Comparative study of thermally conductive fillers for use in liquidencapsulants for electronic packaging

Thermal management plays a very vital role in the packaging of high performance electronic devices. Effective heat dissipation is crucial to enhance the performance and reliability of the packaged devices. Liquid encapsulants used for glob top, potting, and underfilling applications can strongly influence the package heat dissipation. Unlike molding compounds, the filler loading in these encapsulants is restrained. This paper deals with the development and characterization of thermally conductive encapsulants with relatively low filler loading. A comparative study on the effect of different ceramic fillers on the thermal conductivity and other critical properties of an epoxy based liquid encapsulant is presented     

A study of properties of plastics used for

Some water-ingress characteristics of 14-lead dual-in-line plastic packages have been studied at 85°C and 85% relative humidity. The materials studied were basically encapsulation-grade silicones and epoxies, some of which have had wide use by the semiconductor industry. Bulk water absorption by the silicones was much less than by epoxies and there were significant differences between two epoxies having similar basic chemistries but made by different manufacturers. The leads did not contribute to water absorption by silicone packages, but a contribution attributable to the leads was discernible in epoxy packages. An empirical correlation has been found between the measured properties of the materials and packages and available results of accelerated temperature-humidity-bias testing on live devices. A hypothesis is proposed which accounts for some of the observed differences in performance between silicone and epoxy encapsulants.     

Accelerated popcorn testing of high solder-reflow crack resistant molding compounds

In testing the resistance of a molding compound to popcorn failures after solder reflow, there are two basic options for shortening the moisture absorption phase: varying the severity of moisture exposure by varying the temperature and percent relative humidity or maintaining a constant humidity/temperature profile and varying the length of time the compounds are exposed. In addition, the total testing time can be accelerated by the choice of test method. There are three major measurement techniques for evaluating the extent of popcorn cracking: SAM testing; bubble chamber testing; and visual crack inspection. In this paper we will explore the effects of differing lengths of exposure time and the merits of different measurement techniques.A variety of epoxy resins, filler mixtures and adhesion additives were examined in semiconductor molding compounds for solder-reflow crack resistance (popcorn crack resistance). A limited comparison of molding compound high-temperature strength properties and extent of popcorn cracking suggests no strong positive correlation. On the other hand, factors that might have an impact on adhesion properties of the molding compound, such as low melt viscosity resins and putative adhesion additives, appear to have the greatest impact. A molding compound developed with these factors showed no internal or external cracks on 84 lead QFPs (29.2 × 29.2 × 3.68 mm) after 72 h of 85°C/85% R.H. and one 10 s solder dip at 260°C. Nor were any external cracks observed after 168 h of 85°C/85% R.H. and one solder dip. However, minor internal cracks were observed.The most data can be obtained by using bubble chamber testing for large numbers of parts and evaluating a smaller sample of the best of those compounds via SAM testing with crack extension analysis. The length of exposure time affected the parts as expected, with longer times being more severe. There did not appear to be a gradient effect or a threshold level. In general, 72 h allowed the greatest differentiation among the compounds tested for internal defects; external defects were not fully developed until 168 h of moisture exposure.     

Adhesion evaluation on low-cost alternatives to thermosetting epoxy encapsulants

The thermosetting epoxy curing systems have been widely used as encapsulants in the electronic packaging industry. With the continual evolving of electronic product markets, material suppliers have been challenged to provide more options to meet the requirements of advanced, yet cost effective, packaging solutions. In this paper, two low-cost alternative materials have been investigated experimentally regarding their adhesion and reliability performance, and these have then been compared with the thermosetting epoxy systems. One of the materials is thermoplastic bisphenol A epoxy/phenoxy resin, and the other is an interpenetrating polymer network composed of an epoxy curing component and a free radical polymerizable component. Some formulations of the materials being studied could exhibit excellent adhesion, durability and application reliability. While reworkability is expected for these materials, they are promising as cost effective encapsulants for electronic packaging, and may be applied with appropriate processing techniques.     

