Recent advances in isotropic conductive adhesives for electronics packaging applications

Isotropic conductive adhesives (ICAs) have recently received a lot of focus and attention from the researchers in electronics industry as a potential substitute to lead-bearing solders. Numerous studies have shown that ICAs possess many advantages over conventional soldering such as environmental friendliness, finer pitch printing, lower temperature processing and more flexible and simpler processing. However, complete replacement of soldering by ICAs is yet not possible owing to several limitations of ICAs which are mainly related to reliability aspects like limited impact resistance, unstable contact resistance, low adhesion and conductivity etc. Continued efforts for last 15 years have resulted in development of ICAs with improved properties. This review article is aimed at providing a better understanding of ICAs, their principles, performance and significant research and development work addressing the technological utility of ICAs.     

Properties investigation on electrically conductive adhesives based on acrylate resin filled with silver microsheets and silver plating carbon fibers

The introduction of highly electrically conductive fillers (Ag microsheets and silver plating carbon fiber) can functionally improve the electrical conductivity of acrylate resin. In this study, Ag microsheets and Ag/CF were thus introduced into acrylate polymer via solution blending method under ultrasonication in order to improve the electrical conductivity of the acrylate resin. The properties and microstructures of Ag microsheets, CF, Ag/CF and ECAs were performed by scan electron microscope (SEM), X-ray diffraction analysis (XRD), etc. SEM images and XRD results illustrated that the impurities in carbon fiber could be completely removed after the adequately alkali treatment. The SEM images showed that large numbers of metallic silver particles were uniformly and densely coated on the surface of the carbon fibers and hybrid fillers (silver microsheets and Ag/CF) could homogeneously disperse in acrylate resin. Electrical conductivity measurements demonstrated that the electrical conductivity of ECAs increased with the increasing content of hybrid fillers and the percolation threshold of ECAs was 5 wt%. The electrical conductivity of ECAs at its percolation threshold was 15.79 S/cm, which was two orders of magnitude higher than that of the ECAs based on acrylate resin filled with silver microsheets. The increment in Ag/CF contents may decrease 180° peel strength and raise shear strength with low content of Ag/CF. The overall performance of ECAs was optimum with 2 wt% Ag/CF. The TGA analysis indicated that ECAs possess excellent thermal stability.     

Nanocomposite adhesives: Mechanical behavior with nanoclay

The major objective for this research was to examine the role of epoxy-clay nanocomposites in the area of epoxy bonding to porous stone (granite) substrates. Two bisphenol A epoxy systems were selected based on the prior work that determined optimal adhesive properties from a larger set of epoxy systems to determine the role of viscosity on the intercalation and exfoliation of the clay tactiods in the epoxy resin. The systems were characterized and mechanically tested at varying levels of intercalated and exfoliated organic clay tactiods. In the first stage of the work, epoxy-clay systems were characterized by wide-angle X-ray diffraction (WAXD) to detect inter-laminar distances of clay layers and to determine if the mixing procedures had indeed dispersed and exfoliated the clay layers sufficiently. The second stage of the work involved examining mechanical properties of the epoxy-nanoclay systems. Fracture behavior was studied using granite stone substrates in notched double lap configuration. Compressing a wedge between the cover plates induced the fracture. Fracture toughness was approximated by the load at fracture. Tensile properties were measured using cast dog bone tensile samples. The better layered silicate nanocomposite performance was seen with the lower viscosity resin. The most noticeable improvements in mechanical properties for the lower viscosity resin system were found to be maximum stress, elastic modulus, and yield stress. Increased toughness and stress whitening at 1% by weight nanoclay loading revealed that the clay can act as a shear-yielding toughening agent in this epoxy system.     

MXene fillers and silver flakes filled epoxy resin for new hybrid conductive adhesives

The addition of V₂CT_x two-dimensional materials as auxiliary fillers in conductive adhesives can increase the contact area between conductive particles inside the matrix effectively reducing the resistivity of epoxy resin conductive adhesives. The V₂CT_x/Ag/rGO/MWCNTs fillers inside the epoxy resin will connect more Ag-clad Cu particles to form a conductive pathway, but its excessive content will be aggregated inside and thus increase the resistivity of the conductive adhesive. The volume resistivity of ECAs increases from 4.4 × 10⁻⁶ Ω m to 1.15 × 10⁻⁵ Ω m when the V₂CT_x/Ag/rGO/MWCNTs content of 0.1% increases to 0.34%. The Ag-clad Cu particles are interconnected inside the epoxy resin to form an electron transfer network. Inside the epoxy resin substrate Ag-clad Cu particles and V₂CT_x/Ag/rGO/MWCNTs interconnects to form a larger conductive network, so that the conductive adhesive shows good conductive properties.     

