Effect of oxygen partial pressure on co-firing behavior and magnetic properties of LTCC modules with integrated NiCuZn ferrite layers

low-κ dielectric LTCC was developed, to realize successful co-firing with NiCuZn ferrite tapes. A critical high-temperature process in the production of highly integrated LTCC modules is the migration of silver from inner conductors into the LTCC glass phase. Intensive silver migration causes strong deformation of LTCC multilayers during firing in air. Silver migration into the LTCC glass phase depends on oxygen content of the sintering atmosphere and can be minimized by sintering in nitrogen atmosphere. However, partial decomposition of NiCuZn-ferrite and formation of cuprite was observed during sintering in nitrogen and, consequently, the permeability of the ferrite decreases. As shown by a combined XRD/thermogravimetric study the co-firing of LTCC modules with silver metallization and integrated ferrite layer demands precise adjustment of oxygen partial pressure.     

Magnetic properties of Ni-Zn ferrites prepared by microwave sintering method

The effect of zinc ion substitution for nickel on structural and magnetic properties of NiZn ferrites is reported. The spinel ferrite system Ni_1-xZn_xFe₂O₄ with x = 0.2, 0.3, 0.4 and 0.5 was prepared by microwave sintering method. The uniaxially pressed samples were sintered at various temperatures such as 900°C, 1000°C and 1100°C for 30 min. X-ray diffraction patterns of the samples indicate the formation of single-phase cubic spinel structure. SEM micrographs show that grain size increases with increasing zinc content and sintering temperature. The elemental composition of these ferrites was analyzed by EDS. Lattice constant increases with increase in zinc content, obeying Vegard’s law. The effect of composition and sintering temperature on initial permeability as the function of frequency and temperature was studied. The initial permeability of NiZn ferrite increases greatly with increasing Zn content and sintering temperature. The dependence of initial permeability with respect to temperature shows the decrease in the Curie point with increase in zinc content, is the normal behavior of ferrites. The relative loss factor (tand

Interface and ionic interdiffusion in cofired dielectrics/ferrite layer composites

Zinc-magnesium titanate dielectrics/nickel-zinc-copper ferrite layer composites were prepared. An interlayer was designed to relax the interfacial stress because of the mismatch shrinkage between dielectric and ferrite. And as the results, zero camber and crack-free dielectric/interlayer/ferrite composite samples were obtained and the interface was continuous with no delamination. The cofiring interface and ionic interdiffusion between the constituents were investigated. The interdiffusion of the composite can be regarded as the semi-infinite diffusion-couple model and based on this diffusion model, the numerical simulation for the ionic composition distribution was carried out by computer, which was in agreement with the experimental results. The activation energies for the Ti⁴⁺, Ni²⁺, and Fe³⁺ were determined respectively. The difference between apparent activation energies was discussed in this article. The layer composite sintered at 930°C exhibited the dielectric properties: ?? _r ?=?18.2, tan???=?3.01?×?10^?3. Due to their low firing characteristics and realizable co-firing compatibility, the layer composites can serve as the promising medium materials in the multilayer LC filter.     

Preparation, thermal stability and permeability behavior of substituted Z-type hexagonal ferrites for multilayer inductors

Co₂Z-type hexagonal ferrites with iron excess Ba₃Co_2???x Fe_24?+?x O₄₁ (0?≤?x?≤?0.8) and deficiency Ba₃Co_2?+?y Fe_24???y O₄₁ (0?≤?y?≤?0.6) were prepared by an oxalate coprecipitation technique. This synthesis route leads to almost single phase Z-type ferrites for x?=?0 after calcination and sintering at 1330 °C. The Z-type formation is enhanced for x?>?0 and single phase ferrites are obtained for 0.4?≤?x?≤?0.8. The permeability of Z-type ferrites varies with composition x: Maximum permeability of μ′?=?28 is observed for 0.4?≤?x?≤?0.6 for samples sintered at 1330 °C. The frequency dispersion shows broad peaks of μ″ stretching from 200 MHz to >1 GHz. For iron deficient samples 0?≤?y?≤?0.6 multi-phase mixtures were obtained. For Ag-based multilayer inductor applications sintering at 950 °C is required. Co₂Z ferrites with Fe excess are not stable at this temperature as demonstrated by XRD. The permeability of samples sintered at 950 °C is drastically reduced to μ′?=?3. This demonstrates that these materials are not able to provide sufficient permeability for multilayer inductors for high-frequency operations since they are not compatible with the low temperature ceramic cofiring technology.     

