Embedded Capacitor Technology Using Aerosol Deposition

Embedded passives, which achieve miniaturization, cost reduction, and higher performance, are regarded as one of the most promising technologies for a future RF module substrate. Currently, a BaTiO₃/Polymer composite is being used for the embedded capacitors in printed wiring boards. One of the drawbacks of this composite is its relatively low dielectric constant, because the polymer component with a low dielectric constant suppresses the dielectric constant of the whole composite. We propose a resin build-up circuit board with passive functions embedded in a ceramic film without any polymer component for the next-generation low-cost RF modules. We have already manufactured a prototype board with ceramic capacitors embedded in an FR-4 substrate using a unique ceramic deposition technology: aerosol deposition (ASD) in which many kinds of ceramics can be deposited on a substrate at room temperature by making use of accelerated ceramic nanoparticle aerosol bombardment with a nozzle. In this study, first we examine the effects of the characteristics of raw ceramic powder on the crystal structure and the dielectric properties of ASD films. As a result, we confirmed that dense BaTiO₃ dielectric films can be deposited when raw powder without strain is used. From the resulting polarization versus electrical field (P–E curve), we confirmed that paraelectric was observed in the dense films, while the porous BaTiO₃ films deposited using milled powder exhibit a small hysteresis loop. We also clarified that dense BaTiO₃ dielectric films exhibit a nanostructure with a texture consisting of particles under 10 nm in diameter. We also examine the interfacial behavior between BaTiO₃ dielectric films and the Cu electrode, in order to investigate the deposition temperature and the reliability of a BaTiO₃ ASD film under high temperature (250°C), high humidity (100 Rh%), thermal cycle condition (−55°C to 150°C), and bias DC voltage (5 V). We clarified that the BaTiO₃ ASD film satisfies the criteria of reliability in the microelectronic packaging area.     

Characteristics of polyimide/barium titanate composite films

In this study, the characteristics of the polyimide/BaTiO₃ composite films with various amounts of BaTiO₃ were evaluated. Modifier 1-methoxy-2-propyl acetate was added during composite preparation to disperse the BaTiO₃ particles in polyimide matrix. Conversion of polyamic acid (PAA) to polyimide was not completed for the composite film with a high BaTiO₃ loading (90 wt%). Dielectric constant of the film increases from 3.53 to 46.50, at the sweep frequency of 10 kHz, as the BaTiO₃ content increases from 0 to 90 wt% (0–67.5 vol.%), which is mainly due to the relatively high dielectric constant of BaTiO₃ particles in the polyimide matrix. The dielectric losses at 10 kHz is ranging from 0.005 to 0.015, which is due to the switching of the domain wall. Water absorption decreases considerably with increasing BaTiO₃ content. With 10 wt% (2.5 vol.%) BaTiO₃ addition, the water absorption of the composite film reduces 45% from that of pure polyimide. Also, high loading of BaTiO₃ is not beneficial to reduce the water absorption of the composite film.     

Flexible /PET/batio3/ layer–layer composite film with enhanced dielectric properties fabricated by highly loaded /batio3/ coating with acrylic resin as binder

Flexible layer–layer poly(ethylene phthalate) (PET)/BaTiO₃ composite films with enhanced dielectric permittivity were fabricated by spin coating method, consisting of PET substrate film layer and modified BaTiO₃/acrylic resin hybrid coating layer. The thickness of coating layer was less than 3 μm (about 2% of PET film thickness), and therefore, the PET/barium titanate (BT) composite films remained flexible even at high volume fraction of BaTiO₃ fillers. The volume contents of BaTiO₃ were varied from 0 to 80%, and the solid contents of BaTiO₃/acrylic resin were in the range of 51.8–72.9%. Scanning electron microscopy showed strong interaction of finely dispersed BaTiO₃ particles with acrylic resin. Morphological profile also displayed uniform coating layer of modified BaTiO₃/acrylic resin and its strong adhesion with PET film. The dielectric constant of the PET/BaTiO₃ composite films increased by about 26% at 60 vol % BaTiO₃ loading when compared with the pristine PET film, whereas the dielectric loss decreased slightly. In addition, PET‐grafted poly(hydroxylethyl methacrylate) brushes were used as substrate to introduce covalent bonding with the coating layer. Further enhancement of dielectric constant and reduction of dielectric loss were realized when compared with the composite films with bare PET substrate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42508.     