Novel thermally reworkable underfill encapsulants for flip-chipapplications

The flip-chip technique of integrated circuit (IC) chip interconnection is the emerging technology for high performance, high input/output (I/O) IC devices. Due to the coefficient of thermal expansion mismatch between the silicon IC (CTE=2.5 ppm/°C) and the low cost organic substrate such as FR-4 printed wiring board (CTE=18-22 ppm/°C), the flip-chip solder joints experience high shear stresses during temperature cycling. Underfill encapsulant is used to couple the bilayer structure and is critical to the reliability of the flip-chip solder interconnects. Current underfill encapsulants are filled epoxy-based materials that are normally not reworkable after curing. This forms an obstacle to flip-chip on board (FCOB) technology development, where unknown bad dies (UBD) are still a concern. Approaches have been taken to develop the thermally reworkable underfill materials in order to address the nonreworkability problem of the commercial underfill encapsulants. These approaches include introduction of thermally cleavable blocks into epoxides and addition of additives to the epoxies. In the first approach, five diepoxides containing thermally cleavable blocks were synthesized and characterized. These diepoxides were mixed with hardener and catalyst. Then the mixture properties of Tg, onset decomposition temperature, storage modulus, CTE, and viscosity were studied and compared with those of the standard formulation based on the commercial epoxy resin ERL-4221E. These mixtures all decomposed at lower temperature than the standard formulation. Moreover, one mixture, Epoxy5, showed acceptable Tg, low viscosity, and fairly good adhesion. In the second approach, two additives were discovered that provide die removal capability to the epoxy formulation without interfering with the epoxy cure or properties of the cured epoxy system. Furthermore, the combination of the two approaches showed positive results     

Rheology and Thermal Conductivity of Diamond Powder-Filled Liquid Epoxy Encapsulants for Electronic Packaging

The traditional silica-based epoxy system used for electronic packaging has a poor thermal conductivity of less than 1 W/mK and no longer meets the increasingly stringent thermal management requirements of many packaging applications. The current commercial availability of low-cost diamond powders with very high-thermal conductivity makes it possible to consider diamond powder-filled epoxy for high-end product packaging. This paper reports the design, rheology, and experimentally determined thermal conductivity results on the multimodal diamond powder-filled epoxy system for liquid encapsulants. Rheology studies of the monomodal diamond powder in epoxy show the necessity of the use of surfactants when the powder sizes are below 10 $mu {rm m}$. A high-thermal conductivity of 4.1 W/mK was achieved for epoxy-filled by 68% volume loading of diamond powders, which required a multimodal particle size distribution (nine sizes). Comparative measurements of electronic junction temperatures of Si diodes sealed by the diamond powder-filled epoxy and commercial silica-epoxy show a much better thermal performance of the diamond-filled epoxy, which suggests the potential application of the diamond-filled epoxy for packaging high-end electronic products.      

Ion transport in encapsulants used in microcircuit packaging

Most semiconductor devices are encapsulated in epoxy molding compounds. These molding compounds contain ionic contaminants including chloride ions from epichlorohydrin used in the epoxidation of the resin and bromine ions incorporated into the resin as a flame retardant. Chloride ions are known to break down the protective oxide on the surface of aluminum metallization and accelerate corrosion. The encapsulant material is hydrophilic and will absorb moisture from the environment. When the absorbed moisture is combined with ions, there is an opportunity for electrolytic corrosion to occur on the metal surfaces of the device and package elements. However, the rate of corrosion in an encapsulated microcircuit may be expected to depend upon the rate of ion transport through the encapsulant. This paper evaluates two techniques for the measurement of ion diffusion in epoxy molding compounds used for microelectronic encapsulation. The data suggests that ion diffusion rates vary with molding compound formulation, the solution pH and the ion concentration. SEM-EDX analysis and TOF-SIMS analysis indicate that the mode of diffusion of ions in the encapsulants is primarily through the polymer resin matrix as opposed to diffusion at the interface of the resin and the filler particles. Calculated diffusion coefficients were slower than the literature values for moisture diffusion or the diffusion of gases. In fact, under basic conditions, the ions tend to diffuse through the molding compound almost as a front suggesting that the ions bind to the encapsulant and that the diffusion of ions in molding compounds can be modeled using a Type II non-Fickian model.     