Effects of ZnO–xV2O5 substitution on the microstructure and microwave dielectric properties of ZnNb2O6 ceramics

The ZnO–xV₂O₅ substituted ZnNb₂O₆ ceramics with chemical formula Zn(Nb_0.9V _x )₂O_5.5+5x (0?<?x?≤?0.10) were prepared by solid-state reaction route. The densities, microstructures and microwave dielectric properties were investigated according to the different substitution amount of V₂O₅ and sintering temperature. A small amount of substitution of ZnO–xV₂O₅ was effective to lower sintering temperature of ZnNb₂O₆ ceramics from 1,150 °C to 900 °C. The V₂O₅ substitution led to growth of rod-like grains with the help of liquid phase formed from ZnO and V₂O₅. The dielectric properties depended largely on the amount of V₂O₅ substitution and sintering temperature. The dense ceramics with x?=?0.05 were obtained at 950 °C, which had excellent dielectric properties: ?_r?=?24, Q?×?f?=?72,800 GHz and τ_f?=??63.5 ppm/°C. The interface analysis for cofired multilayer composites composed of the present LTCC and metal Ag demonstrated good co-firing chemical compatibility at co-sintering temperature.     

Interfacial investigation of the Co-fired NiCuZn Ferrite/PMN composite prepared by tape casting

The co-firing behavior and interfacial diffusion of the co-fired system of NiCuZn ferrite (abbreviated as NiCuZn) and Pb(Mg_1/3Nb_2/3)O₃ (abbreviated as PMN) relaxor ferroelectric are studied in this work. NiCuZn layers and PMN layers prepared by tape casting were stocked alternately. X-ray diffraction analysis shows no new phase appeared in the mixture of NiCuZn and PMN. Scanning electronic microscopy observation of the bi-layer composite indicates obvious warp at the interface due to the sintering mismatch between ferrite and ferroelectrics. The co-firing property of NiCuZn and PMN is modified by doping appropriate content of Bi₂O₃. By pressing a mixed composition interlayer in the ratio 50:50 between the ferrite and ferroelectric layers, a crack-free multilayer structure could be obtained.     

Low temperature cofirable MnZn ferrite for power electronic applications

A new MnZn ferrite tape material for sintering at 900 °C and its performance in power electronic embedded multilayer inductors of several μH inductance are described. The low sintering temperature is achieved by optimizing powder processing and sintering additives. The material is suited for processing within the low temperature cofired ceramics (LTCC) technology and it is particularly compatible with low loss Ag metallization. Although reduced by a factor of two compared to high-temperature sintered material, its relative amplitude permeability of 700 allows for numerous device applications below the Curie temperature of 260 °C. Volumetric losses are not affected by the new material formulation since increased hysteresis losses are compensated by reduced eddy current losses. Power line filters with ceramic integrated inductors and surface mounted capacitors exhibit a current capacity of up to 10 A and a shift in cutoff frequency compatible with the measured B–H curve of the material. By integration of these inductors with conventional dielectric LTCC tapes a strain-induced permeability quenching is revealed and attributed to magnetostriction. Therefore good thermal matching between tape materials is needed, but the effect also permits construction of variometers and pressure sensors without moving mechanical parts.     

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.     

