Study on interfacial interaction energy of Cu–SAM–epoxy systems in a hot and humid environment

Due to poor adhesion, the interfacial delamination is one of the typical failure modes in electronic packages. In this paper, two kinds of self-assembly monolayers (SAMs), SAMA and SAME, are added to Cu–epoxy interface and the effects of temperature, moisture, and cross-link conversion on the modified interfaces are investigated with molecular dynamics (MD) simulation. The results show that the interfacial interaction energy of the systems with SAMA increases with the increasing temperature, decreasing moisture content, and cross-link conversion. However, the interfacial interaction energy of the systems with SAME decreases with the increasing temperature and moisture content, while it is reluctant to the cross-link conversion. In addition, the simulation reveals that the covalent bonds between SAMA and epoxy enhance the interfacial adhesion of Cu–epoxy. However, the nonbond interactions of SAME and epoxy resin weaken the interfacial adhesion. This paper provides a new method for research and valuation the effects of SAM or other adhesive on interfacial adhesion. MD simulation is an efficient tool in predicting the performances of materials.     

Study of Interfacial Moisture Diffusion at Epoxy/Cu Interface

The delamination at the epoxy/copper interface adversely affects the reliability of IC packages and this is a common failure mode during the qualification process. One of the factors governing the interfacial delamination is the moisture content at the interface. This study has developed an experimental measurement procedure for interfacial moisture diffusion using the Fourier Transform Infrared–Multiple Internal Reflection (FT-IR–MIR) technique with a new calibration method. In this study, interfacial moisture was detected by FT-IR–MIR on an isothermal gloptop epoxy system at selected locations on the epoxy/copper interface of samples which went through 1000 h of 85% relative humidity at 85°C pre-conditioning. By comparing the FT-IR–MIR results for epoxy samples with different pre-conditioning times, the interfacial moisture contents at different positions in the epoxy sample were obtained and a comparison was made. This study has demonstrated that the seepage mechanism along the epoxy/copper interface is the major driver for interfacial delamination under moisture pre-conditioning. It is the prevailing mechanism as compared to the established bulk diffusion mechanism in the epoxy molding compound. Surface analyses conducted on fracture surfaces of button shear test specimens show that interfacial moisture diffusion affects the cuprous oxide content in the epoxy/copper interfacial region and this leads to adhesion degradation.     

Investigation of moisture diffusion in electronic packages by molecular dynamics simulation

Moisture-related failure is one of the main concerns in the integrated circuit (IC) package design. To minimize such failure in multi-layered electronic assemblies and packages, it is important to develop a better understanding of the reliability at a molecular level. In this paper, molecular dynamics (MD) simulations were conducted to investigate the respective moisture diffusion into the epoxy molding compound (EMC) and at the EMC/Cu interface. Moisture diffusion coefficients into the bulk EMC material and at the EMC/Cu interface can be derived from the mean-squared displacements calculated from MD simulations. The MD results showed that the seepage along the EMC/Cu interface is more prevalent when compared to moisture diffusion into the bulk EMC and, thus, rendering it a dominant mechanism causing moisture induced interfacial delamination in plastic packages.     

An energy-based failure criterion for delamination initiation in electronic packaging

The significance of interfacial delamination as a crucial failure mechanism in electronic packaging has been documented in many papers. A number of failure criteria have been used to solve the problems with a pre-crack at the interface. However, in real electronic packages, the size and location of the cracks or/and delamination cannot be predicted. It is not easy to use the traditional fracture criteria to deal with more complicated 3D delamination problems. The epoxy molding compound (EMC)/copper leadframe interface was selected in this study. A series of button shear tests were conducted to evaluate the interfacial adhesion between the EMC and copper. In each test, the failure load acting on the EMC of the button shear sample was measured at different shear angles and a finite element model was used to evaluate the stresses at the EMC/copper interface. In this paper, an energy-based failure criterion is proposed using both the interfacial distortional and hydrostatic strain energy densities as two failure parameters. Stresses were extracted from the numerical simulation in order to calculate the interfacial distortional strain energy density, U _d, and the interfacial hydrostatic strain energy density, U _h, related, respectively, to the shear and tensile modes. U _d and U _h were averaged within a selected region of the finite element model where it exhibits high interfacial strain energy density values.     

