Development of no-flow underfill materials for lead-free solderbumped flip-chip applications

No-flow underfill process in flip-chip assembly has become a promising technology toward a smaller, faster and more cost-efficient packaging technology. The current available no-flow underfill materials are mainly designed for eutectic tin-lead solders. With the advance of lead-free interconnection due to the environmental concerns, a new no-flow underfill chemistry needs to be developed for lead-free solder bumped flip-chip applications. Many epoxy resin/hexahydro-4-methyl phthalic anhydride/metal acetylacetonate material systems have been screened in terms of their curing behavior. Some potential base formulations with curing peak temperatures higher than 200°C (based on differential scanning calorimetry at a heating rate of 5°C/min) are selected for further study. The proper fluxing agents are developed and the effects of fluxing agents on the curing behavior and cured material properties of the potential base formulations are studied using differential scanning calorimetry, thermomechanical analysis, dynamic-mechanical analysis, thermogravimetric analysis, and rheometer. Fluxing capability of the developed no-flow formulations is evaluated using the wetting test of lead-free solder balls on a copper board. The developed no-flow underfill formulations show sufficient fluxing capability and good potential for lead-free solder bumped flip-chip applications     

Assembly of lead-free bumped flip-chip with no-flow underfills

Lead-free solder reflow process has presented challenges to no-flow underfill material and assembly. The currently available no-flow underfill materials are mainly designed for eutectic Sn-Pb solders. This paper presents the assembly of lead-free bumped flip-chip with developed no-flow underfill materials. Epoxy resin/HMPA/metal AcAc/Flux G system is developed as no-flow underfills for Sn/Ag/Cu alloy bumped flip-chips. The solder wetting test is conducted to demonstrate the fluxing capability of the underfills for lead-free solders. A 100% solder joint yield has been achieved using Sn/Ag/Cu bumped flip-chips in a no-flow process. A scanning acoustic microscope is used to observe the underfill voiding. The out-gassing of HMPA at high curing temperatures causes severe voiding inside the package. A differential scanning calorimeter (DSC) used to study the curing degree of the underfill after reflow with or without post-cure. The post-curing profiles indicate that the out-gassing of HMPA would destroy the stoichiometric balance between the epoxy and hardener, and result in a need for high temperature post-cure. The material properties of the underfills are characterized and the influence of underfill out-gassing on the assembly and material properties is investigated. The impact of lead-free reflow on the material design and process conditions of no-flow underfill is discussed.     

Moisture absorption in uncured underfill materials

This paper presents a systematic study on moisture absorption in uncured underfill based on epoxy cured with acid anhydride [methylhexahydrophthalic anhydride (MHHPA)] and epoxy cured with non-acid anhydride curing agent. The influence of absorbed moisture on curing properties, thermomechanical property, and adhesion property of underfill after curing has been investigated. For epoxy cured with non-acid anhydride, the moisture absorption is low, and the absorbed moisture has no significant effect on the properties of cured underfill materials. For epoxy cured with acid anhydride, the moisture absorption before curing can be more than 2.0%, and the absorbed moisture can affect the properties significantly. The absorbed moisture can catalyze the curing reaction between acid anhydride and epoxy. The glass transition temperature of the cured samples is reduced after the underfill absorbs the moisture before curing. The adhesion strength decreases dramatically after the underfill absorbs the moisture before curing.     

No-flow underfill flip chip assembly––an experimental and modeling analysis

In the flip-chip assembly process, no-flow underfill materials have a particular advantage over traditional underfill: the application and curing of the former can be undertaken before and during the reflow process. This advantage can be exploited to increase the flip-chip manufacturing throughput. However, adopting a no-flow underfill process may introduce reliability issues such as underfill entrapment, delamination at interfaces between underfill and other materials, and lower solder joint fatigue life. This paper presents an analysis on the assembly and the reliability of flip-chips with no-flow underfill. The methodology adopted in the work is a combination of experimental and computer-modeling methods. Two types of no-flow underfill materials have been used for the flip chips. The samples have been inspected with X-ray and scanning acoustic microscope inspection systems to find voids and other defects. Eleven samples for each type of underfill material have been subjected to thermal shock test and the number of cycles to failure for these flip chips have been found. In the computer modeling part of the work, a comprehensive parametric study has provided details on the relationship between the material properties and reliability, and on how underfill entrapment may affect the thermal–mechanical fatigue life of flip chips with no-flow underfill.     

