Effect of phosphor doping on the microstructure and dielectric properties of barium titanate ceramics

The effect of phosphor doping on the sintering behaviour, microstructure and dielectric properties of BaTiO₃ has been investigated. Diisopropyl phosphinate is added to high-purity BaTiO₃ powder prepared by the wet chemical method with a final amount of 0.14 wt.% P₂O₅ with respect to the BaTiO₃. Phosphor-doped BaTiO₃ ceramics with a high density and uniform grain size have been produced by using wet processing and pressureless sintering without any binder. A scanning electron microscope, thermometric analysis, X-ray diffraction and an impedance analyser have been used to determine the microstructure as well as the dielectric properties. The phosphor cations can form a liquid phase belonging to the ternary system BaO-TiO₂-P₂O₅, leading to the formation of BaTiO₃ ceramics with high density at low temperature. Phosphor-doped BaTiO₃ ceramics with a high density of 96% D_th are obtained by sintering at 1200°C with a soaking time of 2 h. The dielectric constants of samples sintered at 1150 and 1200°C are as high as 6100 and 5500, respectively; the Curie temperature of samples decreases with decreasing sintering temperature. Doping with a small amount of phosphor can improve the sintering and dielectric properties of BaTiO₃ ceramics.     

Preparation and ferroelectric properties of MnO2 doped BaTi2O5 ceramics by spark plasma sintering from the solid-state-calcined powder

Dense BaTi₂O₅ are fabricated from the conventional calcined powder by using spark plasma sintering and by adding MnO₂ as a dopant. The effects of the sintering temperature and the amount of MnO₂ on the phase purity are symmetrically investigated. A pure BaTi₂O₅ phase is obtained under a condition with the sintering temperature of 1,055 °C and the amount of MnO₂ doping of 0.2 wt% from the conventional powder calcined at 950 °C. The relative density of that ceramics is 98 %. The temperature dependence of dielectric property shows the Curie temperature (T _c) of 446 °C with the peak value of 450. Besides, the ceramics polarization of 0.63 μC/cm² and the coercive field of 2.0 kV/cm at room temperature, respectively.     

Effect of Bi2O3 doping on the dielectric properties of medium-temperature sintering BaTiO3-based X8R ceramics

Medium-temperature sintering X8R ceramics were fabricated based on BaTiO₃-based ceramics with Bi₂O₃ additives. The effects of sintering aids Bi₂O₃ on crystalline structure and electrical properties of BaTiO₃-based ceramics were investigated. The sinterability of BaTiO₃ ceramics was significantly improved by adding Bi₂O₃, whose densification sintering temperature reduced from 1,260 to 1,130 °C. However, the dielectric constant (ε) of BaTiO₃-based ceramics doped with Bi₂O₃ was decreased dramatically. Both low ε phase Bi₄Ti₃O₁₂ and the decrease of the tetragonality (c/a ratio), which are demonstrated by XRD pattern, are resulted in the decrease of ε. The ε of samples doped with 5.5 wt% Bi₂O₃ was higher than the other doped samples. The substitution of Bi³⁺ for the Ba²⁺ in BaTiO₃ resulted in the increase of electrovalence (from +2 to +3) of A-site ion, so the attractive force between A and B (Ti⁴⁺) sites becomes stronger. Thus Ti⁴⁺’s polarization enhances, then ε was increased to some extent. The X8R BaTiO₃-based ceramics could be sintered at as low as 1,130 °C by doping 5.5 wt% Bi₂O₃ additives into the BaTiO₃-based ceramics, with a ε greater than 2,430 at 25 °C, dielectric loss lower than 1.3 % and temperature coefficient of capacitance <±15 % (?55–150 °C).     

