Colloidal processing of polymer ceramic nanocomposite integral capacitors

Polymer ceramic composites form a suitable material system for low temperature fabrication of embedded capacitors appropriate for the MCM-L technology. Improved electrical properties such as permittivity can be achieved by efficient filling of polymers with high dielectric constant ceramic powders such as lead magnesium niobate-lead titanate (PMN-PT) and barium titanate (BT). Photodefinable epoxies as the matrix polymer allow fine feature definition of the capacitor elements by conventional lithography techniques. The optimum weight percent of dispersant is tuned by monitoring the viscosity of the suspension. The dispersion mechanism (steric and electrostatic contribution) in a slightly polar solvent such as propylene glycol methyl ether acetate (PGMEA) is investigated from electrophoretic measurements. A high positive zeta potential is observed in the suspension, which suggests a strong contribution of electrostatic stabilization. By optimizing the particle packing using a bimodal distribution and modified processing methodology, a dielectric constant greater than 135 was achieved in PMN-PT/epoxy system. Suspensions are made with the lowest PGMEA content to ensure the efficiency of the dispersion and efficient particle packing in the dried film. Improved colloidal processing of nanoparticle-filled epoxy is a promising method to obtain ultra-thin capacitor films (<2/spl mu/m) with high capacitance density and improved yield. Capacitance of 35 nF/cm/sup 2/ was achieved with the thinnest films (2.5-3.0 /spl mu/m).     

Novel polymer-ceramic nanocomposite based on new concepts for embedded capacitor application (I)

A rapid growth of mixed-signal integrated circuits is driving the needs of multifunction and miniaturization of the component in electronics applications. Polymer-ceramic composites have been of great interest as embedded capacitor materials because they enabled companies to combine the processability of polymers with the high dielectric constant of ceramics. This paper presents the preparations and performance characterizations of novel polymer-ceramic nanocomposites based on new concepts for embedded capacitor application. First, metal particle nickel-filled nanocomposite with high dielectric constant was evaluated as a candidate for embedded capacitors. Two types of nickel particles were selected with the size of 400 and 150nm, respectively. With proper filler loading and highly dispersed, a high dielectric constant of over 90 was observed with a filler loading ratio of 60-vol%. Second, the surface modification of a barium titanate (BTO) particle was also attempted in nanocomposite. Phthalocyanine-coated BTO (Pc-coated BTO) was selected as filler to prepare the composite. Its dielectric constant was observed as over 80 at 1MHz, which was much higher than that of composite derived from commercial BTO. Last, in order to improve the processability of the nanocomposite, 4, 4'-diphenylmethane bismaleimide (BMI) was selected as a matrix polymer by the combination with polyamide (PA). Higher dielectric constant nanocomposite derived from PA/BMI and Pc-coat BTO was obtained, and its potential application towards embedded capacitors was also evaluated.     

Optimization of Epoxy-Barium Titanate Nanocomposites for High Performance Embedded Capacitor Components

One of the most promising avenues to meet the requirements of higher performance, lower cost, and smaller size in electronic systems is the embedded capacitor technology. Polymer-ceramic nanocomposites can combine the low cost, low temperature processability of polymers with the desirable electrical and dielectric properties of ceramic fillers, and have been identified as the major dielectric materials for embedded capacitors. However, the demanding requirements of mechanical properties and reliability of embedded capacitor components restrict the maximum applicable filler loading (<50vol%) of nanocomposites and thereby limit their highest dielectric constants (<50) for real applications. In this paper, we present a study on the optimization of the epoxy-barium titanate nanocomposites in order to obtain high performance, reliable embedded capacitor components. To improve the reliability of polymer-ceramic nanocomposites at a high filler loading, the epoxy matrix was modified with a secondary rubberized epoxy, which formed isolated flexible domains (island) in the continuous primary epoxy phase (sea). The effects of sea-island structure on the thermal mechanical properties, adhesion, and thermal stress reliability of embedded capacitors were systematically evaluated. The optimized, rubberized nanocomposite formulations had a high dielectric constant above 50 and successfully passed the stringent thermal stress reliability test. A high breakdown voltage of 89MV/m and a low leakage current of about 1.9times10^-11A/cm² were measured in the large area thin film capacitors     

A precise numerical prediction of effective dielectric constant forpolymer-ceramic composite based on effective-medium theory