Electrical and mechanical properties of electrically conductive adhesives from epoxy,micro-silver flakes,and nano-hexagonal boron nitride particles after humid and thermal aging

In this study, we incorporated micro-silver flakes and nano-hexagonal boron nitride (BN) particles into a matrix resin to prepare electrically conductive adhesives (ECAs). The humid and thermal aging results under a constant relative humidity level of 85% at 85 °C revealed that the aged ECAs containing 3 wt% of nano-hexagonal BN particles had high reliability. The contact resistance was low and the shear strength high. Nano-hexagonal BN particles have a good effect on the reliability of ECAs that can be used to improve the properties of ECAs.     

Electrical characterization of individual metal‐coated polymer spheres used in isotropic conductive adhesives

Isotropic conductive adhesives (ICAs) filled with metal‐coated polymer spheres (MPS) have been proposed to improve the mechanical reliability compared to conventional ICAs filled with silver flakes. The electrical properties of MPS play an important role in the electrical performance of macroscopic MPS‐based ICAs. This article deals with the electrical characterization of individual MPS using a nanoindentation‐based flat punch method, in which the resistance and the deformation of single MPS were monitored simultaneously. Four groups of silver‐coated polymer spheres (AgPS) with identical polymer cores but different silver coating thicknesses were tested. The resistance of AgPS decreases gradually with increasing deformation degree of particles, and increases when the deformation of particles is reduced. In addition, the resistance of individual AgPS is dependent on the physical properties of the silver coating, such as thickness, uniformity, and porosity. The thicker the silver coating is, the lower and more stable the resistance of AgPS is. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43764.     

The preparation and performance of high-temperature adhesives for graphite bonding

Two kinds of high-temperature adhesives (HTAs) were prepared. One was composed of phenol-formaldehyde (PF) resin and boron carbide (PF+B₄C), the other was composed of PF resin, B₄C and fumed silica (PF+B₄C+SiO₂). Graphite materials were bonded by the above adhesives and heat-treated at temperatures ranging from 200 to 1500 °C. The joining strength was tested at room temperature. The results show that the graphite joints exhibit satisfactory bonding strength and that ceramics fillers show a marked property modification effect. The strength of graphite joints bonded by PF+B₄C and PF+B₄C+SiO₂ adhesive and treated at 1500 °C are 9.3 and 17.1 MPa, respectively. The property modification mechanism of ceramics fillers is also discussed in this paper. A strong chemical bonding force is introduced at the bonding interface and the volume shrinkage is restrained, which can be responsible for the good adhesive properties of HTAs for graphite bonding.     

High performance electrically conductive adhesives from functional epoxy,micron silver flakes,micron silver spheres and acidified single wall carbon nanotube for electronic package

To develop high performance electrically conductive adhesives (ECAs), bi-modal ECAs were prepared by a matrix resin, micron silver flakes and micron silver spheres, and tri-modal ECAs were prepared by a matrix resin, micron silver flakes, micron silver spheres and acidified single wall carbon nanotube (ASWCNT). With the increase of nano silver spheres, the bulk resistivity of bi-modal ECAs decreased firstly and then increased while tri-modal ECAs' bulk resistivity firstly increased and then decreased with the increase of ASWCNT due to different electrically conductive channels were formed in them. After aged for 500 h under humid and thermal cycle of constant humidity level of 85% relative humidity at 85 °C, the contact resistance shift of bi-modal ECAs was more than 20% and that of tri-modal ECAs was less than 15% showing tri-modal ECAs had lower and more stable contact resistance. The humid and thermal surroundings had bad effect on the mechanical properties of bi- and tri-modal ECAs, after aged for 500 h, they both were reduced about 50–65%. And a bi-modal ECAs and a tri-modal ECAs were optimized and investigated in detail which can be used in electronic packaging.     