Effects of BaNb2O6 addition on microstructure and dielectric properties of BaTiO3 ceramics

(1 ? x)BaTiO₃–xBaNb₂O₆ [(1 ? x)BT–xBN] ceramics with x = 0, 0.005, 0.008, 0.01, 0.02, 0.03 were prepared by a conventional solid-state reaction route. The effect of BN addition on phase composition, microstructure and dielectric properties of BT-based ceramics were investigated by X-ray diffraction, scanning electron microscope and impedance spectroscopy. The results showed that a systematic structure change from the ferroelectric tetragonal phase to pseudo-cubic phase was observed near x = 0.01 at room temperature. It resulted in a considerable change of density, grain size and dielectric properties of the samples when BN was introduced. Meanwhile, it also lowered the sintering temperature of the ceramics. The dielectric constant peak and the variation rate of capacitance at Curie temperature are markedly depressed and broaden with increasing BN content. Especially, the ceramics with x = 0.008 and x = 0.01 showed good dielectric properties over the measured temperature range. Optimal dielectric properties of ε = 3,851, tanδ = 0.7 % at room temperature and Δε/ε₂₅ ≤ ±6.8 % (?55 to 125 °C) were obtained for the BT-based ceramics doped with 0.8 mol% BN, which was obviously superior to BaTiO₃ and BaNb₂O₆ ceramic, and it met the requirements of EIA X7R specifications.     

Phase stability, low temperature cofiring and microwave dielectric properties of BaTi5O11 ceramics with BaCu(B2O5) addition

The effects of BaCu(B₂O₅) (BCB) additions on the sintering temperature, microstructure and microwave dielectric properties of BaTi₅O₁₁ modified with 1.0 wt% CuO (BTC) ceramic have been investigated using X-ray diffraction, scanning electron microscopy and dielectric measurement. The BTC ceramic shows a high sintering temperature (~1,100 °C) and good microwave dielectric properties as Q × f = 44,530 GHz, ε _r = 40.5, τ _f  = 39 ppm/°C. The addition of BCB to BTC effectively reduced the sintering temperature from 1,100 to 925 °C. The reduced sintering temperature was attributed to the BCB liquid phase. The BTC ceramic doped with 4 wt% BCB has a good microwave dielectric properties with Q × f = 25,502 GHz, ε _r = 37.4, τ _f  = 33.1 ppm/°C. The chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Improved microwave dielectric properties of Mg4Nb2O9 ceramics with CaO–B2O3–SiO2 glass additions

The effects of CaO–B₂O₃–SiO₂ (CBS) glass addition on the sintering temperature and dielectric properties of Mg₄Nb₂O₉ ceramics have been investigated using X-ray diffraction, Scanning electron microscopy and Differential thermal analysis. The CBS glass can change to liquid phase at about 750 °C and a small amount of CBS glass addition to Mg₄Nb₂O₉ ceramics can greatly decrease the sintering temperature to about 1,125 °C. It is revealed that the reduced sintering temperature is attributed to the formation of liquid phase. The major phases of the sample are Mg₄Nb₂O₉ and MgNb₂O₆. The relationship between τ _f values and the content of glass additions have the reverse change trends. The Mg₄Nb₂O₉ ceramics with 2wt% glass addition sintered 1,125 °C exhibit good microwave dielectric properties: dielectric constant (ε _r ) of 13 and Q·f value of 69,000 GHz.     

Phase evolutions and electric properties of BaTiO3 ceramics by a low-temperature sintering process

BaTiO₃ (BT) nanoparticles were synthesized by a modified polymeric precursor method in a weak acid solution. The synthesized process of BT precursor with increasing calcination temperature was investigated through thermal analysis (DTA/TG), X-ray diffraction, transmission electron microscope and Fourier-transform infrared spectroscopy. Good dispersive and homogeneous cubic BT nanoparticles were calcined at 800 °C, whereas dense BT ceramics were sintered at ~1,160 °C. The present results showed that the dielectric, piezoelectric and ferroelectric properties of BT ceramics were dependent on the ceramics densification and crystallographic structure. The excellent electric properties (P _r = 10.5 μC/cm², d ₃₃ = 217 pC/N, k _p = 0.32 %) were found at a sintering temperature of 1,160 °C, which was due to the coexistence of tetragonal and orthorhombic phase. The depressed electric properties at higher sintering temperature were associated to oxygen vacancies and impurity phases. In addition, phase evolutions of BT nanoparticles and ceramics were all stated in detail.     