Flexible BaTiO3/SiC@PbTiO3/epoxy composite films with enhanced dielectric performance at high frequency

Flexible polymer composites with high dielectric constants and low dielectric losses at high frequencies are highly desired in microwave and RF applications. However, a high dielectric constant is often obtained at the expense of flexibility because a high loading of filler is needed. In this work, we synthesize a core-shell structured 1D filler by coating high-dielectric-constant PbTiO₃ onto the surface of low-thermal-expansion-coefficient SiC nanofibers, which are then incorporated into the epoxy matrix together with BaTiO₃ nanoparticles to form the multi-phase BaTiO₃/SiC@PbTiO₃/epoxy composite film. A high dielectric constant (35 at 100 Hz and 20 at 5 GHz) and a low dielectric loss (0.023 at 100 Hz and 0.13 at 5 GHz) are achieved as the filling content of SiC@PbTiO₃ and BaTiO₃ is 5.24 wt% and 80 wt%, respectively. Prediction models of the effective dielectric constant of polymer-based composites reveal that a continuous polarization network is constructed in the composites owing to the physical contact between BaTiO₃ and PbTiO₃. The construction of the multi-phase filler provides a feasible way to effectively adjust and improve the dielectric properties of polymer-based composite films.     

Ferroelectric BaTiO3/SrTiO3 multilayered thin films for room-temperature tunable microwave elements

Ferroelectric BaTiO₃/SrTiO₃ with optimized c-axis-oriented multilayered thin films were epitaxially fabricated on (001) MgO substrates. The microstructural studies indicate that the in-plane interface relationships between the films as well as the substrate are determined to be (001)_SrTiO3//(001)_BaTiO3//(001)_MgO and [100]_SrTiO3//[100]_BaTiO3//[100]_MgO. The microwave (5 to 18 GHz) dielectric measurements reveal that the multilayered thin films have excellent dielectric properties with large dielectric constant, low dielectric loss, and high dielectric tunability, which suggests that the as-grown ferroelectric multilayered thin films can be developed for room-temperature tunable microwave elements and related device applications.     

Effect of BaTiO3 on the sensing properties of PVDF composite-based capacitive humidity sensors

Capacitive humidity sensors consisting of materials such as polymers, ceramics, and piezoelectrics are widely used to monitor relative humidity levels. The effect of barium titanate (BaTiO₃) nanoparticles on the humidity sensing properties, dielectric response, thermal stability, and hydrophilicity of the polyvinylidene fluoride (PVDF)-BaTiO₃ composite films is investigated. Hydrophilicity and surface morphology of the PVDF-BaTiO₃ composite films are modified for the development of a good humidity sensor. The nanocomposite solutions are prepared by mixing an optimized concentration (2.5 wt%) of PVDF with different concentrations (0.5, 1, and 2 wt%) of BaTiO₃ nanoparticles. X-ray diffraction, thermogravimetric analysis, field emission scanning electron microscopy, and contact angle measurements are used to characterize the structure, morphology, thermal stability, and hydrophilicity of the spin-coated sensing films. The dielectric study of PVDF-BaTiO₃ composite film shows that as the concentration of BaTiO₃ particles increase, the dielectric constant of the composite films increases as well. PVDF-BaTiO₃ (2.5 wt%-1 wt%) based capacitive sensors show stable capacitive response and low hysteresis as compared to the other concentrations of the PVDF-BaTiO₃ composites. The maximum hysteresis of the capacitive PVDF-BaTiO₃ (2.5 wt%- 1 wt%) humidity sensor is found to be ~2.5%. The response and recovery times of the PVDF-BaTiO₃ (2.5 wt%-1 wt%) based capacitive sensors are determined as 40 s and 25 s, respectively, which are significantly lower than those reported for the other PVDF composite based sensors.     