Study of the fluxing agent effects on the properties of no-flowunderfill materials for flip-chip applications

As one of the key requirements of the no-flow underfill materials for flip-chip applications, a proper self-fluxing agent must be incorporated in the developed no-flow underfill materials to provide proper fluxing activity during the simultaneous solder reflow and underfill material curing. However, most fluxing agents have some adverse effects on the no-flow underfill material properties and assembly reliability. In this paper, we have extensively investigated the effects of the concentration of the selected fluxing agent on the material properties, interconnect integrity and assembly reliability. Through this work, an optimum concentration window of the fluxing agent is obtained and a routine procedure of evaluating fluxing agents is established     

FEM modeling of temperature distribution of a flip-chip no-flow underfill package during solder reflow process

Flip chip on organic substrate has relied on underfill to redistribute the thermomechanical stress and to enhance the solder joint reliability. However, the conventional flip-chip underfill process involves multiple process steps and has become the bottleneck of the flip-chip process. The no-flow underfill is invented to simplify the flip-chip underfill process and to reduce the packaging cost. The no-flow underfill process requires the underfill to possess high curing latency to avoid gelation before solder reflow so to ensure the solder interconnect. Therefore, the temperature distribution of a no-flow flip-chip package during the solder reflow process is important for high assembly yield. This paper uses the finite-element method (FEM) to model the temperature distribution of a flip-chip no-flow underfill package during the solder reflow process. The kinetics of underfill curing is established using an autocatalytic reaction model obtained by DSC studies. Two approaches are developed in order to incorporate the curing kinetics of the underfill into the FEM model using iteration and a loop program. The temperature distribution across the package and across the underfill layer is studied. The effect of the presence of the underfill fillet and the influence of the chip dimension on the temperature difference in the underfill layer is discussed. The influence of the underfill curing kinetics on the modeling results is also evaluated.     

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     

Void Formation Study of Flip Chip in Package Using No-Flow Underfill

The advanced flip chip in package (FCIP) process using no-flow underfill material for high I/O density and fine-pitch interconnect applications presents challenges for an assembly process that must achieve high electrical interconnect yield and high reliability performance. With respect to high reliability, the voids formed in the underfill between solder bumps or inside the solder bumps during the no-flow underfill assembly process of FCIP devices have been typically considered one of the critical concerns affecting assembly yield and reliability performance. In this paper, the plausible causes of underfill void formation in FCIP using no-flow underfill were investigated through systematic experimentation with different types of test vehicles. For instance, the effects of process conditions, material properties, and chemical reaction between the solder bumps and no-flow underfill materials on the void formation behaviors were investigated in advanced FCIP assemblies. In this investigation, the chemical reaction between solder and underfill during the solder wetting and underfill cure process has been found to be one of the most significant factors for void formation in high I/O and fine-pitch FCIP assembly using no-flow underfill materials.     

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     

Underfill of flip chip on organic substrate: viscosity, surface tension, and contact angle

In flip-chip packaging, an underfill is dispensed on one or two adjacent sides of the die. The underfill is driven by a capillary flow to fill the gap between the die and substrate. The application of an underfill reduces the stress to solder bumps and enhances the reliability of the solder joints. Underfill materials consist of epoxy or cyanate ester resins, catalyst, crosslinker, wetting agent, pigment, and fillers. Underfill materials are highly filled with the filler loading ranging from 40% to 70%. In terms of underfill material processing, fast flow and curing are desired for high throughput. The viscosity, surface tension, and contact angle are key material properties affecting the gap filling process. In order to achieve fast filling, it is required that an underfill material has low viscosity and low contact angle at dispensing temperatures. Due to curing of an underfill material at dispensing temperature, the viscosity increases with time, which complicates the underfill flow process. The rheological behavior of several underfill materials was experimentally studied. All the underfill materials showed strong temperature dependence in viscosity before the curing. The time dependent viscosity and curing of underfill materials were examined by a dynamic time sweep test. The effects of viscosity and curing behavior of underfill materials on underfill material processing were investigated. The material with a longer gel time had more stable viscosity at room temperature, and therefore longer pot life. Experimental methods were developed to measure the surface tension and the contact angle of underfills at temperatures over 100 °C. Results showed that the contact angle for underfill on a substrate was time dependent. The interaction between underfill and substrate affects not only gap filling, but also filleting. The effect of surface energies of flip-chip substrates on wetting angles was also studied. Experiment results showed that for the same underfill, the higher the surface energy of substrate, the better the filleting.     