The role of water in delamination in electronic packages: degradation of interfacial adhesion

Polymeric electronic packages subjected to standard Joint Electron Device Engineering Council (JEDEC) reliability testing are known to exhibit weakening and failures at the polymeric adhesive interfaces. Coupling agents are typically used as additives in epoxy-based materials to improve package reliability. Coupling agent chemistry and environment conditions, including pH, temperature and applied stress, are known factors that affect the rate of adhesion degradation and jeopardize the long-term reliability of the package. In this study, the subcritical interfacial debonding process is described. The debonding rates of polymers with silane, titanate and zirconate coupling agents were characterized at different temperatures by shear fracture tests and tapered double cantilever beam tests under mechanical loading and simultaneous exposure to controlled acidic environments. An analytical procedure was developed to delineate the material parameters governing adhesion degradation. Elevated temperature and acidity were shown to have a strong effect on package reliability, but mechanical loading was found to have a minimal effect on the rate of adhesion degradation. The effects of the JEDEC testing conditions on interfacial bond degradation are discussed using the chemical kinetic model.     

Investigation of hygroscopic properties in electronic packages using molecular dynamics simulation

Moisture-induced package failures such as interfacial delamination and pop-corn cracking are common failure phenomena that occur during the solder reflow process in the semiconductor industry. Therefore, the hygroscopic properties of the package materials are crucial factors in the reliability of electronic packaging products. In this work, molecular dynamics (MD) simulation was performed to study the hygroscopic properties, including diffusivity and swelling strain, of epoxy materials with respect to temperature and moisture concentration. Hygroscopic material properties predicted by MD are discussed and compared with the experimental data.     

Adhesion and delamination failure mechanisms in alternating layered polyamide and polyethylene with compatibilizer

The effects of compatibilizer and the number of layers on the interfacial adhesion and delamination model of coextruded microlayer samples consisting of alternating layers of high‐density polyethylene (HDPE) and polyamide 6 (PA6) were studied with T‐peel test. When more maleic anhydride‐grafted HDPE was incorporated into HDPE layer, the interfacial delamination model changed from adhesive to cohesive failure in the case of bilayer samples. For high‐layer samples, the results of X‐ray photoelectron spectroscopy showed that the areal density of copolymers at the interfaces increased with increasing number of layers due to strong and durable shearing forces during microlayer coextrusion. Scanning electron microscopy observation revealed that the interfacial delamination model changed from single‐ to multiple‐interface delamination when the number of layers increased from 16 to 32. The crack propagation included a large number of layer–layer jumps. The peel strength of microlayer samples was found to be greatly influenced by the interfacial delamination mechanisms. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of a tie layer on the delamination toughness of polypropylene and polyamide‐66 microlayers

The effect of a thin tie layer on the adhesion of polypropylene (PP) and polyamide‐66 (PA) was studied by delamination of microlayers. The microlayers consisted of many alternating layers of PP and PA separated by a thin layer of a maleated PP. The peel toughness and delamination failure mode were determined using the T‐peel test. Without a tie layer, there was no adhesion between PP and PA. A tie layer with 0.2% MA provided some adhesion; however, delamination occurred by interfacial failure. Increasing the maleic anhydride (MA) content of the tie layer increased the interfacial toughness. With 0.5% MA, the interfacial toughness exceeded the craze condition of PP, and a transition from interfacial delamination to craze delamination occurred. Crazing ahead of the crack tip effectively reduced the stress concentration at the interface and dramatically increased the delamination toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1461–1467, 1999     

The effect of photooxidation aging on the cohesion and interfacial adhesion behavior of epoxy asphalt with a composite acidic curing system based on molecular simulation

This paper investigated the cross-linking network structure of epoxy asphalt (EA) with the different ratio of composite curing agents, and further determined the effect of photooxidation aging on the tensile and interfacial adhesion behavior of EA with different cross-linking network structures through molecular simulation. Based on the molecular models of EA and the interface model between EA and aggregate, the crosslinking network structural characteristics and tensile mechanical behavior were determined. The interfacial adhesion behavior and the mechanization were further studied. The results indicate that 20-EA and 6-EA have an epoxy resin cross-linked network with uniform pore structure and phase distribution. 2-EA showed a denser cross-linking network and uneven aggregation phenomenon. Photooxidative aging alleviated the aggregation phenomenon. A dense cross-linking network improved the tensile strength and the ability of tensile performance to resist photooxidation aging. The interface of EA-quartz exhibited higher adhesion strength than EA-calcite due to the closer distance and stronger nonbonding interactions between EA and quartz. The low anhydride content and photooxidation aging made EA approach to the aggregate interface, increasing nonbonding interaction and interfacial adhesion strength. In addition, quartz aggregates were more suitable for application in EA mixtures due to the higher interfacial adhesion strength and lower water sensitivity.     

