Stabilizing contact resistance of isotropically conductive adhesives on various metal surfaces by incorporating sacrificial anode materials

The contact resistance stability of isotropically conductive adhesives (ICAs) on non-noble metal surfaces under the 85°C/85% relative humidity (RH) aging test was investigated. Previously, we demonstrated that galvanic corrosion has been shown as the main mechanism of the unstable contact resistance of ICAs on non-noble metal surfaces. A sacrificial anode was introduced into the ICA joint for cathodic protection. Zinc, chromium, and magnesium were employed in the ICA formulations as sacrificial anode materials that have much lower electrode-potential values than the metal pad surface, such as tin or tin-based alloys. The effect of particle sizes and loading levels of sacrificial anode materials were studied. Chromium was not as effective in suppressing corrosion as magnesium or zinc because of its strong tendency to self-passivate. The corrosion potential of ICAs was reduced by half with the addition of zinc and magnesium into the ICA formulation. The addition of zinc and magnesium was very effective in controlling galvanic corrosion that takes place in the ICA joints, resulting in stabilized contact resistance of ICAs on Sn, SnPb, and SnAgCu surfaces during the 85°C/85% RH aging test.     

Development of conductive adhesives for solder replacement

Develops conductive adhesives with stable contact resistance and desirable impact performance. Effects of purity of the resins and moisture absorption on contact resistance are investigated. Several different additives (oxygen scavengers and corrosion inhibitors) on contact resistance stability during elevated temperature and humidity aging are studied, and effective additives are identified. Then, several rubber-modified epoxy resins and two synthesized epoxide-terminated polyurethane resins are introduced into ECA formulations to determine their effects on impact strength. The loss factor, tan δ, of each formulation is measured using a dynamic mechanical analyzer (DMA) and impact strength is evaluated using the National Center for Manufacturing Science (NCMS) standard drop test procedure. Finally, high performance conductive adhesives are formulated by combining the modified resins and the effective additives. It is found that 1) purity of the resins and moisture absorption of the formulation affect the contact resistance stability of an ECA; 2) the oxygen scavengers and corrosion inhibitors can delay contact resistance shift; 3) one of the corrosion inhibitors is very effective in stabilizing the contact resistance; 4) some rubber-modified epoxy resins and the epoxide-terminated polyurethane resins can provide the conductive adhesives with superior impact performance; and 5) conductive adhesives with stable contact resistance and desirable impact performance are developed     

Mechanisms underlying the unstable contact resistance of conductiveadhesives

One critical obstacle of current conductive adhesives is their unstable contact resistance with nonnoble metal finished components during high temperature and humidity aging. It is commonly accepted that metal oxide formation at the interface between the conductive adhesive and the nonnoble metal surface is responsible for the contact resistance shift. Two different mechanisms, simple oxidation and galvanic corrosion, both can cause metal oxide formation, but no prior work has been conducted to confirm which mechanism is the dominant one. Therefore, this study is aimed at identifying the main mechanism for the metal oxide formation and the unstable contact resistance phenomenon of current conductive adhesives. A contact resistance test device, which consists of metal wire segments and conductive adhesive dots, is specially designed for this study. Adhesives and metal wires are carefully selected and experiments are systematically designed. Based on the results of this systematic study, galvanic corrosion has been identified as the underlying mechanism for the metal oxide formation and for the observed unstable contact resistance phenomenon of conductive adhesives     

The contact resistance and reliability of anisotropicallyconductive film (ACF)

The effect of bonding pressure on the electrical and mechanical properties of anisotropic conductive film (ACF) joint using nickel particles and metal-coated polymer ball-filled ACFs was investigated. The contact resistance decreases as the bonding pressure increases. Contact resistance of ACF is determined by the contact area change between particles and contact substrates. Electrical conduction through the pressure engaged contact area between conductive particles and conductor substrates is the main conduction mechanism in ACF interconnection. In addition, environmental effects on contact resistance and adhesion strength such as thermal aging, high temperature/humidity aging and temperature cycling were also investigated. Interestingly, the contact resistances of the excessively bonded samples deteriorated more than those of optimally bonded ones. Increasing contact resistance and decreasing adhesion strength after harsh environmental tests were mainly due to the loss of contact by thermal stress effect and moisture absorption, and also partially due to the formation of metal oxide on the conductive particles     