Effects of Underfill Materials and Thermal Cycling on Mechanical Reliability of Chip Scale Package

The thermomechanical reliability of chip-scale packages (CSPs) with various underfills was evaluated by measure the electrical resistance under thermal shock and four-point bending fatigue tests. The underfill containing cycloaliphatic-type epoxy resin had lower resistance than without cycloaliphatic-type epoxy resin under thermomechanical fatigue test because the cycloaliphatic-type epoxy resin was able to mechanically relax more than the other types. The lifetimes of the CSPs under thermomechanical fatigues were strongly dependent on the properties of the underfill.     

Study of the self-alignment of no-flow underfill for micro-BGA assembly

As a concept to achieve high throughput low cost flip-chip assembly, a process development activity is underway, implementing next generation flip-chip processing based on large area underfill printing/dispensing, IC placement, and simultaneous solder interconnect reflow and underfill cure. The self-alignment of micro-BGA (ball grid array, BGA) package using flux and two types of no-flow underfill is discussed in this paper. A “rapid ramp” temperature profile is optimized for reflow of micro-BGA using no-flow underfill for self-aligning and soldering. The effect of bonding force on the self-alignment is also described. A SOFTEX real time X-ray inspection system was used to inspect samples to ensure the correct misalignment before reflow, and determine the residual displacement of solder joints after reflow. Cross-sections of the micro-BGA samples are taken using scanning electronic microscope. Our experimental results show that the self-alignment of micro-BGA using flux is very good even though the initial misalignment was greater than 50% from the pad center. When using no-flow underfill, the self-alignment is inferior to that of using flux. However, for a misalignment of no larger than 25% from the pad center, the package is also able to self-align with S1 no-flow underfill. However, when the misalignment is 37.5–50% from the pad center, there are 10–14% residual displacement after reflow. The reason is the underfill resistant force inhibiting the self-alignment of the package due to rapid increment of underfill viscosity during reflow. The self-alignment of micro-BGA package using no-flow underfill allows only <25% misalignment prior to the soldering. During assembling, although the bonding force does not influence on the self-alignment of no-flow underfill, a threshold bonding force is necessary to make all solder balls contact with PCB pads, for good soldering. The no-flow underfill is necessary to modify the fluxing/curing chemistry for overcoming the effect of tin metal salt produced during soldering on underfill curing, and for maintaining the low viscosity during soldering to help self-alignment.     

Double-layer no-flow underfill materials and process

The no-flow underfill has been invented and practiced in the industry for a few years. However, due to the interfering of silica fillers with solder joint formation, most no-flow underfills are not filled with silica fillers and hence have a high coefficient of thermal expansion (CTE), which is undesirable for high reliability. In a novel invention, a double-layer no-flow underfill is implemented to the flip-chip process and allows fillers to be incorporated into the no-flow underfill. The effects of bottom layer underfill thickness, bottom layer underfill viscosity, and reflow profile on the solder wetting properties are investigated in a design of experiment (DOE) using quartz chips. It is found that the thickness and viscosity of the bottom layer underfill are essential to the wetting of the solder bumps. Chip scale package (CSP) components are assembled using the double-layer no-flow underfill process. Silica fillers of different sizes and weight percentages are incorporated into the upper layer underfill. With a high viscosity bottom layer underfill, up to 40 wt% fillers can be added into the upper layer underfill and do not interfere with solder joint formation.     