One-step elaboration of flexible transparent conductive electrodes from silver nanowires/polymer nanocomposites

A new simplified low temperature deposition method to manufacture flexible transparent conductive electrodes (FTCE) based on conductive polymer composite filled with silver nanowires (AgNWs) was investigated. Polyurethane/AgNWs composite was deposed on a poly(ethylene terephthalate) substrate as a conductive paint in a thin layer lower than 2 μm. The high aspect ratio nanowires influence on the electrical behavior is followed with surface resistivity and optical transparency experiments. The best compromise was obtained with a conductive layer filled with 2.84 vol.% of AgNWs; it exhibits a surface resistivity of 143 Ω/sq with 73% in transmittance. These transparent conductive composites processing in one step with good touching manipulation resistance demonstrate the real interest for this kind of FTCEs technology without indium tin oxide.     

Shear properties of isotropic conductive adhesive joints under different loading rates

Epoxy-based conductive adhesives have been widely used in the electronic field given the lead-free development of electronic packaging. The conductive adhesive joints must be subjected to shear loads during the service of electronic products considering the mismatch in mechanical properties between packaged chip and substrate. In this study, INSTRON 5544 universal material testing machine was used for tensile–shear tests of isotropic conductive adhesive joint specimens, which were prepared using pure copper plate adherend in the form of single-lap joints. Four loading rates, that is, 0.05, 0.5, 5, and 10 mm/min, were adopted. The relationship between shear load and displacement of two overlapping copper plates is deduced from a mechanical perspective. A mechanical model of the conductive adhesive shear specimen was developed by introducing dimensionless parameters, which are obtained from interfacial fracture energy and shear strength, to interpret the effect of loading rate on the shear properties of the conductive adhesive specimen considering the loading rate. Results show that this model can effectively reflect the relationship between shear load and displacement in the range of 0.05–10 mm/min.     

Relationship between the fracture energy and the mechanical behaviour of pressure-sensitive adhesives

Mechanical behaviours of two pressure-sensitive adhesives (PSAs) families, composed of elastomer copolymers or polyacrylate/acrylic copolymers, are characterised by peel tests. Fracture energy varies linearly according to the applied contact force between two levels, which depends on tackiness and cohesion of the PSA. Local fracture energies are measured by an original peeling system and they are related with the adhesive deformation. Mechanical behaviours of PSAs depend on their composition but majority of fracture energy is dissipated on the first millimetre near the bending zone where fibrils elongation is maximum. Observations of interfaces between PSAs and glass substrate underline that fracture energy varies linearly according to the contact area.     

Hotmelts with improved properties by integration of carbon nanotubes

With the aim of the development of conductive and mechanically improved adhesives, carbon nanotubes (CNTs) were dispersed by melt mixing into a non-reactive polyolefine based hotmelt adhesive. The composite materials, containing 0.5 to 5.0 wt% multi-walled CNTs (MWNTs), showed electrical percolation at about 0.75 wt%. Investigations of the mechanical properties using tensile tests resulted in a significant enhancement of Young's modulus up to 372% and nearly doubling of tensile strength at 5.0 wt%. Even if the hotmelt material is highly elastic compared to typical thermoplastic matrices, the melt mixing resulted in suitable CNT dispersion. The melt viscosity increased with CNT loading, however near the observed electrical percolation threshold the processability was not notably reduced. Most important, next to conductivity at low CNT loadings, also a significant enhancement in the shear strength of bonded joints of AlMg3 up to values of 250% of the pure hotmelt could be obtained. The property profile can be tailored with CNT concentration, indicating the suitability of CNT addition into these hotmelt adhesives.     

Influence of radiant exposure on degree of conversion,water sorption and solubility of self-etch adhesives

The purpose of this study was to investigate the influence of the radiant exposure on the degree of C=C conversion (DC), water sorption (WS), and solubility (S) of the Clearfil SE Bond (CSE) and Filtek LS (LS) self-etch adhesive systems. The primer of the LS (LSP), and bond agents of the CSE (CSEB) and LS (LSB) were tested. Specimens were light-cured using a light-emitting diode (LED) at different radiant exposures (6.1, 12.2, 13.9, and 27.8 J/cm²). DC (n=10) was measured using Fourier-transform infrared spectroscopy (FT-IR). WS and S were determined according to ISO 4049. Data were subjected to two-way ANOVA and Tukey's test at pre-set alpha of 0.05. The highest DC was exhibited by LSP, followed by CSEB and LSB, all with statistical difference (p<0.001). The DC was increased with higher radiant exposure and extended light-curing time (p<0.001). LSB and CSEB showed the lower WS followed by LSP, all with statistical difference (p<0.001). CSEB and LSB presented no significance difference on the S values (p>0.05) and were lower than LSP (p≤0.05). The WS and S were not influenced by the different radiant exposures evaluated (p=0.9548 and p>0.05, respectively). The monomer conversion is related to improvement on the mechanical properties of resinous material, but these properties also depend on the polymer network structure formed.     