A study of contact resistance of conductive adhesives based onanhydride-cured epoxy systems

Electrically conductive adhesives (ECAs) are an environmentally friendly alternative to tin/lead (Sn/Pb) solders in electronics packaging applications. However, current conductive technology is still in its infancy and limitations do exist. One of the critical reliability issues is that contact resistance of silver flake-filled ECAs on nonnoble metals increases in elevated temperature and humidity environments. The main objective of this study is to investigate the contact resistance behaviors of a class of conductive adhesives, which are based on anhydride-cured epoxy systems. Curing profiles, moisture pickup, and shifts of contact resistance of the ECAs on a nonnoble metal, tin/lead (Sn/Pb), during aging are investigated. Also, two corrosion inhibitors are employed to stabilize the contact resistance. The effects of these corrosion inhibitors on contact resistance are compared. It is found that: (1) this class of ECAs shows low moisture absorption, (2) the contact resistance of the ECAs on Sn/Pb decreases first and then increases slowly during 85°C/85% relative humidity (RH) aging, (3) one of corrosion inhibitors is very effective to stabilize contact resistance of these ECAs on Sn/Pb, and (4) the corrosion inhibitor stabilizes contact resistance through adsorption on Sn/Pb surfaces. From this study, it can be concluded that ECAs based on anhydride cured epoxy systems are promising formulations for electronics packaging applications     

High performance conductive adhesives

Isotropic conductive adhesives (ICAs) have been developed as an alternative for traditional tin/lead (Sn/Pb) solders for electronic applications. Compared to mature soldering technology, conductive adhesive technology is still in its infant stage, therefore, there are some limitations for current commercial ICAs. Two critical limitations are poor impact performance and unstable contact resistance with nonnoble metal finished components. These limitations seriously hindered the wide applications of ICA's. No current commercial ICAs show both desirable impact performance and stable contact resistance. In this paper, novel conductive adhesives were formulated using mixtures of an epoxide-modified polyurethane resin and a bisphenol-F type epoxy resin and a corrosion inhibitor. Cure profiles, rheology, and dynamic mechanical properties of the conductive adhesives were studied using a differential scanning calorimeter (DSC), a rheometer, and a dynamic mechanical analyzer (DMA), respectively. Impact strength and contact resistance with several nonnoble metals (Sn/Pb, Sn, and copper) of these conductive adhesives were tested and compared to those of a commercial conductive adhesive. It was found that these in-house conductive adhesives showed superior impact performance and substantially stable contact resistance with nonnoble metal finished components during elevated temperature and humidity aging     

Modeling of particle arrangement in an isotropically conductive adhesive joint

An isotropically conductive adhesive (ICA) is a composite material consisting of a nonconductive polymer binder and conductive filler particles. When the filler content is high enough the nonconductive binder is transformed into a good electrical conductor. This transition can be described by the percolation theory. We present a two-dimensional model to analyze the principal influences of the geometrical and electrical properties of the filler particles on the percolation threshold and the electrical resistance of an ICA joint. With this model, the arrangement of the particles within the joint is calculated by considering different types of forces. Taking into account the electrical properties of the particles, the electrical contact behavior is investigated. The goal of this study is to provide a deeper understanding of the changes of the macroscopic contact behavior due to different environmental impacts.     

Effect of Ag particle size on electrical conductivity ofisotropically conductive adhesives

The present work is to introduce nanoparticles in micro-sized metal particles to study particle distribution in polymer matrix. Previous examinations of the silver-filled particles reveal that the micro-sized particle fillers appear as full density silver flakes, while nanoparticle fillers appear as highly porous agglomerates, similar to open-cell foams. Actually little work has been carried out to study the cross-sectional area of a particle-particle-contact in isotropically conductive adhesives (ICA). In this study, transmission electron microscope is chosen as a main measure to analyze the distribution of different-sized particles. The percentage of the nanoparticles varies from 20 wt% and 50 wt% to full percentage within micro-sized particles, and the total metal content in epoxy resin is 70 wt%. So the change of contact area and contact behavior with various volume ratio of nano-sized and micro-sized particles was investigated. At the same time, the electrical resistivity was measured, which is compared with the different level of the filler loading     