Fabrication of microinductor using Nanocrystalline NiCuZn ferrites

The nanocrystalline Ni_0.53Cu_0.12Zn_0.35Fe₂O₄ was prepared using microwave hydrothermal (M-H) method at a low temperature of 160 °C/30 min. As synthesized powders were characterized using XRD and TEM. The powders were sintered using microwave sintering methods at different sintering temperatures i.e. 750 °C/30 min, 800 °C/30 min, 850 °C/30 min 900 °C/30 min and 950 °C/30 min respectively. The sintered samples were characterized using XRD and SEM. The complex permittivity (ε*) and permeability (μ*) have been measured in the frequency range of 100 kHz to 1.8 GHz. The micro inductors were fabricated with the help of microwave sintered sample by using screen-printing method and co-firing. The electrical properties such as inductance and Quality factor of the prepared inductors were measured over a wide frequency range.     

The effect of Bi substitution on phase formation and low temperature sintering of Y-type hexagonal ferrite

Polycrystalline Y-type hexagonal ferrite, with composition of Ba_2?x Bi _x Zn_0.8Co_0.8+x Cu_0.4Fe_12?x O₂₂ (x?=?0～0.4), was prepared by the solid state reaction method. The effect of Bi substitution on phase formation, sintering process and magnetic properties were investigated in detail. The phase formation process was characterized by the means of powder X-ray diffraction (XRD). Bi³⁺ can substitute Ba²⁺ in Y-type hexagonal ferrite as divalent metal ion Co²⁺ substitute Fe³⁺ at the same time for electrovalence balance. As Bi amount is less than 0.3, the phase formation of Y-type hexagonal ferrite will not be destroyed. As Bi amount further increases, the lattice mismatch induced by the difference in ionic radii of Bi³⁺ and Ba²⁺ ions prevents the formation of pure Y-type phase. The samples with proper Bi substitution (0.05?<?x?<?0.3) have much lower phase formation temperature than that of the samples without Bi substitution. Bi substitution can also promote the sintering process. As x?>?0.1, the samples can be sintered well under 900 °C without any other addition. These materials are suitable for multilayer chip inductive components and devices.     

Ni–Mn–Fe–Cr–O negative temperature coefficient thermistor compositions: Correlation between processing conditions and electrical characteristics

A study has been carried out to correlate the effect of sintering temperature on the microstructural, electrical and reliability aspects of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ (x = 0 to 0.3 and y = 0 to 0.3) negative temperature coefficient thermistor compositions prepared by solid-state route. The calcined and sintered compositions were characterized by X-ray diffraction and Scanning Electron Microscopy. The existence of cubic spinel single-phase region was determined by sintering Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ samples in air at temperatures 1150 to 1250 °C. X-ray diffraction patterns of samples sintered above 1200 °C shows additional Bragg reflections of a rock salt structured NiO phase besides normal cubic spinel. A maximum B-value of 4044 K was obtained for Ni_0.75Mn_1.95Cr_0.25Fe_0.05O₄ composition at a sintering temperature 1250 °C/3 h. The reliability of the thermistor compositions were evaluated by performing accelerated ageing based on thermal cycling test. We found that chromium enhances the reliability of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ (x = 0 to 0.3 and y = 0 to 0.3) based NTC thermistor compositions. A maximum reliability of +0.25% resistance drift was observed at sintering temperature 1200 °C for 0.25 mol% chromium content. Excellent reliability of Ni_0.75Mn_{(2.25−x−y)}Cr _x Fe _y O₄ NTC thermistor compositions makes it ideal candidates for high-performance thermal sensor applications.     