High-temperature reliability of Flip Chip assemblies

Flip Chip technology has been widely accepted within microelectronics as a technology for maximum miniaturization. Typical applications today are mobile products such as cellular phones or GPS devices. For both widening Flip Chip technology’s application range and for addressing the automotive electronics’ volume market, developing assemblies capable of withstanding high temperatures is crucial. A typical scenario for integrating electronics into a car is a control unit within the engine compartment, where ambient temperatures are around 150 °C, package junction temperatures may range from 175 °C to 200 °C and peak temperatures may exceed these values.If Flip Chip technology is used under harsh environment conditions, it is clear that especially the polymeric materials, i.e., underfiller, solder mask or the organic substrate base material, are challenged. Generally, the developmental goal for encapsulants compatible with high-temperature applications are materials with high T_g and low degradation even at temperatures >200 °C.According to these demands, a test group of advanced underfill encapsulants has been used for assembling Flip Chip devices. These test vehicles were built using lead-free and lead-containing solders such as SnAgCu and eutectic PbSn and standard FR4 substrates, for evaluating the reliability potential of state-of-the-art underfillers. Material analysis is performed for studying both material degradation as well as temperature-dependent thermo-mechanical and adhesive properties. For assessing reliability, temperature cycling is performed with different maximum test temperatures ranging from 150 °C to 175 °C. The device status is intermediately analyzed by using electrical measurement for detecting bond integrity and acoustomicroscopy for determining the occurrence and growth of delaminations. Extensive failure analysis is added to investigate device failure mechanisms, especially related to the respective test temperature.In summary, an empirical status of the high-temperature potential of state-of-the-art underfillers and material combinations is attained and an outlook on future demands and developments is provided.     

Cyanate Ester-Based Encapsulation Material for High-Temperature Applications

Cyanate ester resin-based composite materials have been proposed as potential encapsulants for high-temperature applications. The objective of this study is to develop a cyanate ester-based encapsulant, which can also serve as a flip-chip underfill as well as for traditional encapsulation. Two different materials, quartz and alumina fillers, have been studied. The impact of shapes and sizes of the fillers on the overall thermomechanical properties has been investigated. The adhesion strengths of the materials to the ceramic substrate, Kovar lid, and silicon die have also been characterized. The modulus of the resin and the shape of the fillers play a pivotal role in minimizing thermal stress, generated by coefficient of thermal expansion mismatches. Smaller filler particles were found to have better adhesion to the cyanate ester resin. The high-temperature performance of the cyanate ester-based encapsulants was evaluated by thermal aging at 300°C for up to 500 h.     

Demonstrated reliability of plastic-encapsulated microcircuits formissile applications

For the past decade, overall reliability improvement and product availability have enabled plastic encapsulated microcircuits (PEM) to move from consumer electronics beyond the relatively large and reliability-conscious automotive market, into the military market. Based on the analysis of the worst-case PEM scenario for military applications, demonstrating the moisture reliability under long-term (20 years) dormant storage environments has become the last hurdle for PEM. Studies have demonstrated that PEM can meet the typical missile environments in long-term storage. To further validate PEM reliability in missile applications, Texas Instruments (TI) conducted three separate studies involving 6 years of PEM moisture-life monitoring and assessment, testing of the standard PEM electrical characteristics under the military temperature ranges (-55°C to +125°C), and assessing their robustness in moisture environments after the assembly processes. These TI studies support the use of PEM in missile (or similar) applications. Effective focus on part and supplier selection, supplier teaming, and process monitoring is necessary to maintain the PEM reliability over the required environments at the lowest cost. This paper assesses PEM reliability for a selected missile storage environment using the industry-standard moisture testing, such as biased HAST or 85°C/85%RH (relative humidity), for demonstrating the PEM moisture survivability. The moisture reliability (MTTF) or average moisture lifetime of PEM is assessed to correlate PEM capability to anticipated field-performance environments     

Recent advances in plastic packaging of flip-chip and multichipmodules (MCM) of microelectronics

The success in consumer electronics in the 1990's will be focused on low-cost and high performance electronics. Recent advances in polymeric materials (plastics) and integrated circuit (IC) encapsulants have made high-reliability very-large-scale integration (VLSI) plastic packaging a reality. High-performance polymeric materials possess excellent electrical and physical properties for IC protection. With their intrinsic low modulus and soft gel-like nature, silicone gels have become very effective encapsulants for larger, high input/output (I/O) (in excess of 10 000), wire-bonded and flip-chip VLSI chips. Furthermore, the recently developed silica-filled epoxies underfills, with the well controlled thermal coefficient of expansion (TCE), have enhanced the flip-chip and chip-on-board, direct chip attach (DCA) encapsulations. Recent studies indicate that adequate IC chip surface protection with high-performance silicone gels and epoxies plastic packages could replace conventional ceramic hermetic packages. This paper will review the IC technological trends, and IC encapsulation materials and processes. Special focus will be placed on the high-performance silicone and epoxy underfills, their chemistries and use as VLSI device encapsulants for single and multichip module applications     