Simultaneous enhancement of dielectric properties and temperature stability in BaTiO3-based ceramics enabling X8R multilayer ceramic capacitor

Modified BaTiO₃ ceramics that possess high dielectric permittivity and acceptable temperature stability have been widely utilized as multilayer ceramic capacitors (MLCCs) for high-frequency bypass and power filtering in automotive applications. However, since the increasing demand for high-capacity and small-size, high-permittivity materials that can serve as dielectric layers in MLCCs are urgently required. In this work, we design and fabricate a special BaTiO₃-0.03Mg-0.02Y-0.02CaZrO₃ ceramic with a high dielectric permittivity of 3000 and the dielectric variation below ±13% in the temperature range of -55–150°C, fulfilling the requirements of X8R capacitors. To achieve these results, we employed grain size engineering and cation doping, using BaTiO₃ precursors with a particle size of 240 nm to prepare the BaTiO₃-based ceramics with fine grains, while Mg and Y co-doping was used for improving the temperature stability due to dielectric dispersion. Utilizing these high-permittivity BaTiO₃-based materials, we fabricated MLCCs that satisfy the X8R criterion, possessing a high dielectric constant of 2950 and a high breakdown field (410 kV/cm).     

Novel polymer–ceramic nanocomposite based on high dielectric constant epoxy formula for embedded capacitor application

Embedded capacitor technology can increase silicon packing efficiency, improve electrical performance, and reduce assembly cost compared with traditional discrete capacitor technology. Developing a suitable material that satisfies electrical, reliability, and processing requirements is one of the major challenges of incorporating capacitors into a printed wiring board (PWB). Polymer–ceramic composites have been of great interest as embedded capacitor material because they combine the processability of polymers with the high dielectric constant of ceramics. A novel nanostructure polymer–ceramic composite with a very high dielectric constant (ε_r ～110, a new record for the highest reported ε_r value of a nanocomposite) was developed in this work. A high dielectric constant is obtained by increasing the dielectric constant of the epoxy matrix (ε_r >6) and using the combination of lead magnesium niobate–lead titanate (PMN–PT)/BaTiO₃ as the ceramic filler. This nanocomposite has a low curing temperature (<200°C); thus, it is multichip‐module laminate (MCM‐L) process‐compatible. An embedded capacitor prototype with a capacitance density of 50 nF/cm² was manufactured using this nanocomposite and spin‐coating technology. The effect of the composite microstructure on the effective dielectric constant was studied. This novel nanocomposite can be used for integral capacitors in PWBs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1084–1090, 2002     

Thermal and electrical properties of nitrile‐containing polyimide/BaTiO3 composite films

Polyimide composite films were prepared by mixing the BaTiO₃ particles into poly(amic acid) solution followed by film casting and thermal imidization under controlled temperature conditions. The poly(amic acid) was synthesized by solution polycondensation reaction of 4,4′‐oxydiphthalic anhydride with 2,6‐bis(4‐aminophenoxy)benzonitrile, using N‐methyl‐2‐pyrrolidone as solvent. The surface of BaTiO₃ particles was modified by treating with an aminosilane coupling agent, 3‐aminopropyltriethoxysilane. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to characterize the structure and properties of the composites. The influence of BaTiO₃ content on the composite film properties was evidenced. The films exhibited good thermal stability having the initial decomposition temperature above 520°C. They had stable dielectric properties over large intervals of temperature and frequency. The dielectric constant and the dielectric loss increased with the increase of BaTiO₃ content. The dynamic mechanical analysis and dielectric spectroscopy revealed subglass transitions γ and β. At higher temperature an α‐relaxation that corresponds to the glass transition and a conductivity process were evidenced. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Temperature dependence of electrical resistivity and dielectric characteristics of poled and BaZrO3 modified BaTiO3 ceramics

Samples of pure BaTiO₃, pure BaZrO₃ and intermediates containing from 5 up to 30% BaZrO₃ were carefully prepared by the usual ceramic procedure followed by X-ray diffraction analysis to ensure the complete reaction. Well sintered and translucent ceramic bodies were obtained. Measurements of dielectric constant (?), dielectric loss (tan δ) and a.c. resistivity (?) were undertaken as a function of temperature up to 250°C and at various frequencies of 10–50 Kc/s before and after polarization (800 V). The effect of poling field is discussed on the basis of the presence of spontaneous polarization in BaTiO₃ lattice. Finally, it was established that the introduction of Zr⁴⁺ ions in BaTiO₃ lattice occurs in three steps: firstly, filling of Ba²⁺ vacancies, secondly solid solution formation from BaZrO₃ in BaTiO₃ lattice and thirdly, occupying interstitial sites in BaTiO₃ lattice.     