High-frequency welding of polypropylene using dielectric ceramic compounds in composite adhesive layers

In this study, high-frequency welding of polypropylene by melting composite adhesive layers containing dielectric ceramics was investigated. Various dielectric ceramics were mixed in a fixed ratio with polypropylene to make the composite adhesive layers, and the resulting dielectric properties were measured using an impedance analyser. The highest loss factor in the composite adhesive layer was found when 40 vol% silicon carbide (SiC) was used in the mixture. Dynamic viscoelasticity measurements showed that all composite adhesive layers softened at approximately 170 °C and melted (fluidised) at approximately 190 °C. Each composite adhesive layer was inserted between two polypropylene plates, and irradiated at a frequency of 40 MHz. The composite adhesive layers that included 20 vol% anatase-titanium oxide, 20 vol% or 40 vol% zinc oxide and 20 vol% or 40 vol% SiC melted in 40–70 s. The bond strength of the welded material obtained was high, and the adherend failure occurred by a tensile lap shear test. The heating efficiencies of the composite adhesive layers by high-frequency radiation were related to the tanδ/ε′ value of the composites.     

Progressive Failure Analysis of Reinforced-Adhesively Single-Lap Joint

The failure behavior of reinforced-adhesively single-lap joints was investigated experimentally and numerically. The reinforced adhesive was produced by mixing waste composite particles and an epoxy-based commercial adhesive. The single-lap joint was prepared with an adhesive and unidirectional fiber glass/epoxy composite plates with a (0°/90°)₃ stacking sequence. Three types of adhesive were used: an un-reinforced adhesive (ADH), an adhesive mixed with glass fiber-reinforced epoxy resin composite plate particles (GFRC), and an adhesive mixed with carbon fiber-reinforced epoxy resin composite plate particles (CFRC). The adhesive thickness (ta) and overlap length (lap) were 0.4, 0.8, 1.2, and 1.6 mm and 10, 20, 30, and 40 mm, respectively. Progressive failure analysis was performed with the ANSYS? 11.0 finite element program using ANSYS? parametric design language (APDL) code. In the numerical study, the failure loads of the composite and the adhesive were determined with the Hashin failure criteria and the Tresca failure criteria, respectively. The difference between the experimental and numerical studies ranged from 2% to 10%. The failure load of reinforced-adhesively single-lap joints was 1.3–22.8% higher than that of the un-reinforced adhesive.     

Tensile strength of two-part epoxy paste adhesives: Influence of mixing technique and micro-void formation

Two-part epoxy paste adhesives are frequently used to bond metals and composite materials in many structural applications. After mixing two reactive parts (by weight or volume ratio), adhesive paste is applied to the substrate surfaces and cured at elevated temperatures. Air-entrapment during mixing and/or application process often produces micro-voids in the adhesive bondlines and influences the strength of the bonded joints. In this work, void formation was investigated using two adhesive mixing techniques: (a) dual-cartridge and static-mixer with a dispenser and (b) hand-mix. Flat adhesive sheets were cured by mixing a two-part epoxy adhesive, and bulk specimens with notches were cut using CNC-machining. Using X-ray microtomography scans, the micro-voids were detected and material porosity was evaluated. Furthermore, tensile tests were performed on the specimens and two-dimensional digital image correlation (2D DIC) was employed to analyse the surface strain concentrations near the notches. The fracture surfaces were examined using optical and scanning electron microscopy. The results indicated that mixing technique influences the formation of micro-voids and thus the tensile strength of two-part epoxy paste adhesives.     

Post-curing process and visco-elasto-plastic behavior of two structural adhesives

The aim of this paper is to reveal original visco-elasto-plastic phenomena for two commercial epoxy adhesives (D609 and E20HP) subjected to uniaxial tension and compression. First, a post-curing heat treatment is proposed by means of thermal analyses in order to ensure stable mechanical properties. Bulk adhesive specimens are prepared to analyze the mechanical response of both materials. Monotonic tensile and compressive tests are carried out at different strain rates. Both adhesives exhibit first a linear elastic behavior but once a yield stress is reached, a visco-elasto-plastic behavior appears. Creep tensile tests are also carried out and confirm that strain rate phenomena take place and that non-negligible negative volumetric inelastic strains appear. Cyclic tests are also performed and reveal ratcheting effects. The applicability of the results to thin bondlines is discussed. The experimental observations must be taken into account in any model which aims at predicting accurately the behavior of the adhesives considered in this paper.     