Adherence of self-assembled monolayers on gold and their effects for high-performance anisotropic conductive adhesives

To improve the electrical property of the anisotropic conductive adhesive (ACA) joints, self-assembled monolayer (SAM) compounds are introduced into the interface between the metal filler and the substrate bond pad. The formation of the SAM on gold and the thermal stability were investigated by measuring the contact angles of SAM compounds with a hydrophilic or hydrophobic tail groups such as octadecanethiol (ODT), mercpatoacetic acid (MAA), and 1,4-benzenedithiol (dithiol) on the Au surface. Epoxy resins with two different curing temperatures were used as polymer matrices of the ACA formulations. The SAM-treated ACA joints showed much lower resistance at the same applied current than nontreated joints, and the effect on the low curing temperature epoxy matrices was more significant.     

Research on the contact resistance,reliability, and degradation mechanisms of anisotropically conductive film interconnection for flip-chip-on-flex applications

Although there have been many years of development, the degradation of the electrical performance of anisotropically conductive adhesive or film (ACA or ACF) interconnection for flip-chip assembly is still a critical drawback despite wide application. In-depth study about the reliability and degradation mechanism of ACF interconnection is necessary. In this paper, the initial contact resistance, electrical performance after reliability tests, and degradation mechanisms of ACF interconnection for flip-chip-on-flex (FCOF) assembly were studied using very-low-height Ni and Au-coated Ni-bumped chips. The combination of ACF and very-low-height bumped chips was considered because it has potential for very low cost and ultrafine pitch interconnection. Contact resistance changes were monitored during reliability tests, such as high humidity and temperature and thermal cycling. The high, initial contact resistance resulted from a thin oxide layer on the surface of the bumps. The reliability results showed that the degradation of electrical performance was mainly related to the oxide formation on the surface of deformed particles with non-noble metal coating, the severe metal oxidation on the conductive surface of bumps, and coefficient of thermal expansion (CTE) mismatch between the ACF adhesive and the contact conductive-surface metallization. Some methods for reducing initial contact resistance and improving ACF interconnection reliability were suggested. The suggestions include the removal of the oxide layer and an increase of the Au-coating film to improve conductive-surface quality, appropriate choice of conductive particle, and further development of better polymeric adhesives with low CTE and high electrical performance.     

Spatial distribution of metal fillers in isotropically conductive adhesives

The dc electric conductance of isotropically conductive adhesive (ICA) was studied. Assuming completely random distribution of the metal fillers in the ICA, it was demonstrated that the percolation volume percentage of the metal fillers can be significantly reduced by adding nano-size fillers (nanofillers) into the system originally containing only micro-size fillers (microfillers). However experiments show that, due to the surface tensions, nanofillers tend to gather around microfillers as well as to form clusters themselves so the resistivity of the ICA increases following the increase of the nanofillers' volume percentage. In the present work, these cluster effects are investigated by simulating the detailed random walks of the nanofillers and microfillers in the system It is concluded that the cluster effects of the nanofillers deteriorate the electric conductivity of the ICA because the microfillers separate from each other so that it is more difficult to form the electrical conduction path in the ICA.     

A novel approach to stabilize contact resistance of electrically conductive adhesives on lead-free alloy surfaces

Electrically conductive adhesive (ECA) is an alternative for the toxic lead-based solders. However, unstable electrical conductivity has long been a haunting problem. Galvanic corrosion at the ECA/pad interface has recently been found to be the major mechanism for this decay. Applying a more active metal or alloy on a dissimilar metal couple in contact can prohibit galvanic corrosion. In this study, powders of aluminum, magnesium, zinc, and two aluminum alloys were added in an ECA and applied on five pad surfaces. The aging of the bulk resistivity and contact resistance of the ECA/metal surface pairs were studied. The two alloys significantly suppressed the increase of the contact resistance on all tested metal surfaces.     