Influence of La–B–Zn glass on the sintering and microwave dielectric properties of Ca–Nd–Ti ceramics

The effects of La₂O₃–B₂O₃–ZnO (LBZ) glass on the sintering behaviors, phase structures, microstructures and the microwave dielectric properties of perovskite type Ca_0.6Nd_0.26TiO₃ (CNT) ceramics were studied. It indicates that the LBZ glass has an obvious effect on lowering the sintering temperature without damaging the microwave dielectric properties of the CNT ceramics. Small amounts of LBZ glass significantly lowered the sintering temperatures of CNT ceramics and obtained excellent microwave dielectric properties. However, too much LBZ glass is leading to inferior dielectric properties. The CNT ceramics doped with 3 wt% LBZ can be well sintered at 975 °C for 4 h and shows good properties: ε_r = 87.87, Q × f = 8132 GHz (f = 3.3 GHz), τ_f = +244.63 ppm/°C.     

Effects of MnO2 doping on microstructure and microwave dielectric properties of Ba4.2Nd9.2Ti18O54–NdAlO3 ceramics

MnO₂ doped Ba_4.2Nd_9.2Ti₁₈O₅₄–NdAlO₃(13 wt%) (BNT–NA) microwave dielectric ceramics with the near zero τ _f and the wide range of sintering temperature were prepared by conventional solid state method. The effects of Mn⁴⁺ doping on the microstructures and microwave dielectric properties of BNT–NA ceramics were investigated. XRD patterns showed only a single BaNd₂Ti₅O₁₄ phase was identified in all samples and there was no second phase. The sintering temperature decreased from 1,380 to 1,320 °C as MnO₂ content increased from 0.1 to 0.9 wt%. The MnO₂ doped BNT–NA ceramics could be densified at a lower sintering temperature. The MnO₂ additive had a positive effect on lowing sintering temperature of BNT–NA ceramics. The τ _f varied from negative to positive with the increase of MnO₂. Excellent microwave dielectric properties were achieved in Ba_4.2Nd_9.2Ti₁₈O₅₄–NdAlO₃ ceramics doped with 0.3 wt% MnO₂ and sintered at 1,380 °C for 2 h: ε _r  = 66.5, Q × f = 13,948 GHz, τ _f  = 0.4 ppm/°C.     

Effect of synthesized BaTiO3 doping on the dielectric properties of ultra temperature-stable ceramics

The high performance X9R ceramics could be sintered at as low as 1,120?°C by doping 3?mol% synthesized BaTiO₃ (SB) additives into the BaTiO₃-based ceramics, with a dielectric constant greater than 2,200 at 25?°C and dielectric loss lower than 1.7?%. The effects of SB additives on the microstructure and dielectric properties of BaTiO₃-based ceramics were investigated. The dielectric constant of BaTiO₃-based ceramics doped with 3?mol% SB was increased due to the promotion of the densification of ceramics. With SB content up to 4.5?mol%, Ti⁴⁺’s polarization was depressed, which resulted in the decrease of augmented dielectric constant at 25?°C. The partial solid solution was formed between Pb(Ti, Sn)O₃ and BaTiO₃, and the substitutions of Pb at A-sites and Sn at B-sites were existed. The strengthen of Ti–O bonds and higher Curie point of Pb(Ti_0.55Sn_0.45)O₃ was helpful to increased the Curie point of the ceramics effectively. Doped with SB additives, the volume of ferroelectric core was increased, and the sharp peak intensity at Curie point was increased accordingly. Capacitance temperature characteristics was improved attributed to the mutual effects of SB and Pb(Ti_0.55Sn_0.45)O₃. The formation of core–shell structure was sensitive to the sintering temperature, so the dielectric properties of ceramics were highly depended on the sintering temperature.     