Nanostructure polymer-ceramic composite with high dielectric constant (ϵ_τ~90) has been developed for embedded capacitor application. This polymer-ceramic system consists of lead magnesium niobate-lead titanate (PMN-PT) ceramic particle and modified high-dielectric constant low-viscosity epoxy resin. In order to obtain precise prediction of effective dielectric constant of this composite, an empirical prediction model based on self-consistent theory is proposed. The electrical polarization mechanism and interaction between epoxy resin and ceramic filler has been studied. This model can establish the relevant constitutional parameters of polymer-ceramic composite materials such as particle shape, composition, and connectivity that determine the dielectric properties of the composite. This model is simpler, uses fewer parameters and its prediction compares better with experiment (error <10%). The precision and simplicity of the model can be exploited for predictions of the properties and design of nanostructure ferroelectric polymer-ceramic composites. The effective-medium theory (EMT) has been proved a good tool to predict effective properties of nanocomposites     

High dielectric constant polymer-ceramic (Epoxy varnish-barium titanate) nanocomposites at moderate filler loadings for embedded capacitors

Polymer-ceramic nanocomposites are the major candidate dielectrics for embedded capacitors. Due to the poor adhesion and poor thermal stress reliability at high filler loadings, commercially available polymer-ceramic composites can only achieve a maximum dielectric constant of ∼30. However, a high dielectric constant of ∼50–200 is required to make the layout area small enough for embedding applications. In this work, we systematically studied the material formulations in order to obtain a high dielectric constant (κ>50) at the lowest ceramic filler loading. It was found that material design and processing were critical. By modifying the epoxy matrix with a chelating agent and using bimodal fillers and a proper amount of dispersing agent, dielectric constants ∼50 were obtained at moderate filler loadings.     

Numerical prediction of failure paths at a roughened metal/polymer interface

Debonding of polymer–metal interfaces often involves both interfacial and cohesive failure. This paper extends the investigation of Yao and Qu presented in [Yao Q, Qu J. Interfacial versus cohesive failure on polymer–metal interfaces in electronic packaging – effects of interface roughness. J Electr Packag 2002;124;127–34] towards a numerical fracture mechanics model that is used to quantitatively predict the relation between cohesive and adhesive failure on a metal–polymer interface. As example, an epoxy–aluminum interface is investigated. The competition between adhesive and cohesive failure depending on surface roughness parameters will be studied. Understanding of these phenomena could enable the optimization of interface properties for different applications.     

Dielectric constant of barium titanate/cyanoethyl ester of polyvinyl alcohol composite in comparison with the existing theoretical models

A unique method has been introduced to measure the dielectric constant of polymer/ceramic composites using an effective medium instead of using the general methods of preparing bulk sintered pellets or films. In this work, a new and a simple method has been applied to measure the dielectric constant of polyvinyl cyanoethylate/barium titanate composites. The results are obtained by dispersing the ceramic powders in the polymer of a relatively low dielectric constant value. The dielectric constant of the composites is measured with varying ceramic volume percentages. The obtained results are compared with the many available theoretical models that are generally in practice to predict the dielectric constant of the composites. Then these results are extrapolated to comprehend the dielectric constant values of ceramic particles as these values form the base for the design of the composite. The precision and simplicity of the method can be exploited for predictions of the properties of nanostructure ferroelectric polymer/ceramic composites.     

Embedded Capacitors in Printed Wiring Board: A Technological Review

This paper reviews the technology of embedded capacitors, which has gained importance with an increase in the operating frequency and a decrease in the supply voltage of electronic circuits. These capacitors have been found to reduce the number of surface-mount capacitors, which can assist in the miniaturization of printed wiring boards. This paper describes various aspects of embedded capacitors, such as electrical performance, available dielectric materials, manufacturing processes, and reliability. Improvement in electrical performance is explained using a cavity model from the theory of microstrip antennas. The advantages and disadvantages of dielectric materials such as polymers, ceramics, polymer–ceramic composites, and polymer–conductive filler composites are discussed. Various manufacturing techniques that can be used for the fabrication of embedded capacitors are also discussed. Embedded capacitors have many advantages, but failure of an embedded capacitor can lead to board failure since these capacitors are not reworkable. The effect of various environmental stress conditions on the reliability of embedded capacitors is reviewed.     