Synthesis and characterization of novel Ca2Zn4Ti15O36 microwave ceramics derived from sol-gel powder

A novel microwave dielectric ceramics with composition of Ca₂Zn₄Ti₁₅O₃₆ (CZT) have been synthesized at different sintering temperatures, using citrate sol-gel derived powder. The sintering behavior and the phase identification of the powders were evaluated using differential thermal analysis-thermo gravimetric analysis and X-ray powder diffraction analysis techniques. The phase of CZT can be observed in the powder calcined at 900 °C. The single-phase of CZT, however, can only be obtained at sintering temperature of 1,000 °C or above. The single-phase CZT ceramics can be sintered into dense at 1,100 °C, exhibiting excellent microwave dielectric properties of ? _r?=?48.1, Q?×?f?=?27,000 GHz, and τ _f?=?+53.5 ppm/°C. The effects of sintering temperature on the density, microstructure, and dielectric properties of the sintered ceramics were investigated. The mechanism responsible for the change of dielectric properties with sintering temperature was also discussed.     

Liquid phase effect of La2O3 and V2O5 on microwave dielectric properties of Mg2TiO4 ceramics

Dielectric ceramics of Mg₂TiO₄ (MTO) were prepared by solid-state reaction method with 0.5–1.5 wt.% of La₂O₃ or V₂O₅ as sintering aid. The influences of La₂O₃ and V₂O₅ additives on the densification, microstructure and microwave dielectric properties of MTO ceramics were investigated. It is found that La₂O₃ and V₂O₅ additives lowered the sintering temperature of MTO ceramics to 1300 °C and 1250 °C respectively, whereas the pure MTO exhibits highest density at 1400 °C. The reduction in sintering temperature with these additives was attributed to the liquid phase effect. The average grain sizes of the MTO ceramics added with La₂O₃, and V₂O₅ found to decrease with an increase in wt%. The dielectric constant (ε_r) was not significantly changed, while unloaded Q values were affected with these additives, and the values were in the range of 92,000–157,550 GHz and 98,000–168,000 GHz with the addition of La₂O₃ and V₂O₅, respectively. The dielectric properties are strongly dependent on the densification and the microstructure of the MTO ceramics. The decrease in Q×f _o value at higher concentration of La₂O₃ and V₂O₅ addition was owing to inhomogeneous grain growth and the liquid phase which is segregated at the grain boundary. In comparison with pure MTO ceramics, La₂O₃ and V₂O₅ additives effectively improved the densification and dielectric properties with lowering of sintering temperature. The proposed loss mechanisms suggest that the oxygen vacancies and the average grain sizes are the influencing factors in the dielectric loss of MTO ceramics.     

Crystal structure and the effect of annealing atmosphere on the dielectric properties of the spinels MgAl2O4, NiFe2O4, and NiAlFeO4

The non-transition metal spinel MgAl₂O₄ and the transition metal spinels (NiFe₂O₄, NiAlFeO₄) have been prepared by standard ceramic processing method in the air. The effect of annealing atmosphere on the dielectric properties after sintering has been studied. The annealing atmospheres were N₂, O₂, and N₂–H₂ mixture. Dielectric constant ? _r and tangent loss tanδ have been characterized by varying the measuring temperature and frequency (5 Hz–5 MHz) using the impedance analyzer. The ? _r and tanδ of the non-transition metal spinel MgAl₂O₄ remained unchanged even with varying the annealing atmosphere. While the dielectric properties of the transition metal spinels, NiFe₂O₄ and NiAlFeO₄ were critically dependent on the annealing atmosphere. Crystal structural models for the samples manufactured in air have been tested by the Rietveld refinement method for both the centrosymmetric Fd-3m and the noncentrosymmetric F-43m. The electron density distributions were determined by the whole pattern fitting based on the maximum entropy method (MEM). The dielectric properties of the samples have been also discussed in terms of the structure and electron distribution analysis results.     

Low-temperature sintering and microwave dielectric properties of ZnTiO3-based LTCC materials

The low-temperature sintered microwave dielectric ceramics with composition of ZnTiO₃-0.25TiO₂ were prepared by adding a small amount of low-melting compounds CuO-V₂O₅-Bi₂O₃ (CVB). The phase relationship and dielectric properties as a function of sintering temperature and the additional amount were studied. It is demonstrated that the addition of low-melting CVB can suppress the formation of Zn₂TiO₄ at low temperature, but decrease the decomposition temperature of ZnTiO₃. The sintering temperature has a significant effect on the stability of ZnTiO₃ and dielectric properties of sintered ceramics. CVB addition can promote the densification of ceramics through liquid-phase sintering. The dense 2wt% CVB-doped ZnTiO₃-0.25TiO₂ ceramics prepared at 850 °C have excellent dielectric properties of ??=?30, Q×f?=?32,000 GHz, and τ _f ?=?+12 ppm/ °C.     