Electrically conductive adhesives with a focus on adhesives that contain carbon nanotubes

On the basis of an analysis of results presented in the literature, the currently existing knowledge about relationships between the microstructural and physical properties of hard coatings is discussed. Particular emphasis is placed on the role of microstructural features, such as grain boundaries, nonequilibrium structures, impurities, and texture, in controlling the film hardness. On the basis of an analysis of results presented in the literature, the currently existing knowledge of electrically conductive adhesives (ECAs) is discussed. Particular focus is placed on the results obtained with ECAs that contain carbon nanotubes (CNTs) as conductive fillers. The review is divided in curable ECAs based on epoxy resins, and noncurable conductive hot melts and pressure‐sensitive adhesives based on thermoplastic polymers. More literature results were found for epoxy/conductive filler ECAs than for other adhesives. Confirming the assessments made in a book by Li et al., which refers to nanotechnologies in ECAs, we found that only a reduced number of articles allude to polymer/CNT ECAs. Our analysis of the results includes a study of the balance between the viscosity, immediate adhesion, solidification process, electrical conductivity, and mechanical properties of the adhesives. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Sintering behavior and effect of silver nanoparticles on the resistivity of electrically conductive adhesives composed of silver flakes

In this paper, silver nanoparticles with size of 30–50 nm were synthesized by reducing silver nitrate with sodium borohydride and sodium citrate and using PVP as an adsorption agent in the ethanol solution. The experimental results indicate that the morphologies and sintering behaviors of both kinds of silver nanoparticles are impacted by glutaric acid and sintering temperature. The electrically conductive adhesives (ECAs) filled with micro-sized silver flakes and silver nanoparticles as hybrid fillers were fabricated and the electrical properties were investigated based on the fraction of the silver nanoparticles of the total of silver flakes and the curing temperature, etc. The incorporation of the untreated/treated silver nanoparticles into the polymer matrix with 65?wt% silver filler the resistivity increased in almost all cases, especially the high fraction and the low curing temperature. The curing temperature has influence on the resistivity of the ECAs filled with micro-sized silver flakes and the silver nanoparticles due to the sintering of the silver nanoparticles. The addition of 10% treated silver nanoparticles into the ECAs with 60?wt% silver fillers, the resistivity is slightly lower than that of the ECAs with micro-sized silver flakes. In the system of the ECAs with the high loading of silver fillers, the untreated/treated silver nanoparticles have little effect on the electrical conductivity. The results suggest that the morphology and distribution of silver fillers are the key to affect the conductivity of ECAs when nanoparticles are included in the system.     

Improving performance of polyvinyl acetate (PVA) as a binder for wood by combination with melamine based adhesives

In this study blending PVA with MUF and MF was evaluated as an approach to enhance the performance of PVA towards water and elevated temperatures. MF and MUF were added to PVA at different proportions: 15%, 30%, 50%, 70% and 100%. Blends of PVA with MF and MUF were used as adhesives to bond wood joints. The shear strength of wood joints was measured at dry and wet states, and elevated temperatures. Thermogravimetric analysis was used to study thermal stability of PVA and its blends with MF and MUF. The structural changes caused by the inclusions were characterized by Fourier transforms infrared spectroscopy (FT-IR). The results showed that shear strength of wood joints were improved by the addition of MF and MUF to PVA in all conditions. Adding small amounts of MUF or MF (as low as 15%) enhanced the performance of wood joints towards water and elevated temperatures. The extent of improvement was sometimes so high that the strength of glue line surpassed strength of wood in wet conditions leading to wood failure rather than glue failure. MF had more effectiveness in improving shear strength of wood joints than MUF in all conditions. Thermal stability of PVA was increased by MF but the effect of MUF on thermal stability of PVA was dependent on MUF proportions and temperatures. FT-IR analyses showed that there are some chemical bonds between PVA and MF. Considering costs, effectiveness and formaldehyde emission, adding 15% MF to PVA seems the optimal proportion of MF in the PVA blends.