Modeling ceramic filled polymer integrated capacitor formationusing neural networks

Integrated decoupling capacitors for MCM-L/D technology are an important component for next-generation electronic packaging applications. This paper presents a statistically designed experiment for systematic characterization of the dielectric constant and loss tangent of integrated capacitors formed by mixing lead magnesium niobate (PMN) particles into polyimide and benzocyclobutene (BCB) polymer dielectric layers. We determine these quantities as a function of the type of polymer material, a volume fraction of ceramic in the polymer matrix, a polymer cure time, and polymer cure temperature. These factors have been examined by means of a D-optimal experiment. Results indicate manipulation of each of the four factors over the ranges examined lead to considerable variation in dielectric constant and loss tangent. Based on data from these experiments, we train neural networks to model this process variation as a function of above variables. Using this methodology, we determine proper combinations of polymer/ceramic materials and processing conditions to achieve desirable electrical properties     

一种内埋式电容器用钛酸钡/环氧复合材料的研制

基于钛酸钡和丁腈橡胶的高介电常数特性,研制了一种可用于内埋式电容器的钛酸钡/环氧复合材料.以丁腈橡胶作为添加剂,用共混法制备钛酸钡/环氧复合材料,探讨了钛酸钡和丁腈橡胶含量对复合材料介电常数、介电损耗因子、体积电阻率及击穿电压等介电性能的影响.实验结果表明,丁腈橡胶可以提高钛酸钡/环氧复合材料的介电常数.在钛酸钡体积分数为40%时,通过添加15%的丁腈橡胶,复合材料的介电常数可从25提高到41,体积电阻率达1011Ω·m,击穿电压达8 kV/mm,而介电损耗因子仍小于0.02.为工业化低成本生产内埋式电容器材料提供了一种新的方法.     

Polyhedral Oligosilsesquioxane‐Modified Boron Nitride Nanotube Based Epoxy Nanocomposites: An Ideal Dielectric Material with High Thermal Conductivity

Dielectric polymer composites with high thermal conductivity are very promising for microelectronic packaging and thermal management application in new energy systems such as solar cells and light emitting diodes (LEDs). However, a well‐known paradox is that conventional composites with high thermal conductivity usually suffer from the high dielectric constant and high dielectric loss, while on the other hand, composite materials with excellent dielectric properties usually possess low thermal conductivity. In this work, an ideal dielectric thermally conductive epoxy nanocomposite is successfully fabricated using polyhedral oligosilsesquioxane (POSS) functionalized boron nitride nanotubes (BNNTs) as fillers. The nanocomposites with 30 wt% fraction of POSS modified BNNTs exhibit much lower dielectric constant, dielectric loss tangent, and coefficient of thermal expansion in comparison with the pure epoxy resin. As an example, below 100 Hz, the dielectric loss of the nanocomposites with 20 and 30 wt% BNNTs is reduced by one order of magnitude in comparison with the pure epoxy resin. Moreover, the nanocomposites show a dramatic thermal conductivity enhancement of 1360% in comparison with the pristine epoxy resin at a BNNT loading fraction of 30 wt%. The merits of the designed composites are suggested to originate from the excellent intrinsic properties of embedded BNNTs, effective surface modification by POSS molecules, and carefully developed composite preparation methods.     

Topological‐Structure Modulated Polymer Nanocomposites Exhibiting Highly Enhanced Dielectric Strength and Energy Density

Dielectric materials with high electric energy densities and low dielectric losses are of critical importance in a number of applications in modern electronic and electrical power systems. An organic–inorganic 0–3 nanocomposite, in which nanoparticles (0‐dimensional) are embedded in a 3‐dimensionally connected polymer matrix, has the potential to combine the high breakdown strength and low dielectric loss of the polymer with the high dielectric constant of the ceramic fillers, representing a promising approach to realize high energy densities. However, one significant drawback of the composites explored up to now is that the increased dielectric constant of the composites is at the expense of the breakdown strength, limiting the energy density and dielectric reliability. In this study, by expanding the traditional 0–3 nanocomposite approach to a multilayered structure which combines the complementary properties of the constituent layers, one can realize both greater dielectric displacement and a higher breakdown field than that of the polymer matrix. In a typical 3‐layer structure, for example, a central nanocomposite layer of higher breakdown strength is introduced to substantially improve the overall breakdown strength of the multilayer‐structured composite film, and the outer composite layers filled with large amount of high dielectric constant nanofillers can then be polarized up to higher electric fields, hence enhancing the electric displacement. As a result, the topological‐structure modulated nanocomposites, with an optimally tailored nanomorphology and composite structure, yield a discharged energy density of 10 J/cm³ with a dielectric breakdown strength of 450 kV mm^–1, much higher than those reported from all earlier studies of nanocomposites.     

