existant ferroelectric phases by suppressing the growth of the NaBa₂Nb₅O₁₅ crystals.     

Effect of SiO<Subscript>2</Subscript> Addition to BaO-ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass on Dielectric and Thermal Properties for Application to Barrier Ribs of Plasma Display Panels

The effect of SiO₂ addition to barium zinc borate (BaO-ZnO-B₂O₃, BZB) glass on dielectric and thermal expansion properties was investigated. When SiO₂ was added to the glass batch to form a SiO₂-BaO-ZnO-B₂O₃ (SBZB) glass, the dielectric constant decreased significantly from 15.5 to 9.9. When SiO₂ (quartz) was further added to the SBZB in the form of filler particles to yield ceramic filler-reinforced SBZB microcomposites, the dielectric constant was further decreased. The coefficient of thermal expansion (CTE) of SBZB was slightly lower than the allowable range, while the filler addition to SBZB correspondingly increased CTE to the allowable range. Thus, the addition of SiO₂ to BZB glass to form SBZB glass and further addition to SBZB in the form of ceramic filler were shown to be amenable ways to tailor the dielectric constant as well as CTE of the barrier rib glass for the PDP application.     

Glass-ceramics of barium strontium titanate for high energy density capacitors

Barium strontium titanate glass-ceramics were successfully produced with one major crystalline phase when Al₂O₃ was added to the melt. A dielectric constant of 1000 and a breakdown strength of 800 kV/cm was achieved; however the energy density was only measured to be 0.3–0.9 J/cm³. These energy density values were lower than anticipated due to the presence of dendrites and pores in the microstructure. Using BaF₂ as a refining agent improved the microstructure and doubled the energy density for BST 80/20 samples. However, no refining agent reduced the increasing amount of hysteresis that developed with increasing applied electric field. This phenomenon is believed to be due to interfacial polarization.     

Electrical properties of bismuth germanate (Bi2GeO5) ferroelectric glass-ceramics prepared by two different methods

Abstract

Ferroelectric Bi₂GeO₅ glass-ceramics were fabricated using conventional and incorporation method. Glasses have been prepared from BiO_1.5-GeO₂-BO_1.5 ternary glass system by focusing on the region of 59?mol%BiO_1.5: 23?mol%GeO₂: 18?mol%BO_1.5. The resulting glass was analyzed by using differential thermal analysis (DTA) for determining the crystallization temperature (T_p). Then, the prepared glass pieces were heat treated at T_p. Effects of different fabrication methods on structure and electrical of the glass-ceramics were investigated. X-ray diffraction result of all glass-ceramics suggested that the main peak of glass-ceramics matched the orthorhombic structure of the pure Bi₂GeO₅ phase. Microstructures of the prepared glass-ceramics have been found to change from rod-like crystallites to bulk crystallites on modifying the fabrication method. The Bi₂GeO₅ glass-ceramics prepared by incorporation method presented higher dielectric constant than those of the Bi₂GeO₅ glass-ceramics prepared by conventional method. Moreover, the Bi₂GeO₅ glass-ceramic prepared by incorporation method possesses a large value of P_max (0.94 µC/cm²) comparing to that of the glass-ceramics prepared by conventional method (P_max = 0.73 µC/cm²). Thus, this study suggests that the incorporation method can effectively modify the microstructure of Bi₂GeO₅ glass-ceramics, resulting in the improvement of dielectric and ferroelectric properties.     

Preparation and characteristics of fine-grained ferroelectric glass-ceramic composites via a modified hybrid route at low temperature sintering

Dense, homogeneous and fully developed fine-grained ferroelectric Pb(Zr_0.53Ti_0.47)O₃?Cbased glass-ceramics have been successfully prepared at a low-sintering temperature of 850?C900°C by a modified hybrid process in air. The influence of the PbO-B₂O₃-SiO₂ (abbreviated as PBS) glass-gel content on the microstructure, dielectric, and ferroelectric properties of such glass-ceramics has been investigated. The temperature dependence of the dielectric constant indicated that the fine-grained Pb(Zr_0.53Ti_0.47)O₃ (abbreviated as PZT(53/47)) based glass-ceramic shows the characteristic dispersion at the Curie point. Ferroelectric hysteresis loop analyses have been performed to manifest the ferroelectric nature of the highly crystallized PZT(53/47) phase prepared by this modified novel hybrid process despite containing higher wt% glass-gel contents. The best dielectric and ferroelectric properties in a typical sample with 5% by weight of glass-gel content were found to have dielectric constant and loss tangent of 920 and 0.02 at 1 kHz, respectively. The saturation polarization (P _s ), and remanent polarization (P _r ) as well as the coercive field (E _c ) are 21.9 ??C/cm², 10.8 ??C/cm² and 2.19 kV/mm, respectively.     

Fabrication of bulk glass from the eutectic melt in Y2O3-CaO-Al2O3 system

We have studied glass formable region in the Y₂O₃-CaO-Al₂O₃ system. An optimal composition for the amorphous phase formation was found in the pseudo-eutectic 12CaO⋅7Al₂O₃-CaYAlO₄ system. An amorphous bulk plate of 10 × 25 × 1.8 mm was successfully fabricated using a simple molding technique. The fabricated glass plate showed an IR absorption edge at around 5.6 μm. The crystallization of the glass sample was observed above 890^∘C by an X-ray diffraction (XRD) and Thermogravimetry and Differential thermal analysis (TG-DTA).     

Phase evolution and Sn-substitution in LiMn2O4 thin films prepared by pulsed laser deposition

LiMn₂O₄ thin films prepared on a Pt/Ti/SiO₂/Si(100) substrate by pulsed laser deposition were studied with focusing on the effects of different processing conditions and Sn substitution on phase evolvement and surface microstructure. Major experimental parameters include substrate temperature up to 770 °C and working oxygen pressure of 50–250 mTorr. LiMn₂O₄ thin films became highly crystallized with increased grain sizes as the substrate temperature increased. Second phases such as LiMnO₂ and Li₂Mn₂O₄ were found at the temperature of 300 and 770 °C, respectively. As an optimum condition, films grown at 450 °C showed a homogeneous spinel phase with well-defined crystallinity and smooth surface. A high pressure of oxygen tended to promote crystallization and grain growth. Working pressure did not affect significantly the phase formation of the thin films except that unexpected LiMn₃O₄ phase formed at the lowest oxygen pressure of 50 mTorr. Tin-substituted thin films showed lower Mn–O stretching vibrations, which suggests that more Li-ions can be inserted into vacant octahedral sites of the spinel structure.