Low-temperature sintering and dielectric properties of the Bi(Nb1−x Ta x )O4 system

Low-temperature sintering and dielectric properties of the Bi(Nb_1?x Ta _x )O₄ (x?=?0.1, 0.3, and 0.5) system was investigated as a function of the zinc borosilicate (ZBS) glass content with a view to applying this system to LTCC technology. The addition of 7 wt% ZBS glass ensured a successful sintering below 900°C. The complete solid solution of Bi(Nb, Ta)O₄ with an orthorhombic structure was formed and the high temperature form of Bi(Nb, Ta)O₄ with a triclinic structure was not observed. The second phase of Bi₂SiO₅ was observed for all compositions. The non-relative liquid phase sintering (NLPS) occurred and the one-stage sintering was conducted. The Q?×?f values were improved by the addition of Ta. Bi(Nb_0.7Ta_0.3)O₄ with 7 wt% ZBS glass sintered at 900°C demonstrated 35.8 in the dielectric constant (? _r), 2,200 GHz in the quality factor (Q?×?f ₀), and ?48 ppm/°C in the temperature coefficient of resonant frequency (τ _f).     

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.     

Dielectric,ferroelectric and ferromagnetic properties of x Ni0.8Zn0.2Fe2O4-(1-x) Pb0.99La0.02Zr0.65Ti0.35O3 composites

For the present study, two phase ceramic (ferroelectric-ferrite) composites using La substituted lead zirconate titanate (PLZT) and Ni-Zn ferrite (NZF) with compositional formula x Ni_0.8Zn_0.2Fe₂O₄-(1-x) Pb_0.99La_0.02Zr_0.65Ti_0.35O₃ (x?=?0, 0.05, 0.10 and 0.15) were synthesized by conventional solid state reaction route. From X-ray analysis, it was confirmed that no chemical reaction took place between individual phases. Dielectric properties were studied as a function of temperature and frequency. Decrease in dielectric constant and increase in dielectric loss was observed with increasing ferrite content. Anomalous behavior in paraelectric region was observed for all the composite samples (x?=?0.05, 0.10 and 0.15) at low frequencies. To study ferroelectric and ferromagnetic properties, P-E and M-H hysteresis loops were recorded respectively. Effect of electric field on magnetization was studied for all composite samples to confirm magnetoelectric coupling.     

Sintering and dielectric properties of (Ta2O5)1−x (TiO2) x polycrystalline ceramics

(Ta₂O₅)_1?x (TiO₂) _x system ceramics has been studied intensively as a promising dielectric material for next generation of high density dynamic random access memories instead of SiO₂ and Si₃N₄. It is found that the dielectric permittivity of (Ta₂O₅)_1?x (TiO₂) _x ceramics was dependent of fabrication process. But in the previous work, their calcining and sintering time were too long, generally for 24 h or even more. A relatively quick sintering process was provided which calcining and sintering time can be decreased to 12 h at 1200°C and 1 h at 1550°C, respectively. This kind of sintering process can save a lot of energy and time that is in favor of the industrial production. Under this sintering process, the composition dependent dielectric properties of (Ta₂O₅)_1?x (TiO₂) _x ceramics have been studied in a wide range of composition (0.01?≤?x?≤?0.20), and the dielectric constants of most compositions can be drastically enhanced. The maximum dielectric value can reach 216 at composition x?=?0.04. In the meantime, the mechanism of improvement of ceramic dielectric constants sintered at 1550°C was also discussed.     

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.