The origin of interfacial delamination in Au/ceramic cofired LTCC structure

The interfacial delamination of electrode/ceramic multilayer structure will seriously damage the reliability of low temperature co-fired ceramic (LTCC) module in practical applications. In this work, three kinds of glasses employed in Au electrode are designed and prepared to study the abnormal expansion and delamination process in the Au/ceramic LTCC multilayer structure. The interfacial delamination in the co-fired structure is found to be attributed to the abnormal expansion of glass in respect to Au electrode at high temperature, which is originated from the enlarged closed pores during the co-firing process. This conclusion is further confirmed by co-firing the sample in a low-pressure condition. The mechanism and elimination of interfacial delamination here provides a feasible solution for the design of novel glasses in Au electrode for LTCC applications.     

偶联剂改性沥青与卵碎石集料界面性能研究

为了改善酸性卵碎石集料与沥青粘附性,利用硅烷偶联剂KH550对沥青进行改性.采用针入度、延度、软化点试验分析了偶联剂掺量对沥青性质的影响.采用红外光谱分析、沥青-卵碎石粉交互作用能力测试、低温黏结性试验和沥青混合料水敏感性试验,研究了偶联剂对沥青与卵碎石集料的界面作用.结果表明:经过偶联剂处理的卵碎石粉末的红外光谱存在明显的CH2吸收带,证明了在偶联剂作用下卵碎石表面生成了聚硅氧烷.沥青的软化点随偶联剂掺量的增多先增大后减小,延度和针入度随偶联剂掺量的增多先减小后增大.偶联剂掺量为0.6％时,沥青-卵碎石粉体系的车辙因子G*/sinδ与交互作用系数B值最高.在该掺量下,卵碎石低温脱石量降低了50.7％;相对未改性沥青混合料,水敏感性试验后偶联剂改性沥青混合料的残留劈裂强度比提高了7.9％.硅烷偶联剂显著提高了卵碎石与沥青的界面性能.     

Investigation of coating failure on the surface of a water ballast tank of an oil tanker

The current crude oil tanker is constructed as a double-hull structure which consists of an oil tank and a water ballast tank whose surface is coated with epoxy paint to prevent corrosion. Since the cracks that developed in the epoxy coating have caused corrosion of the interface of the water ballast tank, the identification of the parameters for crack development is important. In addition, the moisture absorption by the epoxy coating can cause deterioration of bond strength, which results in delamination of the coating and accelerates the corrosion at the interface. In this study, after the mechanical and thermo-mechanical properties of epoxy paints were measured, the residual stresses induced by the temperature change and cure shrinkage were calculated by the finite element analysis, which were compared with the experimental results. Also, the pull-off tests were performed to investigate the deterioration of the bond strength of epoxy coatings due to moisture absorption. It was found that the thermo-mechanical properties such as the coefficient of thermal expansion and glass transition temperature of the coating materials had dominant effects on the crack resistance rather than the cure shrinkage; the moisture penetration to the bonding interface caused interfacial failure and a significant deterioration of bond strength.     

Effect of tie-layer thickness on the adhesion of ethylene-octene copolymers to polypropylene

The adhesion of some ethylene-octene copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to evaluate their suitability as compatibilizers for PP/HDPE blends. A one-dimensional model of the compatibilized blend was fabricated by layer-multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie-layer inserted at each interface. The thickness of the tie-layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. The delamination toughness was measured in the T-peel test. Generally, delamination toughness decreased as the tie-layer became thinner with a stronger dependence for tie layers thinner than 2 μm. Inspection of the crack-tip damage zone revealed a change from a continuous yielded zone in thicker tie layers to a highly fibrillated zone in thinner tie layers. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. A blocky copolymer (OBC) consistently exhibited better adhesion to PP than statistical copolymers (EO). A one-to-one correlation between the delamination toughness and the reported performance of the copolymers as compatibilizers for PP/HDPE blends confirmed the key role of interfacial adhesion in blend compatibilization.     