核壳橡胶在环氧模塑料中分散及增韧改性研究

应用于环氧模塑料时,核壳橡胶的团聚在正常挤出工艺过程中无法再次分散,它的团聚使得环氧模塑料塑封后的塑封体在CSAM图像中产生黑点。将核壳橡胶与表面活性剂在树脂体系中进行混合预搅拌,能够有效地将已打散的核壳橡胶粒子完全隔离开,从而达到分散核壳橡胶粒子的目的。分散好的核壳橡胶在环氧模塑料中能够提高塑封料的飞边性能,降低塑封料的模量,对应力的吸收有促进作用,从而提高环氧模塑料的可靠性。     

Development of reworkable underfill from hybrid composite of freeradical polymerization system and epoxy resin

The application of the underfill encapsulant is to enhance the solder joint fatigue life in the flip chip assembly, typically up to an order of magnitude, as compared to the nonunderfilled devices. Most of the current underfills, however, are primarily thermosetting epoxy resin curing system based materials, which transform into an infusible three dimensional network structure, and exhibit appreciable adhesion and reliability, but lack of desirable reworkability after curing. From the standpoint of polymeric material chemistry, other thermoplastic or thermosetting polymer materials could be of great economic/cost interest as encapsulants for some microelectronic packaging applications. In this paper, the experimental focus was devoted to the study of adhesion, reliability and reworkability of the free radical polymerization (FRP) system, as well as its hybrid composites or blends with phenoxy resin or epoxy resin (EPR), which could be potential underfill materials. The study encompassed formulation screening based on adhesion measurement, and assessment on reliability and reworkability performance for selected compositions developed so far     

EMC所用环保阻燃剂介绍及优缺点比较

随着人们健康环保意识的增强,寻求环保化、低毒化、高效化、多功能化的阻燃剂已成为阻燃剂行业的必然趋势。对于环保模塑料来讲,必须有相对应的符合法令要求的产品。用环保阻燃剂替代原先使用的溴锑阻燃剂加入到基础配方中制备了环保塑封料,文章简单介绍了目前市场上主要的有机及无机阻燃剂的种类,并重点讲述了在环氧塑封料中引用各环保阻燃剂...     

Studies of latent catalyst systems for pot-life enhancement of flipchip underfills

Underfill encapsulant is the material used in flip-chip devices that fills the gap between the integrated circuit (IC) chip and the organic board, and encapsulates the solder interconnects. This underfill material can dramatically enhance the reliability of flip-chip devices as compared to nonunderfilled devices. Current underfill encapsulants generally consist of epoxy resin, anhydride hardener, catalyst, silica filler, and other additives to enhance the adhesion, flow, etc. Catalyst determines underfill properties including pot-life, cure speed, and cure temperature. However, long pot-life and fast cure at relatively low temperature (~150°C) are desirable, as such, it requires a room temperature latent catalyst which would be able to catalyze the epoxy curing efficiently at desirable temperature. Currently, the pot-life of commercial underfills at room temperature is normally less than one day. The underfills have to be stored in the freezer at -40°C and in the dry ice for shipping. The objective of this work was to test various catalyst systems that have the potential to enhance the pot-life of the underfill without adversely affecting its curing. The pot-lives of the underfill with various catalysts were obtained from their viscosity versus time relationships, which were established by measuring the viscosities of the underfill with these catalysts periodically using a stress-controlled rheometer. The curing of the underfills was studied using a differential scanning calorimetry (DSC). The pot-life and curing data of the underfill pre-mixed with each of these catalysts are presented in this paper     

New hybrid electronic molding compounds

This paper describes the performance characteristics of a new class of electronic molding compounds for semiconductor encapsulation. These new materials are identified as silicone-epoxy hybrid polymers. They were evaluated by testing integrated circuits molded in the hybrid system and comparing these results with those obtained with current state-of-the-art commercial silicone and epoxy molding compounds. Results are given for long-term life testing under environmental conditions of high temperature/high humidity and salt atmosphere. Temperature humidity bias data on linear integrated circuits tested by a semiconductor manufacturer are also presented. The effects of temperature and humidity on the molded plastic as measured by moisture absorption and dimensional stability are shown.     