Effects of SrO–B2O3–SiO2 glass additive on dielectric properties of Ba(Fe0.5Nb0.5)O3 ceramics

SrO–B₂O₃–SiO₂ (SBS) glass powders were prepared and employed as sintering aids to reduce the sintering temperature of Ba(Fe_0.5Nb_0.5)O₃ (BFN) ceramics. The effects of glass content on the dielectric properties and breakdown strength of BFN ceramics have been investigated. The volume density characterization results of (1 ? x) BFN ? x SBS ceramics indicate that the sintering temperature of BFN ceramics decreased by 200–350 °C with SBS glass addition (when x = 0, 0.01, 0.03 and 0.05). The XRD patterns show BFN ceramics indicate cubic crystal structure and without the formation of a secondary phase. The dielectric constant and dielectric loss decreased gradually with increasing glass content, and the dielectric loss decreased by one order of magnitude with SBS glass addition (when x = 0.05). The breakdown strength of (1 ? x) BFN ? x SBS ceramics increase with increasing glass content, in which is about 33.90 kV/cm with SBS glass addition (when x = 0.05). These improvements in the dielectric characteristics of BFN ceramics have great scientific significance for their applications.     

Study on properties of Ca2Zn4Ti15O36 ceramics with CaO-B2O3-SiO2 glass

The effects of CaO-B₂O₃-SiO₂ (CBS) glass additions on the sintering temperatures and dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics have been investigated using X-ray diffraction, Scanning electron microscopy. A small amount of CBS glass addition to Ca₂Zn₄Ti₁₅O₃₆ ceramics can greatly decrease the sintering temperature to about 975 °C. It is revealed that the reduced sintering temperature is attributed to the formation of liquid phase. The major phases of the samples are Ca₂Zn₄Ti₁₅O₃₆ and rutile. The more glass added, the more rutile phase formed. The τ_f values shift towards negative first and then toward positive with the increasing glass additions. The Ca₂Zn₄Ti₁₅O₃₆ ceramics with 4 wt% glass addition sintered 1,050 °C for 2 h exhibit good microwave dielectric properties: Q·f values of 31,000 GHz and dielectric constant (ε _r ) of 44.7.     

The structure and properties of 0.95MgTiO3–0.05CaTiO3 ceramics doped with Co2O3

The effects of Co₂O₃ addition on the sintering behavior, phase formation, microstructure and microwave dielectric properties of 0.95MgTiO₃–0.05CaTiO₃ ceramics have been investigated. The structure and microstructure of the ceramics were investigated using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. These results suggested that Co₂O₃ addition not only contributes in lowering the sintering temperature but also inhibits the formation of second phase MgTi₂O₅ in 0.95MgTiO₃–0.05CaTiO₃ ceramics. Moreover, the decomposition of Co₂O₃ would inhibit the Ti⁴⁺ from being restored to Ti³⁺, which had the positive effect on the Q × f value. A fine combination of microwave dielectric properties (ε _r = 20.48, Q × f = 76,485 GHz, τ _f  = 2.43 ppm/°C) was achieved for 0.95MgTiO₃–0.05CaTiO₃–0.01Co₂O₃ ceramics sintered at 1300 °C for 4 h, which satisfied microwave applications in resonators, filters and antenna substrates.     

