Effects of Au and Pd Additions on Joint Strength, Electrical Resistivity, and Ion-Migration Tolerance in Low-Temperature Sintering Bonding Using Ag2O Paste

A new bonding process using an Ag₂O paste consisting of Ag₂O particles mixed with a triethylene glycol reducing agent has been proposed as an alternative joining approach for microsoldering in electronics assembly, which currently uses Pb-rich, high-temperature solders. Ag nanoparticles were formed at approximately 130°C to 160°C through a reduction process, sintered to one another immediately, and bonded to a metal substrate. An Au-coated Cu specimen was successfully bonded using the Ag₂O paste. The resulting joint exhibited superior strength compared with joints fabricated using conventional Pb-rich solders. To improve ion-migration tolerance, the Ag₂O paste was mixed with Au and Pd microparticles to form sintered Ag-Au and Ag-Pd layers, respectively. The additions of Au and Pd improved the ion-migration tolerance of the joint. Regarding the mechanical properties of the joints, addition of secondary Au and Pd both resulted in decreased joint strength. To match the joint strength of conventional Pb-10Sn solder, the mixing ratios of Au and Pd were estimated to be limited to 16?vol.% and 7?vol.%, respectively. The electrical resistivities of the sintered layers consisting of 16?vol.% Au and 7?vol.% Pd were lower than that of Pb-10Sn solder. Thus, the additive fractions of Au and Pd to the Ag₂O paste should be less than 16?vol.% and 7?vol.%, respectively, to avoid compromising the mechanical and electrical properties of the sintered layer relative to those of contemporary Pb-10Sn solder. Following the addition of Au and Pd to the paste, the ion-migration tolerances of the sintered layers were approximately 3 and 2 times higher than that of pure Ag, respectively. Thus, the addition of Au was found to improve the ion-migration tolerance of the sintered Ag layer more effectively and with less sacrifice of the mechanical and electrical properties of the sintered layer than the addition of Pd.     

A Low-Temperature Bonding Process Using Mixed Cu–Ag Nanoparticles

A low-temperature bonding process to form joints with high strength and ionic migration resistance using mixed Cu–Ag nanoparticles was studied. Although it was difficult to obtain strong joints using Cu nanoparticles, with the addition of Ag nanoparticles to the Cu nanoparticles the bonding strength of the Cu-to-Cu joints increased. The joints formed by the mixed Cu–Ag nanoparticles at 350°C exhibited a high bonding strength of ~50 MPa. Counterelectrodes made of the mixed Cu–Ag nanoparticles had four times higher ionic migration resistance compared with counterelectrodes made only of Ag nanoparticles.     

A Low-Temperature Pressureless Bonding Process Using a Trimodal Mixture System of Ag Nanoparticles

A low-temperature pressureless bonding process using a mixture of trimodal-sized Ag nanoparticles was proposed to form excellent Cu-to-Cu joints. Cu-to-Cu joints formed using the mixed Ag nanoparticles at 350°C for 5 min showed bonding strength of 13.7 MPa, in spite of the bonding process without pressure. Elongated dimples observed on the fracture surface of the Cu-to-Cu joint strongly support the effect of the trimodal mixture system of Ag nanoparticles in the low-temperature pressureless bonding process.     

Pressureless Bonding by Use of Cu and Sn Mixed Nanoparticles

Because of high thermal and electrical conductivity, high melting point, and low cost, bonding by sintering of Cu nanoparticles is promising as a new method to replace the Pb-rich solders currently used in high-temperature applications. However, it is difficult to achieve sufficient strength by using this method because, in the absence of applied pressure, oxidized surfaces inhibit sintering. In this study, we report pressureless bonding of Cu plates with Ni layers by use of Cu and Sn mixed nanoparticles. Bonding was achieved without pressure from 250°C to 350°C in hydrogen by use of pure Cu nanoparticles, and by using mixtures of Cu and Sn nanoparticles in which the amount of Sn varied from 10 to 50 wt.%. The highest strength bonds were obtained by use of Cu–10 wt.% Sn mixed nanoparticles, because the sinterability of the Cu nanoparticles is enhanced by diffusion of Sn into Cu to form an appropriate amount of Cu–Sn intermetallic compounds (IMC) and diminish microvoids. However, when the amount of Sn was greater than 10 wt.%, Cu–Sn IMC were formed to such an extent that the significant reduction of Cu-rich layers led to reduced strength. When the bonding temperature was 350°C, Sn diffused into Cu so much that microvoids were formed in the Sn-rich layer. Because the number of microvoids increased as the amount of Sn was increased, the shear strength could not be enhanced by bonding at higher temperature when the amount of Sn was greater than 30 wt.%.     