Measuring the through-plane elastic modulus of thin polymer films in situ

Due to the ongoing increase of the transistor density on a chip, industry has replaced the silicon oxide dielectric layers, traditionally used in the back-end interconnect stack, by low-K polymer films with a thickness down to several hundred nanometers. The use of these polymer dielectric films has introduced new failure modes. To have a better understanding of these failures, knowledge of the mechanical properties is necessary. Due to surface effects, the material properties of thin films may differ in the in-plane and trough-plane direction. Most techniques available for measuring these properties are only capable of obtaining the in-plane modulus. To have an in situ measurement of the through-plane modulus, a parallel plate capacitor (PPC) under hydrostatic pressure is used in combination with an interdigitated electrode (IDE) to capture the change in dielectric constant. Since it is believed to be mechanical isotropic, a benzocyclobutene (BCB) film is used to provide a reference measurement. The through-plane elastic modulus and change in permittivity for a 1 μm thick film sandwiched by two aluminum electrodes on a silicon wafer are reported. Two circular PPCs and four IDEs were tested at a pressure of 0, 5, 7.5 and 10 MPa. An initial relative dielectric constant of the film of 2.66 ± 0.05 was obtained. This yields a change in constant equal to 1.241 × 10⁻⁴ ± 2.1 × 10⁻⁵ per MPa pressure at room temperature. The through-plane modulus showed a linear elastic behavior equal to 4.73 ± 0.46, 4.11 ± 0.39 and 3.64 ± 0.31 GPa for 20°, 50° and 75 °C, respectively. The modulus at room temperature is in good agreement with the values found in literature.     

Aqueous-Develop,Photosensitive Polynorbornene Dielectric: Properties and Characterization

The properties of a new aqueous-base-develop, negative-tone photosensitive polynorbornene have been characterized. High-aspect-ratio features of 7:1 (height:width) were produced in 70-μm-thick films in a single coat with straight side-wall profiles and high fidelity. The polymer films studied had contrast of 12.2 and low absorption coefficient. To evaluate the polymer’s suitability to microelectronics applications, epoxy crosslinking reactions were studied as a function of processing condition through Fourier-transform infrared spectroscopy, nanoindentation, and dielectric measurements. The fully crosslinked films had an elastic modulus of 2.9 GPa and hardness of 0.18 GPa.     

Conductivity photoquenching effect in polymer–ferrocene composites

Based on a nonpolar polymer—i.e., high-density polyethylene, polar polyvinylidene fluoride, and di-π-cyclopentadienyl iron (π-(C₅H₅)₂Fe, ferrocene)—matrix composites are obtained that exhibit the conductivity photoquenching effect. Charge states and photoelectret and photoconductive properties of films of these composites are studied. In the visible region, the degree of conductivity photoquenching of matrix composites depends heavily on charge transport features in the heterogeneous polymer-ferrocene system and on reversible changes in electrical and chemical properties of ferrocene structures upon exposure to the electric field and light. A possible mechanism of the conductivity photoquenching effect in polymer-ferrocene composites is proposed that adequately accounts for experimental results. As light is turned off, the dark current is restored, which indicates the reversibility of the observed effect. The negative photoconductivity does not appear when CdS is used instead of ferrocene in composites of polymers under study. The negative photoconductivity effect increases when the third component, i.e., CdS photosensitive semiconductor, is introduced into the polymer-ferrocene composite.     

Charging–discharging characteristics of a wound aluminum polymer capacitor

This study characterized aluminum polymer capacitors, especially when they are charging and discharging. Tests were conducted under various conditions. The following environments were considered: three high-temperature conditions, two high temperature/high humidity conditions, and room temperature. Various operating conditions were also considered, such as charging–discharging, operating, and storage. The test results showed that the capacitance of the wound polymer aluminum capacitor degraded with charging–discharging at low temperature. At lower temperatures, this characteristic accelerated but was mitigated with a dry electrolyte. The degraded capacitances partially recovered when the capacitors were stored at a high temperature. These characteristics were not observed for a conventional liquid aluminum capacitor. This unreported special characteristic of polymer aluminum capacitors should be considered when designing systems such as power electronics. Polymer capacitors are known for their high reliability, especially at high temperatures. At low temperatures, however, the charging–discharging characteristic should be carefully considered. This paper reports on this characteristic of polymer capacitors for consideration by industries.     