Preparation and Characterization of a Novel Epoxy Molding Compound with Low Storage Modulus at High Temperature and Low Glass-Transition Temperature

Epoxy molding compound (EMC) has been widely used as a main material for encapsulation and protection of semiconductor packages because of its low cost, high moisture resistance, high heat resistance, and good mechanical performance. Due to the extensive application of lead-free solder in place of Sn-Pb, soldering temperature is higher than before; this demands that EMC, which is usually used for lead-free solder, should have extremely low thermal stress and excellent stability at elevated temperatures. In this work, 1,3-propanediol bis(4-aminobenzoate) (PBA) was added to an EMC product to form a novel epoxy molding compound (FEMC). PBA had very limited effect on the process feasibility of EMC, and caused reduction of the storage modulus by 40% to 50% at high temperatures and reduction of the glass-transition temperature by more than 10°C, which are very helpful to reduce thermal stress buildup during high-temperature soldering processes. The increases of the tab pull force of copper- and silver-plated lead frames within EMC due to PBA were up to 58% and 117%, respectively. With increasing PBA content in the EMC, water absorption increased in a linear fashion, so the amount of PBA added to the EMC should be limited, preferably to not more than 1%.     

Measurement of the temperature dependent constitutive behavior of underfill encapsulants

Reliable, consistent, and comprehensive material property data are needed for microelectronic encapsulants for the purpose of mechanical design, reliability assessment, and process optimization of electronic packages. In our research efforts, the mechanical responses of several different capillary flow snap cure underfill encapsulants are being characterized. A microscale tension-torsion testing machine has been used to evaluate the uniaxial tensile stress-strain behavior of underfill materials as a function of temperature and strain rate. A critical step to achieving accurate experimental results has been the development of a sample preparation procedure that produces mechanical test specimens that reflect the properties of true underfill encapsulant layers. In the developed method, 75-125/spl mu/m (3-5 mil) thick underfill uniaxial tension specimens are dispensed and cured using production equipment and the same processing conditions as those used with actual flip chip assemblies. A three parameter hyperbolic tangent empirical model has been shown to provide accurate fits to the observed underfill nonlinear stress-strain behavior over a range of temperatures and strain rates. In addition, the first measurements of underfill mechanical behavior at cryogenic temperatures have been made.     

Development of virtual reliability methodology for area-arraydevices used in implantable and automotive applications

The number of thermal cycles, the temperature range, and the time of dwell used for qualifying a microelectronic package should be based on the type of application the package is intended for. However, in the absence of specific guidelines, the industrial practice is to subject the devices to military-standard qualification tests without adequate consideration for the application the devices are intended for. This work aims at developing temperature cycling guidelines for packages used in implantable medical devices and automotive applications taking into consideration the thermal history associated with the field conditions. Numerical models have been developed that take the time- and temperature-dependent behavior of the solder joints and the viscoelastic behavior of the underfill besides the temperature-dependent orthotropic properties of the substrate for a flip-chip on board (FCOB) assembly and a flip chip chip-scale package (FCCSP) on organic board assembly. The models account for solder reflow process, underfill cure process, and burn-in testing of the devices. Qualification temperature cycling guidelines have been developed for implantable devices based on the information collected in terms of shipping, EM sterilization, and implantation temperature profiles, and for the automotive devices based on the representative field conditions     

Characterization of the electrochemical behavior of gastrointestinal fluids using a multielectrode sensor probe

A characterization of gastrointestinal fluids has been performed by means of an electrochemical sensor that has potential for clinical in vivo and in vitro monitoring applications. The sensor comprised a three-electrode cell with a counter, reference, and four working electrodes, Au, Pt, Ir, and Rh. Cyclic voltammetry was used to obtain chemical information from faecal water (in vitro) and gut model (in vivo) fluids. Stable voltammetric responses were obtained for both fluids at these noble metal working electrodes. The responses differed in shape that demonstrated the discrimination capability and the potential for practical use as a tool for gastrointestinal fluid investigation. The analysis of the stability profiles in faecal water over a 14-h duration has indicated a possible adsorption mechanism with the formation of a biolayer on the sensor surface. The stability in gut model fluids over a 42-h duration has demonstrated a more stable profile, but the mechanisms involved are more complicated to determine.