Adhesion characterization of no-flow underfills used in flip chipassemblies and correlation with reliability

Adhesion is one of the key properties of underfills used in flip chip assemblies. This paper characterizes the adhesion strengths of no-flow underfill materials to various die passivations using the shear test techniques. A novel shear test vehicle with planner underfill layers between the die and substrate is presented. The adhesion strengths and failure modes of the no-flow underfill materials during shear testing correlate well with their thermal shock reliability test results. Underfill adhesion related failures such as delamination and crack are investigated and correlated between flip chip assemblies and shear test vehicle assemblies without solder joint interconnects     

Development of new no-flow underfill materials for both eutectic Sn-Pb solder and a high temperature melting lead-free solder

In recent years, no-flow underfill technology has drawn more attention due to its potential cost-savings advantages over conventional underfill technology, and as a result several no-flow underfill materials have been developed and reported. However, most of these materials are not suitable for lead-free solder, such as Sn/Ag (m.p. 225/spl deg/C), Sn/Ag/Cu (m.p. 217/spl deg/C), applications that usually have higher melting temperatures than the eutectic Sn-Pb solder (m.p. 183/spl deg/C). Due to the increasing environmental concern, the demand for friendly lead-free solders has become an apparent trend. This paper demonstrates a study on two new formulas of no-flow underfill developed for lead-free solders with a melting point around 220/spl deg/C. As compared to the G25, a no-flow underfill material developed in our research group, which uses a solid metal chelate curing catalyst to match the reflow profile of eutectic Sn-Pb solder, these novel formulas employ a liquid curing catalyst thus provides ease in preparation of the no-flow underfill materials. In this study, curing kinetics, glass transition temperature (Tg), thermal expansion coefficient (TCE), storage modulus (E') and loss modulus (E') of these materials were studied with a differential scanning calorimetry (DSC), a thermo-mechanical analysis (TMA), and a dynamic-mechanical analysis (DMA), respectively. The pot-life in terms of viscosity of these materials was characterized with a stress rheometer. The adhesive strength of the materials on the surface of silicon chips were studied with a die-shear instrument. The influences of fluxing agents on the materials curing kinetics were studied with a DSC. The materials compatibility to the solder penetration and wetting on copper clad during solder reflow was investigated with both eutectic Sn-Pb and 95.9Sn/3.4Ag/0.7Cu solders on copper laminated FR-4 organic boards.     

Recent advances in flip-chip underfill: materials, process, and reliability

In order to enhance the reliability of a flip-chip on organic board package, underfill is usually used to redistribute the thermomechanical stress created by the coefficient of thermal expansion (CTE) mismatch between the silicon chip and organic substrate. However, the conventional underfill relies on the capillary flow of the underfill resin and has many disadvantages. In order to overcome these disadvantages, many variations have been invented to improve the flip-chip underfill process. This paper reviews the recent advances in the material design, process development, and reliability issues of flip-chip underfill, especially in no-flow underfill, molded underfill, and wafer-level underfill. The relationship between the materials, process, and reliability in these packages is discussed.     

Novel reworkable fluxing underfill for board-level assembly

Underfills are traditionally applied for flip-chip applications. Recently, there has been increasing use of underfill for board-level assembly including ball grid arrays (BGAs) and chip scale packages (CSPs) to enhance reliability in harsh environments and impact resistance to mechanical shocks. The no-flow underfill process eliminates the need for capillary flow and combines fluxing and underfilling into one process step, which simplifies the assembly of underfilled BGAs and CSPs for SMT applications. However, the lack of reworkability decreases the final yield of assembled systems. In this paper, no-flow underfill formulations are developed to provide fluxing capability, reworkability, high impact resistance, and good reliability for the board-level components. The designed underfill materials are characterized with the differential scanning calorimeter (DSC), the thermal mechanical analyzer (TMA), and the dynamic mechanical analyzer (DMA). The potential reworkability of the underfills is evaluated using the die shear test at elevated temperatures. The 3-point bending test and the DMA frequency sweep indicate that the developed materials have high fracture toughness and good damping properties. CSP components are assembled on the board using developed underfill. High interconnect yield is achieved. Reworkability of the underfills is demonstrated. The reliability of the components is evaluated in air-to-air thermal shock (AATS). The developed formulations have potentially high reliability for board-level components.     