Isotropic conductive adhesives filled with low-melting-point alloyfillers

Conventional isotropic conductive adhesives (ICAs) are composed of a polymeric matrix and silver (Ag) flakes. As an alternative to lead-bearing solder, ICAs offer a number of benefits, but limitations do exist for ICA technology. ICAs filled with silver flakes generally show higher initial contact resistance, unstable contact resistance, and inferior impact strength. In this study, a new class of isotropic conductive adhesives was developed by using two different fillers, silver flakes and a low-melting-point-alloy filler, into the ICA formulations. After curing, the metallurgical connections between silver particles, and between silver particles and nickel (Ni) substrate were observed using scanning electron microscopy (SEM). Electrical properties including bulk resistance, initial contact resistance, and contact resistance shifts of the ICA were investigated and compared to those of a commercial ICA, an in-house ICA filled with only the silver flake, and a eutectic Sn/Pb solder. It was found that: (1) the low-melting-point alloy filler could wet the silver flakes and nickel substrate to form metallurgical connections, (2) this ICA had much lower bulk resistance than the commercial ICA and the in-house ICA filled with only the silver flake, and (3) this ICA showed especially low initial contact resistance and more stable contact resistance during aging on nickel metal compared to the ICA filled only with silver flakes     

Electrical Resistance and Microstructural Changes of Silver–Epoxy Isotropic Conductive Adhesive Joints Under High Humidity and Heat

In this study, the degradation mechanism of chip resistors mounted with Ag–epoxy isotropic conductive adhesive (ICA) under two different environmental conditions, i.e., humidity exposure (85°C/85% relative humidity) and thermal cycling (TC, –40°C to 125°C), was examined by monitoring the change in electrical resistance and by transmission electron microscopy. The effect of the terminal finishes (Sn/Ni or Au/Ni) of the chip components on joint stability during those two tests was also examined. The electrical resistance of the Sn/Ni-plated chip component joined with Ag–epoxy ICA during both environmental tests increased with exposure time. On the other hand, the electrical resistance of the Au/Ni-plated chip component joined with Ag–epoxy ICA remained unchanged during both tests. In the case of the Sn/Ni-plated chip joint, Sn oxides such as SnO, SnO₂, and Sn-Cl-O were formed inhomogeneously on the surface of the Sn plating during the humidity exposure test. Under the TC test, microcracks were also observed at the Sn/epoxy and the Ag filler/epoxy interfaces. A Ni₃Sn intermetallic compound (IMC) was formed at the interface between Sn and Ni, and the Ni₃Sn₄ IMC was also formed at the Sn surface. In contrast, no oxide was found in the Au/Ni-plated chip joint during the humidity exposure test. Also, no IMC was found in that joint during the TC test. It is suggested that oxides, microcracks, and IMCs cause the electrical degradation of Sn/Ni-plated chip components joined with Ag–epoxy ICA.     

Effect of autoclave test on anisotropic conductive joints

This paper reports that the stress-corrosion cracking induced by autoclave test condition reduces the mechanical strength of anisotropic conductive joints and also increases the contact resistance by allowing more moisture to reach the aluminium metallization. The use of anisotropic conductive joints with bumpless chips allows a reduction in the costs of the flip chip bonding process. The epoxy-based anisotropic conductive adhesive film (ACF) absorbs moisture and experiences hygroscopic swelling, hence degrading adhesion strength and elasticity in hazardous environments, e.g. if moisture at high vapour pressure, and test temperature near to its glassy temperature (T_g) are applied. Contact resistances also show an increasing trend that is similar to that typical of a corrosion process. It is most probably due to the formation of an oxidation layer on top of the aluminium metallization and to the hygroscopic swelling of the ACF. The elastic properties of ACF joints reduce by about 50% after 384 h test time. In this study, 336 h of autoclave test is the critical test duration to affect the electrical and mechanical properties of an ACF joint.     

