Control of Microwave Dielectric Properties in the System BaO ⋅ Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>—BaO ⋅ Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>

BaO ⋅ Nd₂O₃ ⋅ 4TiO₂—based ceramics were prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1200–1450^∘C. Microstructures were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM); microwave dielectric properties were determined at 3 GHz by the Hakki and Coleman method. Product densities were at least 95% theoretical. The addition of up to 1 wt% Al₂O₃ to the starting mixtures reduced the sintering temperatures by at least 100^∘C. Incorporation of small levels of Al into the structure (initially Ti sites) led to an increase in Q × f values, from 6200 to 7000 GHz, a decrease in relative permittivity (ε_r) from 88 to 78, and moved the temperature coefficient of resonant frequency (τ_f) towards zero. The addition of 0.5 wt% Al₂O₃ with 8 wt% Bi₂O₃ improved densification, increased both ε_r (to 88) and Q× f (to 8000 GHz) and moved τ_f closer to zero. Ceramics in the system (1 − x)BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + xBaO ⋅ Al₂O₃ ⋅ 4TiO₂ exhibited very limited solid solubility. The end member BaO ⋅ Al₂O₃ ⋅ 4TiO₂ was tetragonal in structure with the following dielectric properties: ε_r = 35; Q× f = 5000 GHz; τ_f = −15ppm/^∘C. Microstructures of the mixed Nd-Al compositions contained two distinct phases, Nd-rich needle-like grains and large Al-rich, lath-shaped grains. Products with near zero τ_f were achieved at compositions of approximately 0.14BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + 0.86BaO ⋅ Al₂O₃ ⋅ 4TiO₂, where Q× f = 8200 GHz and ε_r = 71.     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

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).     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ε _r ), high quality factor (Q × f), and small temperature coefficient of resonant frequency (TCF) are required for the application of chip passive components in wireless communication low temperature co-fired ceramics (LTCC). In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₅Nb₆O₂₈ ceramics were investigated as a function of B₂O₃-CuO content. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250^∘C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ε _r of 37, TCF of −12 ppm/^∘C. The addition of B₂O₃-CuO was revealed to lower the sintering temperature of Ba₃Ti₅Nb₆O₂₈, 900^∘C and to enhance the microwave dielectric properties: Q × f of 32,500 GHz, ε _r of 40, TCF of 9 ppm/^∘C. From the X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

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.     

Microwave Dielectric Properties of CuO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript> Ceramics with Low Sintering Temperature

Microwave dielectric properties of low temperature sintering ZnNb₂O₆ ceramics doped with CuO-V₂O₅-Bi₂O₃ additions were investigated systematically. The co-doping of CuO, V₂O₅ and Bi₂O₃ can significantly lower the sintering temperature of ZnNb₂O₆ ceramics from 1150 to 870C. The secondary phase containing Cu, V, Bi and Zn was observed at grain boundary junctions, and the amount of secondary phase increased with increasing CuO-V₂O₅-Bi₂O₃ content. The dielectric properties at microwave frequencies (7–9 GHz) in this system exhibited a significant dependence on the relative density, content of additives and microstructure of the ceramics. The dielectric constant ( _r) of ZnNb₂O₆ ceramics increased from 21.95 to 24.18 with increasing CuO-V₂O₅-Bi₂O₃ additions from 1.5 to 4.0 wt%. The quality factors (Q× f) of this system decreased with increasing CuO-V₂O₅-Bi₂O₃ content and ranged from 36118 to 67100 GHz for sintered ceramics, furthermore, all Q× f values of samples with CuO-V₂O₅-Bi₂O₃ additions are lower than that of un-doped ZnNb₂O₆ ceramics sintered at 1150C for 2 h. The temperature coefficient of resonant frequency ( _f) changed from –33.16 to –25.96 ppm/C with increasing CuO-V₂O₅-Bi₂O₃ from 1.5 to 4.0 wt%     