Sintering behavior and microwave dielectric properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO doped (Zr<Subscript>0.8</Subscript>Sn<Subscript>0.2</Subscript>)TiO<Subscript>4</Subscript> ceramics

(Zr_0.8Sn_0.2)TiO₄ (ZST) ceramics were fabricated via conventional solid-state reaction method. Sintering behavior, phase composition, microstructure and microwave dielectric properties of Y₂O₃–ZnO doped ZST ceramics were investigated. Only a single ZST phase was identified by X-ray diffraction patterns. The variation tendencies of dielectric constants as well as Q × f values were in accordance with the bulk densities. The appropriate Y₂O₃ and ZnO additions could not only efficiently lower the sintering temperature to 1240 °C, but also noticeably improve the densification and microwave dielectric properties of ZST ceramics. But excessive additives deteriorated the microstructures and comprehensive properties of samples. A dielectric constant ε _r of 39.73, a Q × f value of 48,545 GHz (at 5.5 GHz), and a τ _f value of ?2.13 ppm/°C were obtained for 1 wt% ZnO doped ZST ceramics with 0.5 wt% Y₂O₃ addition sintered at 1240 °C.     

Low temperature cofirable Li2Zn3Ti4O12 microwave dielectric ceramic with Li2O–ZnO–B2O3 glass additive

The effects of Li₂O–ZnO–B₂O₃ (LZB) glass additive on the sintering behavior, phase composition, microstructure and microwave dielectric properties of Li₂Zn₃Ti₄O₁₂ ceramics were investigated. The addition of a small amount of LZB glass can reduce the sintering temperature of Li₂Zn₃Ti₄O₁₂ ceramics from 1,075 to 900 °C without much degradation of the microwave dielectric properties. Only a single-phase Li₂Zn₃Ti₄O₁₂ is formed in Li₂Zn₃Ti₄O₁₂ ceramic with LZB addition. Typically, the 1.5 wt% LZB glass-added Li₂Zn₃Ti₄O₁₂ ceramic sintered at 900 °C for 2 h can reach a high relative density of 97.5 % and exhibits good microwave dielectric properties, i.e., relative dielectric constant (ε _r ) = 19.1, quality factor (Q) = 7083.5 at 9 GHz, and temperature coefficient of resonant frequency (τ _f ) = ? 48.9 ppm/°C. In addition, the ceramic could be co-fired well with an Ag electrode, which is made it as a promising dielectric ceramic for low temperature co-fired ceramics technology application.     

Preparation of the LTCC composite ceramics with low permittivity

In this work, the LTCC composite ceramics containing ??-alumina and quartz based on the binary system BaO?CB₂O₃ were prepared by traditional solid-state preparation process at a sintering temperature of 900 °C. Sintering mechanism and physical properties of the LTCC composite ceramics are investigated and discussed in detail in terms of their mineral phase composition. The results indicate that, by the chemical combination of barium hydroxide octahydrate and an aqueous solution of boric acid, a barium borate phase can be formed form the binary system BaO?CB₂O₃ and consequently supply a liquid sintering aid for the fabrication of LTCC composite ceramics at a sintering temperature of 900 °C. The introduction of ??-alumina to the binary system BaO?CB₂O₃ can improve the sintering behavior whereas the presence of quartz in the composite ceramics is important to achieve low permittivity. By the combination of ??-alumina, quartz and BaO?CB₂O₃ composition, the dense LTCC composite ceramics, which is characterized by excellent dielectric properties (permittivity: 3.56; 4.83; dielectric loss: 3 × 10^?4; 4 × 10^?4), can be fabricated availably.     

Preparation and dielectric properties of BaTiO3-based X8R ceramics co-doped with BIT and CBS glass