High piezoelectric properties of BaTiO3-xLiF ceramics sintered at low temperatures

BaTiO₃-xLiF ceramics were prepared by a conventional sintering method using BaTiO₃ powder about 100 nm in diameter. The effects of LiF content (x) and sintering temperature on density, crystalline structure and electrical properties were investigated. A phase transition from tetragonal to orthorhombic symmetry appeared as sintering temperatures were raised from 1100 °C to 1200 °C or as LiF was added from 0 mol% to 3 mol%. BaTiO₃-6 mol% LiF ceramic sintered at 1000 °C exhibited a high relative density of 95.5%, which was comparable to that for pure BaTiO₃ sintered at 1250 °C. BaTiO₃-4 mol% LiF ceramic sintered at 1100 °C exhibited excellent properties with a piezoelectric constant d₃₃ = 270 pC/N and a planar electromechanical coupling coefficient k_p = 45%, because it is close to the phase transition point in addition to high density.     

Microstructures and dielectric properties of spark plasma sintered Ba0.4Sr0.6TiO3/CaCu3Ti4O12 composite ceramics

(1 − x)Ba_0.4Sr_0.6TiO₃/xCaCu₃Ti₄O₁₂ composite ceramics were prepared by spark plasma sintering. Sintering behavior, microstructures and dielectric properties of the composite ceramics were investigated by XRD, SEM, EDS and dielectric spectrometer. Dense composite ceramics consisting of Ba_0.4Sr_0.6TiO₃ phase and CaCu₃Ti₄O₁₂ phase were prepared at 800 °C for 0 min. The dielectric loss of the composite ceramic decreased with increasing amount of Ba_0.4Sr_0.6TiO₃, and the high dielectric constant were retained. Moreover, the better temperature stability of dielectric constant was obtained. These improvements of dielectric characteristics have great scientific significance for potential application.     

Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

Deterioration behavior analysis of dysprosium and thulium co-doped barium titanate ceramics for multilayer ceramic capacitors

An accelerated testing method for barium titanate (BaTiO₃) dielectrics was proposed to elucidate deterioration behavior of dielectric constant based on the life-temperature relation. The accelerated degradation test (ADT) which was designed using various temperature ranges below and above Curie temperature (T_c) was focused on the optimized composition of dysprosium (Dy) and thulium (Tm) co-doped BaTiO₃. The statistical analysis of the failure time data was performed to determine the optimum distribution as a goodness-of-fitness test. A scale parameter (η) and activation energy (E_α) were calculated in order to predict the life time of the co-doped BaTiO₃, and there was difference between the expected life times according to the acceleration temperature rating of the ADT. The difference of deterioration mechanism around T_c could be deduced from the change of lattice parameter and polarization behavior. The drastic decrease of tetragonality and ferroelectric property caused by the phase transition of the co-doped BaTiO₃ was verified in the temperature above T_c. Accordingly, the acceleration factor over T_c should be considered as reliability study of the BaTiO₃ dielectrics for multilayer ceramic capacitors (MLCCs).     

Microstructure and dielectric properties of Dy/Mn doped BaTiO3 ceramics

Dy/Mn doped BaTiO₃ with different Dy₂O₃ contents, ranging from 0.1 to 5.0 at% Dy, were investigated regarding their microstructural and dielectric characteristics. The content of 0.05 at% Mn was constant in all the investigated samples. The samples were prepared by the conventional solid state reaction and sintered at 1290°, and 1350 °C in air atmosphere for 2 h. The low doped samples (0.1 and 0.5 at% Dy) exhibit mainly fairly uniform and homogeneous microstructure with average grain sizes ranged from 0.3 μm to 3.0 μm. At 1350 °C, the appearance of secondary, abnormal, grains in the fine grain matrix and core–shell structure were observed in highly doped Dy/BaTiO₃. Dielectric measurements were carried out as a function of temperature up to 180 °C. The low doped samples sintered at 1350 °C, display the high value of dielectric permittivity at room temperature, 5600 for 0.1Dy/BaTiO₃. A nearly flat permittivity–temperature response was obtained in specimens with 2.0 and 5.0 at% additive content. Using a Curie–Weiss and modified Curie–Weiss low, the Curie constant (C), Curie like constant (C′), Curie temperature (T_C) and a critical exponent (γ) were calculated. The obtained values of γ pointed out the diffuse phase transformation in highly doped BaTiO₃ samples.     