Effects of Anisotropic Conductive Film Viscosity on ACF Fillet Formation and Chip-On-Board Packages

In this paper, the effects of anisotropic conductive film (ACF) viscosity on ACF fillet formation and, ultimately, on the pressure cooker test (PCT) reliability of ACF flip chip assemblies were investigated. The ACF viscosity was controlled by varying the molecular weight of the epoxy materials. It was found that the ACF viscosity increased as the increase of molecular weight of the epoxy materials. However, there was little variation of the thermomechanical properties among the evaluated ACFs with different viscosites. Also, the results showed that the ACFs have no differences in moisture absorption rate, die adhesion strength, and degree-of-cure. In scanning electron microscopy images, the lower ACF viscosity resulted in the smoother ACF fillet shape and the higher fillet height. From the results of PCT, the ACF flip chip assembly with the smoother fillet shape showed better reliability in terms of contact resistance changes. After 130 h of PCT, the flip chip assembly with lower ACF viscosity also showed a lesser degree of delamination at the ACF/chip interface.     

Effect of elastic recovery on the electrical contact resistance in anisotropic conductive adhesive assemblies

The successful design of anisotropic conductive adhesive (ACA) assemblies depends mainly on the accurate prediction of their electrical contact resistance. Among the parameters that influence this resistance, the bonding force used to compress the conductive particles against the conductive tracks during the assembly process is very important. This paper investigates how the contact resistance changes as the bonding force is removed at the end of the assembly process when the epoxy resin used to bond the surfaces has cured. The final contact resistance is determined by examining, through theoretical, experimental and numerical analyzes, the evolution of the residual stress as the elastic recovery of the compressed conductive particles and tracks takes place when the bonding force is removed. An iterative algorithm derived from methods found in fracture mechanics analysis is used to determine the relationship between the contact resistance, the adhesive strength and the stiffness of the cured resin. It is shown that smaller values of adhesive strength yield higher contact resistance values; and similarly, smaller values of modulus of elasticity of the resin lead to higher contact resistance values.     

Three-dimensional interconnect with excellent moisture resistance for low-cost MMICs

The moisture resistance of three-dimensional (3-D) interconnects using organic insulator films and Au metals has been investigated to ascertain the feasibility of housing monolithic-microwave integrated circuits with these interconnects in inexpensive nonhermetic packages. By comparing polyimide and benzocyclobutene (BCB) for organic insulator films, it was found that although polyimide has higher moisture absorption than BCB, it has a greater moisture resistance. This suggests that moisture absorption is not the dominant factor in moisture resistance and that BCB has higher water permeability than polyimide. As an adhesion layer between Au metal and insulator film, W and WN have better moisture resistance than WSi and WSiN; adhesion layer compositions containing Si oxidize easily. Further, the metal patterning method has an effect on moisture resistance in terms of leakage current. Reactive ion etching (RIE) with SF/sub 6/ gas is necessary in order to completely remove the metal atom residue left after ion milling with Ar gas. An interconnect using polyimide insulator film, W or WN adhesion metal, and metal patterned by ion milling and RIE, did not fail in terms of contact resistance and leakage current under stress of 85/spl deg/C and 85% relative humidity with a bias for 1000 h.     

Development of conducting adhesive materials for microelectronic applications

Electrically and/or thermally conducting adhesive materials are classified into two categories depending on their conduction modes: isotropic and anisotropic materials. Silver-particle filled epoxy is the most common example of the class of isotropic materials which are conductive in all directions. This material has been long used in the electronic applications as a die-bonding material, where its good thermal conduction rather than its electrical conduction property is utilized. The silver-filled epoxy material has several limitations for high performance electrical interconnections, such as low electrical conductivity, increase in contact resistance during thermal exposure, low joint strength, corrosion issue due to silver migration, difficulty in rework, and so forth. The anisotropic conducting material provides electrical and/or thermal conduction only in one direction. An anisotropic conducting film (ACF) is used for interconnecting TAB mounted chips to a liquid crystal display panel, where fine pitch interconnection and low temperature assembly are required. In this paper, a brief review of the state-of-art conducting adhesive technology is provided. Subsequently, development of new conducting adhesive materials is presented for several different applications, which include high temperature materials for ceramic substrates, and low temperature materials for organic substrates.