A novel flip chip technology using nonconductive resin sheet

The process flow of this new packaging system is as follows. First, epoxy base resin sheet is laminated onto substrate to cover the substrate surface including land electrodes. Bumped chip alignment and attachment was done through the resin sheet, in the second stage with pressure and temperature. The bumps under the chip penetrate with removal of resin sheet material eventually reaching to the metal land of the substrate in this process. Metal connection and curing of the interface resin have been completed in the third stage. This new process has the potential to make flip chip packages simple compared with the current process using liquid resin with dispensing system. The throughput time can be reduced to less than 10 s/unit in actual model case even for large flip chip package which has over 15×15 (mm) square area IC chips. The other advantages are thermal stability of material in the process, moisture related performance, and warpage control performance. For current underfill process the only choice is to use anhydride type resin system which has many disadvantages. This new process made it possible to introduce moisture and thermally stable epoxy resin with phenol curing system for flip chip packaging. Drastic process ability improvement can be achieved by the new process and material. As a typical improvement of thermal shock performance, it was confirmed that the life of chip damage is over 10 times longer by flip chip bonding parameters which can be controlled only by this new flip chip packaging process     

Modeling of the curing kinetics of no-flow underfill in flip-chip applications

No-flow underfill has greatly improved the production efficiency of flip-chip process. Due to its unique characteristics, including reaction latency, curing under solder reflow conditions and the desire for no post-cure, there is a need for a fundamental understanding of the curing process of no-flow underfill. Starting with a promising no-flow underfill formulation, this paper seeks to develop a systematic methodology to study and model the curing behavior of this underfill. A differential scanning calorimeter (DSC) is used to characterize the heat flow during curing under isothermal and temperature ramp conditions. A modified autocatalytic model is developed with temperature-dependent parameters. The degree of cure (DOC) is calculated; compared with DSC experiments, the model gives a good prediction of DOC under different curing conditions. The temperature of the printed wiring board (PWB) during solder reflow is measured using thermocouples and the evolution of DOC of the no-flow underfill during the reflow process is calculated. A stress rheometer is used to study the gelation of the underfill at different heating rates. Results show that at high curing temperature, the underfill gels at a lower DOC. Based on the kinetic model and the gelation study, the solder wetting behavior during the eutectic SnPb and lead-free SnAgCu reflow processes is predicted and confirmed by the solder wetting tests.     

Reliability of microBGA assembly using no-flow underfill

In this paper, the reliability of the microBGA assembly using no-flow underfill is studied by thermal shock and bending cycle. Recently, a more promising underfill technology so-called “no-flow underfill” has been invented to cope with the limitations, which promises low cost assembly. The research results of self-alignment about no-flow underfill show that the self-alignment of microBGA using no-flow underfill is inferior to that using flux. There is residual displacement more or less in various offset volumes. Therefore, the effect of no-flow underfill on reliability of microBGA assembly needs to be investigated systematically. In this study, samples are reflowed with an optimized “rapid ramp” temperature profile, and using flux and no-flow underfill, respectively. One group of samples are subjected to thermal shock at temperature −40–125°C, and dwell time 15 min. Another group of samples is subjected to cyclic bending at a bending speed of 300 mm/min between 500 and −500 μ at the center of a microBGA package. The fatigue lifetime distribution is examined with the aid of “Weibull” method to investigate the effect of no-flow underfill on the reliability of microBGA assembly, and the failure mechanism is investigated by using the scanning electron microscope. Our experiment results show that the no-flow underfill can greatly enhance the mechanical fatigue lifetime. The underfilled material improves the stress distribution in solder joints. For assemblies with no underfills, the fracture always occurs in the outermost solder joint. The issue is improved by underfilling with no-flow underfill. However, the no-flow underfill cannot improve the thermal reliability of microBGA assembly, because the coefficient of thermal expansion (CTE) of no-flow underfill is too great at present. It is necessary to reduce the no-flow underfill CTE, so as to apply actually to BGA and CSP etc. Moreover, it is displayed that the fatigue lifetime of the residual displacement solder is less than 50% of that of the non-misaligned solder. The residual displacement is formed when the misalignment is >25% during mounting. Therefore, when the no-flow underfill is used in microBGA assembly, care must be taken to keep the mount position, and misalignment <25%.