Dielectric behavior of Bi2/3Cu3Ti4O12 ceramic and thick films

The paper reports on synthesis, sintering and microstructure of Bi_2/3Cu₃Ti₄O₁₂, a lead-free, high-permittivity material with internal barrier layer capacitor behavior. Complex impedance and capacitance of the ceramic and thick films were studied as a function of frequency (10 Hz–2 MHz) and temperature (−170 to 400°C). Dc electrical conductivity of the samples was measured in the temperature range 20–400°C. Broad and high maxima of dielectric permittivity versus temperature plots were observed reaching 60,000 for ceramic and 5,000 for thick films. The maxima decrease and shift to higher temperatures with increasing frequency. Two arcs ascribed to grains and grain boundaries were found in the plots of imaginary part versus real part of impedance. Analysis of the impedance spectra indicates that Bi_2/3Cu₃Ti₄O₁₂ ceramic could be regarded as electrically heterogeneous system composed of semiconducting grains and less conducting grain boundaries. The developed thick film capacitors with dielectric layers based on Bi_2/3Cu₃Ti₄O₁₂ exhibit dense microstructure, good cooperation with Ag electrodes, high permittivity up to 5,000 and relatively low temperature coefficient of capacitance in the temperature range 100–300°C. Broad maxima in the dielectric permittivity versus temperature curves may be attributed to Maxwell–Wagner relaxation.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Ni-Cu-Zn Ferrites for low temperature firing: II. Effects of powder morphology and Bi2O3 addition on microstructure and permeability

The morphology of Ni-Cu-Zn ferrite powders obtained by milling of a calcined raw materials mixture strongly effects the densification behavior during sintering at 900^∘C. In order to obtain dense samples sub-micron powders with enhanced reactivity are required. The addition of Bi₂O₃ as sintering additive is beneficial: the density of samples sintered at 900^∘C increases with the bismuth oxide concentration up to 0.75 wt.%. The process of liquid phase sintering was studied by dilatometry. The grain size of the sintered samples slightly increases for 0.25 wt.% Bi₂O₃ compared to bismuth-free samples, whereas for 0.3–0.5 wt.% Bi₂O₃ additions bimodal grain growth is observed with a significant fraction of very large grains. For > 0.5 wt.% Bi₂O₃ a homogeneous coarse-grained microstructure is obtained. The permeability increases for small bismuth oxide additions, but decreases for a Bi-oxide content of more than 0.5%. Maximum permeability of μ_i = 900 is observed for intermediate Bi₂O₃ concentrations. PACS codes: 75.50 Gg; 81.20 Ev; 81.40 Rs     

Thermoelectric properties of p-type Bi0.5Sb1.5Te3 compounds fabricated by spark plasma sintering

P-type thermoelectric Bi_0.5Sb_1.5Te₃ compounds were prepared by the spark plasma sintering method with temperature ranges of 300–420^∘C and powder sizes of ∼75 μm, 76–150 μm, 151–250 μm. As the sintering temperature increased, the electrical resistivity and thermal conductivity of the compound were greatly changed due to an increase in the relative density. The Seebeck coefficient and electrical resistivity were varied largely with decreasing the powder size. Subsequently, the compound sintered at 380^∘C with the powders of ∼75 μm showed the maximum figure-of-merit of 2.65 × 10⁻³K⁻¹ and the bending strength of 73 MPa.     

Thermal and dielectric properties of ZnO-B2O3-MO3glasses (M = W, Mo)

Glasses in the ZnO-B₂O₃-MO₃(M = W, Mo) ternary were examined as potential replacements to PbO-B₂O₃-SiO₂-ZnO glass frits with the low firing temperature (500–600^∘C) for the dielectric layer of a plasma display panels (PDPs). Glasses were melted in air at 950–1150^∘C in a narrow region of the ternary using standard reagent grade materials. The glasses were evaluated for glass transition temperature (T _g ), softening temperature (T _d ), the coefficient of thermal expansion (CTE), dielectric constant (ε _r ), and optical property. The glass transition temperature of the glasses varied between 470 and 560^∘C. The coefficient of thermal expansion and the dielectric constant of the glasses were in the range of 5–8 × 10^{− 6}/^∘C and 8–10, respectively. The addition of MO₃to ZnO-B₂O₃binary could induce the expansion of glass forming region, the reduction of T _g and the increase in the CTE and the dielectric constant of the glasses. Also, the effect of the addition of MO₃to ZnO-B₂O₃binary on the transmittance in the visible-light region (350–700 nm) was investigated.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