The effects of Bi₄Ti₃O₁₂ (BIT) on phase purity and dielectric properties of BaTiO₃ (BT) ceramics have been investigated. Results show that BT samples doped with 1–3 mol% BIT adopt a single phase. However, secondary phase Bi₂Ti₂O₇ is observed when BIT content exceeds 3 mol%. Tetragonality and the Curie temperature (T _C) firstly increase and then decreases with an increase in BIT content. The 3 mol% BIT-doped BT ceramic sintered at 1,250 °C exhibits good dielectric properties of ε_r = 2,692, tan δ = 0.0152, ρ_v = 5.8 × 10¹² Ω cm, and the variation of dielectric constant as compared with that at room temperature is about ?20 % at ?55 °C and less than 11 % at 150 °C. It is found that the addition of calcium borosilicate glass (CBS) in BT-BIT ceramics can effectively lower the sintering temperature from 1,250 to 1,050 °C and further enhance the capacitance temperature stability. The permittivity decreases with an increase in CBS content from 1 to 10 wt%. Secondary phase BaBi₄Ti₄O₁₅ exists in the CBS doped BT-3BIT systems. All of CBS doped samples satisfy the X8R specification. Typically, the sample with 3 wt% CBS has ε_r = 1,789, tan δ = 0.0115, ρ_v = 9.67 × 10¹² Ω cm. The variation of permittivity as compared with that at room temperature is about ?12 % at ?55 °C and less than ± 11 % at 150 °C. The as-prepared materials have great potential as EIA X8R-type multilayer ceramic capacitors.     

Low temperature sintering of Li2(Mg0.3Zn0.7)Ti3O8-0.12TiO2 microwave dielectric ceramics with controllable grain size

The effects of BaO-B₂O₃-SiO₂ (BBS) frit on sinterability, microstructure and microwave dielectric properties of Li₂(Mg_0.3Zn_0.7)Ti₃O₈-0.12TiO₂ (LMZT) ceramics were systematically investigated. BBS frit can effectively lower the sintering temperature of LMZT ceramics to below 900 °C. Suitable BBS frit addition can accelerate the growth of the LMZT grains while inhibit the abnormal grain growth at the same time. The LMZT ceramics with 2 wt% BBS frit sintered at 900 °C for 3 h show homogeneous microstructure composed of 5–10 μm grains and excellent dielectric properties: ε _r  = 24.1, Q × f = 21,980 GHz, τ _f  = ?4.1 ppm/ °C. It is compatible with Ag electrodes, which makes it a potential candidate material for low temperature co-fired ceramics technology application.     

Low-temperature sintering and microwave dielectric properties of Mg<Subscript>3</Subscript>B<Subscript>2</Subscript>O<Subscript>6</Subscript>-LMZBS composites

The Mg₃B₂O₆ ceramics with lithium magnesium zinc borosilicate (LMZBS) glass were prepared at a lower sintering temperature. The effects of the glass addition on the densification, phase development, microstructure and microwave dielectric properties of the Mg₃B₂O₆ ceramics were investigated. The addition of LMZBS glass improved the densification and lowered the sintering temperature of Mg₃B₂O₆ ceramics from 1,300 to 950 °C. X-ray diffraction patterns showed that Mg₃B₂O₆ transformed into Mg₂B₂O₅ and a new phase, Li₂ZnSiO₄, crystallized from the glass phase. Because of the high dielectric performance of these phases, Mg₃B₂O₆ mixed with 55 wt% LMZBS sintered at 950 °C for 3 h had ε_r = 6.8, Q × f = 50,000 GHz, and τ_f = ?64 ppm/°C at 7.28 GHz. The chemical compatibility of ceramic-glass composites with Ag was also investigated for LTCC.     

Enhancing the microwave dielectric properties of Nd (Mg0.5Sn0.5)O3 ceramics by substituting Nd3+ with Ca2+

The microwave dielectric properties of Nd_(1?2x/3)Ca_x(Mg_0.5Sn_0.5)O₃ ceramics were examined to evaluate their exploitation for mobile communication. Nd_(1?2x/3)Ca_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the Nd_2.9/3Ca_0.05(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with the sintering temperature. Nd_2.9/3Ca_0.05(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1,550 °C for 4 h had the following properties: a density of 6.86 g/cm³, a dielectric constant (ε_r) of 19.3, a quality factor (Q × f) of 99,000 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?65 ppm/°C.