Fabrication of porous thick films using room-temperature aerosol deposition

A novel technique for the rapid room-temperature deposition of porous ceramic, glass, or metal thick films using the aerosol deposition (AD) method is presented. The process is based on the co-deposition of the desired film material and a second water-soluble constituent, resulting in a ceramic-ceramic composite. Following the subsequent removal of water-soluble end member, a network of pores is retained. To demonstrate the process, porous BaTiO₃ thick films were fabricated through co-deposition with NaCl. Microstructural images show the clear development of a porous structure, which was found to enhance the dielectric properties over dense thick films, possibly related to the lower extent of internal residual stress. This simple but highly effective porous structure fabrication can be applied to any film and substrate material stable in water and is promising for the application of AD-processed films in gas sensors, solid oxide fuel cells, and humidity sensors.     

Direct integration of dielectric all-ceramic thick films on a polymer substrate using room temperature fabrication

Direct integration of all-ceramic thick films and a polymer substrate has been realized for the first time without high temperature processing using the Room Temperature Fabrication method.Printable Li₂MoO₄-BaTiO₃ composite pastes with 0, 10, and 20 vol.% of BaTiO₃ were fabricated from the respective ceramic powders and water without organic additives or vehicles. The pastes were stencil printed on a polyimide substrate and dried at 120 °C without pressing or lamination.Using scanning electron microscopy, the films were observed to be in seamless contact with the substrate and to have a uniform microstructure. Relative permittivities of the ceramic films increased from 4.2 to 7.2 (at 2.5 GHz) and 4.5 to 7.5 (at 9.9 GHz) according to the vol.% content of the added BaTiO3, with corresponding dielectric losses from 10⁻³ to 10^-2.The results show that the room temperature fabrication method enables 2D printing of all-ceramic thick films on temperature-sensitive substrates.     

Sintering mechanism and dielectric properties of LiTaO3 matrix composites with the addition of Al2O3 particles

Highly densified Al₂O₃/LiTaO₃ (ALT) ceramic composites were fabricated by hot-pressing in a nitrogen atmosphere. The addition of Al₂O₃ particles could significantly improve the densification of LiTaO₃. Sintering mechanism of the LiTaO₃ ceramic incorporated with Al₂O₃ particles is proposed. Dielectric constant of 5 vol.% Al₂O₃/LiTaO₃ (5ALT) composite ceramic was slightly increased in the range from 30 kHz to 10⁶ Hz, but the dielectric loss was lowered in the whole range from 10³ Hz to 10⁶ Hz. Piezoelectric constant (d₃₃) of the 5ALT ceramic composite is about 50% of that of LiTaO₃ single crystal.     

Improved dielectric properties and energy density of PVDF composites using PVP engineered BaTiO<Subscript>3</Subscript> nanoparticles

This work systematically investigates the effect of modifier polyvinylpyrrolidone (PVP) on the microstructure, dielectric and energy storage properties of BaTiO₃/PVDF composites. The results demonstrate that the BaTiO₃ nanoparticles modified by PVP are uniformly dispersed in the composites, and the defects including cracks and voids are obviously decreased in contrast to the composites with unmodified BaTiO₃ nanoparticles. Due to the enhanced interfacial polarization, the composites with BaTiO₃@PVP show improved dielectric properties compared with the composites with unmodified BaTiO₃ nanoparticles. For instance, at 1 kHz, the dielectric constant and dielectric loss of the composite with 50 vol% of BaTiO₃@PVP nanoparticles are 80.4 and 0.085, while of which the BaTiO₃/PVDF are 35 and 0.265, respectively. The discharge energy density of the composites is largely improved with PVP engineered BaTiO₃ nanoparticles. The composite with 30 vol% BaTiO₃@PVP achieves a discharged energy density of 4.06 J/cc at 240 kV/mm, which is 116% larger than that of pure PVDF (1.88 J/cc). This research provides an effect modifier to prepare high performance dielectric materials.     

Effect of the filler morphology on the crystallization behavior and dielectric properties of the polyvinylidene fluoride-based composite

Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO₃-Fe₂O₃ powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO₃-Fe₂O₃ core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.