Effects of Mn-doping on TSDC and degradation of BaTiO3

The effects of Mn-doping on TSDC (Thermally Stimulated Depolarization Current) and electrical degradation of BaTiO₃ have been investigated. TSDCs of un-doped BaTiO₃ and Ba(Ti_1−x Mn_x)O_3−δ exhibited the three sharp TSDC peaks around phase transition temperatures. TSDC of Ba(Ti_0.995Mg_0.005)O_2.995 increased gradually from 50^∘C and this anomalous depolarization current kept going up well above the Curie temperature (∼130^∘C). TSDCs of un-doped BaTiO₃ and Ba(Ti_0.995Mn_0.005)O_3−δ decreased in the temperature range above the Curie point, whereas a slight increase in TSDC was confirmed at the specimen of Ba(Ti_0.99Mn_0.01)O_3−δ. TSDCs of Ba(Ti_0.995−y Mg_0.005Mn_y)O_3−δ (y = 0.005, 0.01) were lower than that of Ba(Ti_0.995Mg_0.005)O_2.995.     

Ferroelectric properties of heterolayered lead zirconate titanate thin films

Heterolayered Pb(Zr_{1 − x} Ti _x )O₃ thin films consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers were successfully deposited via a multistep sol-gel route assisted by spin-coating. These heterolayered PZT films, when annealed at a temperature in the range of 600–700^∘C show (001)/(100) preferred orientation, demonstrate desired ferroelectric and dielectric properties. The most interesting ferroelectric and dielectric properties were obtained from the six-layered PZT thin film annealed at 650^∘C, which exhibits a remanent polarization of 47.7 μC/cm² and a dielectric permittivity of 1002 at 100 Hz. Reversible polarization constituents a considerably high contribution towards the ferroelectric hysteresis of the heterolayered PZT films, as shown by studies obtained from C-V and AC measurement.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Synthesis of Pb(Ni1/3Nb2/3)0.72Ti0.28O3 perovskite ceramics by a reaction-sintering process

Pb(Ni_1/3Nb_2/3)_0.72Ti_0.28O₃ (PNNT) perovskite ceramics produced by a reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂, Nb₂O₅ and TiO₂ was pressed and sintered directly into PNNT ceramics. PNNT ceramics of 100% perovskite phase were obtained. For PNNT sintered for 2 h in PbO compensated atmosphere, maximum density reaches a value 8.49 g/cm³ (99.8% of the theoretical value) at 1250^∘C. A maximum dielectric constant 20600 occurred around 37^∘C at 1 kHz in PNNT sintered at 1250^∘C for 2 h.     

Dielectric properties of nanocrystalline TiO2 prepared using spark plasma sintering

Ultra fine rutile powders (below 50 nm) were prepared via the sol-gel process and bulk type TiO₂ specimens were fabricated using spark plasma sintering (SPS). The TiO₂ specimen sintered at a low temperature (720^∘C) exhibited a highly relative density (97%) and a nano-sized grain structure (200 nm). Dielectric properties of spark plasma sintered TiO₂ specimens including dielectric constants (k) and losses (tan δ) were measured. The TiO₂ specimen, obtained by SPS, showed a high dielectric constant (∼780) and a low tan δ (∼0.005), and a relaxation behavior at 1 MHz. After the subsequent annealing process of the TiO₂ specimen in O₂ flow, the dielectric constants remarkably decreased (k = 100s). These dielectric properties of nanocrystalline TiO₂ specimens prepared by SPS were discussed in terms of space charges produced by the reduction of Ti⁴⁺ ions and crystallographic orientations of grains.     

Calculation of the intrinsic dead layers thicknesses from Au/Ba0.5Sr0.5TiO3/Pt thin film capacitors

Ferroelectric Ba_0.5Sr_0.5TiO₃ (BST) films were prepared on Pt/Ti/SiO₂/Si substrates by the sol-gel process. The films were spin-coated at 2000 rpm for 30 secs and then pyrolysed for 5 mins at the temperature of 350^∘C. This coating procedure was repeated for 3, 4, 5 and 6 times to obtain BST films with different thicknesses. After coating the films with the desired repetition times, the films were finally annealed in a conventional furnace at temperatures ranging from 600^∘C to 800^∘C with a 50^∘C interval in between. The films obtained with an annealing procedure of 750^∘C were polycrystalline with the presence of an impurity BaCO₃ phase. The capacitance and leakage current were measured and used to extract information on the metal-BST interface. With the series capacitance model and modified Schottky emission equation, the thickness of the dead layers for Au/BST and Pt/BST interfaces were calculated to be less than 6 nm and 5 nm, respectively.