Enabling High-Energy-Density High-Efficiency Ferroelectric Polymer Nanocomposites with Rationally Designed Nanofillers

Ferroelectric polymers have been regarded as the preferred matrix for high-energy-density dielectric polymer nanocomposites because of their highest dielectric constants among the known polymers. Despite a library of ferroelectric polymer-based composites having been demonstrated as highly efficient in enhancing the energy density, the charge–discharge efficiency remains moderate because of the high intrinsic loss of ferroelectric polymers. Herein, a systematic study of the oxide nanofillers is presented with varied dielectric constants and the vital role of the dielectric match between the filler and the polymer matrix on the capacitive performance of the ferroelectric polymer composites is revealed. A combined experimental and simulation study is further performed to specifically investigate the effect of the nanofiller morphology on the electrica properties of the polymer nanocomposites. The solution-processed ferroelectric polymer nanocomposite embedded with Al₂O₃ nanoplates exhibits markedly improved breakdown strength and discharged energy density along with an exceptional charge–discharge efficiency of 83.4% at 700 MV m⁻¹, which outperforms the ferroelectric polymers and nanocomposites reported to date. This work establishes a facile approach to high-performance ferroelectric polymer composites through capitalizing on the synergistic effect of the dielectric properties and morphology of the oxide fillers.     

High-Temperature Capacitor Polymer Films

Film capacitor technology has been under development for over half a century to meet various applications such as direct-current link capacitors for transportation, converters/inverters for power electronics, controls for deep well drilling of oil and gas, direct energy weapons for military use, and high-frequency coupling circuitry. The biaxially oriented polypropylene film capacitor remains the state-of-the-art technology; however, it is not able to meet increasing demand for high-temperature (>125°C) applications. A number of dielectric materials capable of operating at high temperatures (>140°C) have attracted investigation, and their modifications are being pursued to achieve higher volumetric efficiency as well. This paper highlights the status of polymer dielectric film development and its feasibility for capacitor applications. High-temperature polymers such as polyetherimide (PEI), polyimide, and polyetheretherketone were the focus of our studies. PEI film was found to be the preferred choice for high-temperature film capacitor development due to its thermal stability, dielectric properties, and scalability.     

Reduced Temperature Coefficient of Capacitance (TCC) of Embedded Capacitor Films (ECFs) for Organic Substrates using SrTiO3 and Multifunctional Epoxy

Epoxy/ceramic composites have attracted great interest as embedded capacitor materials, mainly due to the process compatibility of epoxy with printed circuit boards (PCBs). However, one of the potential problems of epoxy/ceramic composites is the temperature dependence of their dielectric properties. This study focuses mainly on reducing the temperature coefficient of capacitance (TCC) of epoxy/ceramic composites using multifunctional epoxy and SrTiO₃ powder. The TCC of an epoxy/ceramic composite mainly depends on the properties of its epoxy and ceramic powder. Using multifunctional epoxy, the epoxy resin showed two glass-transition temperatures, resulting in a lower dimensional change after the first glass-transition temperature. Additionally, the TCC of epoxy/SrTiO₃ ECFs can be decreased by increasing the SrTiO₃ powder content. As a result, reduced TCC of epoxy/ceramic composite capacitors using a multifunctional epoxy and SrTiO₃ powder was successfully demonstrated for embedded capacitors in organic substrates.     

Epoxy/BaTiO/sub 3/ composite films and pastes for high dielectric constant and low-tolerance embedded capacitors fabrication in organic substrates

Epoxy/BaTiO/sub 3/ composite embedded capacitor films (ECFs) were newly designed for high dielectric constant and low-tolerance (less than /spl plusmn/5%) embedded capacitor fabrication for organic substrates. In terms of material formulation, ECFs are composed of a specially formulated epoxy resin and latent curing agent, and in terms of a coating process, a comma roll coating method is used for uniform film thickness in large area. The dielectric constant of ECF in high frequency range (0.5/spl sim/3 GHz) is measured using the cavity resonance method. In order to estimate dielectric constant, the reflection coefficient is measured with a network analyzer. The dielectric constant is calculated by observing the frequencies of the resonant cavity modes. Calculated dielectric constants in this frequency range are about 3/4 of the dielectric constants at 1 MHz. This difference is due to the decrease of the dielectric constant of the epoxy matrix. The dielectric relaxation of barium titanate (BaTiO/sub 3/: BT) powder is not observed within measured frequency. An alternative material for embedded capacitor fabrication is epoxy/BaTiO/sub 3/ composite embedded capacitor paste (ECP). It uses similar materials formulation like ECF and a screen printing method for film coating. The screen printing method has the advantage of forming a capacitor partially in the desired part. However, the screen printing makes surface irregularities during mask peel-off. Surface flatness is significantly improved by adding some additives and by applying pressure during curing. As a result, a dielectric layer with improved thickness uniformity is successfully demonstrated. Using epoxy/BaTiO/sub 3/ composite ECP, a dielectric constant of 63 and specific capacitance of 5.1 nF/cm/sup 2/ were achieved.