Adhesion of polyethylene blends to polypropylene

The effect of chain microstructure on adhesion of ethylene copolymers to polypropylene (PP) was studied using coextruded microlayers. Adhesion was measured by delamination toughness G using the T-peel test, and interfacial morphology was examined by atomic force microscopy. Good adhesion to PP was achieved with homogeneous metallocene catalyzed copolymers (mPE) with density 0.90 g cm⁻³ or less. Good adhesion was attributed to entanglement bridges. In contrast, a heterogeneous Ziegler-Natta catalyzed copolymer (ZNPE) of density 0.925 g cm⁻³ exhibited poor adhesion to PP due to an amorphous interfacial layer of low molecular weight, highly branched fractions that prevented effective interaction of ZNPE bulk chains with PP. Blending mPE with ZNPE eliminated the amorphous interfacial layer and resulted in epitaxial crystallization of ZNPE bulk chains with some increase in G. Increasing the mPE content of the blend past the amount required to completely resolve the amorphous interfacial layer of ZNPE resulted in a steady, almost linear, increase in G. Phase separation of mPE and ZNPE during crystallization produced an interface with regions of epitaxially crystallized ZNPE bulk chains and other regions of entangled mPE chains. Entanglement bridges imparted much better adhesion than did epitaxially crystallized lamellae.     

Molecular mechanics modelling of interfacial energy and flexibility on cellulose

Molecular mechanics modelling is used to calculate the energies of interaction, hence the molecular level energy of adhesion at the interface with crystalline cellulose I of three different photopolymerizable primers and of a polyester varnish at the interface with the primer/cellulose assembly. The energy of interactions for just one of the primers with the statistically most common conformation of amorphous cellulose has also been obtained for comparison. Experimental results of adhesion by a standard peel test and by thermomechanical analysis, in which the effect of viscoelastic energy dissipation by crack tip propagation has been respectively minimized or is not present, hence in which the energy of interfacial interaction is nothing else but the work of adhesion, correlated well with the energies of interaction calculated by molecular mechanics. An equation correlating the energy of interaction at each finish/cellulose interface with the deflection derived by thermomechanical analysis, and with the number of internal bond rotational degrees of freedom as well as the degree of networking of the finish, has been derived and is presented. A relationship between the intrinsic fracture energy Go and the molecular mechanics-derived energy of interaction at the interface equating this to the square of the work of adhesion is obtained and is presented.     

沸水对PI/CF复合材料界面作用机理的研究

研究了聚酰亚胺(PI)／碳纤维(CF)复合材料界面在沸水中的稳定性。结果表明,经沸水浸泡后的复合材料层间剪切强度和界面剪切强度均有所提高,且随水煮时间的延长而增大;试样断面观察表明,水没有对复合材料界面产生破坏作用,力学性能的变化与基体／纤维界面粘结的湿热稳定性有直接关系;沸水对界面的作用机理是,在PI／CF复合材料的界面区,树脂的水解使氢键的数量增加,形成了防水层,阻碍了水沿界面的侵入,同时水松驰了界面局部应力。     

Study of adhesion failure due to molding compound additives at chip surface in electronic devices

Today the microelectronics market requires devices with failure levels approaching zero. To attain this goal all production processes must be subjected to extreme quality control. Molding is one of the most critical assembly processes in power plastic packages. This is related to the complexity of phenomena which may occur at the interfaces involved in this process. This paper reports an adhesion study of epoxy-phenolic molding compounds to the most relevant surfaces encountered in power devices assembled in plastic packages such as copper oxide-hydroxide, nickel oxide-hydroxide, aluminium oxide-hydroxide, and silicon 'nitride'. The study was carried out by combining delamination (scanning acoustic microscopy) and pull strength data with the interface chemistry studied using ESCA. Different adhesion failure mechanisms were found to be operative in these systems. These mechanisms are related to either the chemical nature and thickness of the inorganic layer or the segregation of various additives such as wax, polyoxyalkylene ethers, and alkylsiloxanes, contained in the molding compound.     

强界面PVC-U/nano-CaCO3的制备与力学性能研究

使用自主合成的端羧基聚酯和端叔胺基羧酸分别对水乳液中的nano-CaCO3进行表面处理,制备了可与PVC形成界面分子物理纠缠或热可逆交联的强界面结合能力的nano-CaCO3.研究了PVC-U/nano-CaCO3的力学性能与CaCO3的表面性质、填充量及表面处理剂分子量等因素的关系.研究结果表明,提高界面结合强度可改善CaCO3在基材中的分散状况并提高PVC-U/nano-CaCO3的屈服强度,却对于提高PVC的冲击能力无明显效果.     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.