Chip to Chip Bonding Using Cu Bumps Capped with Thin Sn Layers and the Effect of Microstructure on the Shear Strength of Joints

Chip to chip bonding techniques using Cu bumps capped with thin solder layers have been frequently applied to 3D chip stacking technology. We studied the effect of joint microstructure on shear strength. Joints were formed by joining Sn/Cu bumps on a Si die and Sn/Cu layers on another Si die at 245–330°C using a thermo-compression bonder. Three different types of microstructures were fabricated in the joints by controlling the bonding temperature and time, (1) a Sn-rich phase with a Cu₆Sn₅ phase at the Cu interfaces, (2) a Cu₆Sn₅ phase in the interior with a Cu₃Sn phase at the Cu interfaces, and (3) one single Cu₃Sn phase throughout the whole joint. The joint having a single Cu₃Sn phase had the highest shear strength. Specimens were aged up to 2000 h at 150°C and 180°C. During aging, the microstructures of all joints were transformed in a single Cu₃Sn phase. The shear strength of the joints was very sensitive to the formation of Cu₃Sn and microvoids. Microvoids formed in the solder joints with a Cu₆Sn₅ phase with and without a Sn-rich phase during aging and decreased the shear strength of the joints. Conversely, aging did not induce the formation of microvoids in the joints which originally had only a Cu₃Sn phase and the shear strength was not decreased.     

AlN-to-Metal Direct Bonding Process Utilizing Sintering of Ag Nanoparticles Derived from the Reduction of Ag<Subscript>2</Subscript>O

Bonding between AlN and metals conventionally requires a surface modification process at high temperature such as metallization. The AlN-to-metal direct bonding process by sintering of Ag nanoparticles derived from in situ reduction of Ag₂O microparticles mixed with diethylene glycol is examined. Bonding was conducted at 300–500 °C after a preheating process at 100 °C, and the shear strength exceeded 20 MPa for the joint bonded at 500 °C. The role of preheating in the direct bonding of AlN and Ag was identified. The Ag nanoparticles generated during preheating at 100 °C cover the AlN surface, and they are converted into a thin Ag film. The thin film promotes the formation of a bonding layer, owing to the effective adhesion of the sintered Ag to the film, and contributes to the bonding of Ag and AlN. No interfacial reaction layer is observed. The same bonding process can be applied to other ceramics with poor wettability.     

A Hermetic Seal Using Composite Thin-Film In/Sn Solder as an Intermediate Layer and Its Interdiffusion Reaction with Cu

A bonding joint between Cu metallization and evaporated In/Sn composite solder is produced at a temperature lower than 200°C in air. The effects of bonding temperature and duration on the interfacial bonding strength are studied herein. Cross sections of bonding joints processed at different bonding conditions were examined by scanning electron microscopy (SEM). The optimal condition, i.e., bonding temperature of 180°C for 20 min, was chosen because it gave rise to the highest average bonding strength of 6.5 MPa, and a uniform bonding interface with minimum voids or cracks. Good bond formation was also evidenced by scanning acoustic imaging. For bonding couples of patterned dies, a helium leak rate of 5.8 × 10⁻⁹ atm cc/s was measured, indicating a hermetic seal. The interfacial reaction between Cu and In/Sn was also studied. Intermetallic compounds (IMCs) such as AuIn₂, Cu₆Sn₅, and Cu₁₁In₉ were detected by means of x-ray diffraction analysis (XRD), and transmission electron microscopy (TEM) accompanied by energy-dispersive x-ray (EDX) spectroscopy. Chemical composition analysis also revealed that solder interlayers, Sn, and In were completely converted into IMCs by reaction with Cu. All the IMCs formed in the joints have remelting temperatures above 300°C according to the Cu-In, Cu-Sn, and Au-In phase diagrams. Therefore, the joint is able to sustain high service temperatures due to the presence of these IMCs.     

Effects of Phenolic Resin Addition on the Electrical Conductivity and Mechanical Strength of Nano-Copper Paste Formed Cu-Cu Joints

Cu-Cu joints bonded by nano-copper pastes with different amounts of phenolic resin were developed at a low temperature (240°C) and a low pressure (1 MPa). The shear strengths of the joints were measured and the bonding layers were observed by scanning electron microscopy. The electrical conductivity of the joints was tested by a parameter analyzer. The results indicated that 2% phenolic resin in the pastes doubled the shear strength of Cu-Cu joints compared to joints made with 0%, 5% and 8% phenolic, because it filled the voids and coated sintered Cu nanoparticles in the joints without affecting the electrical conductivity of the Cu-Cu joint. This was because 2% phenolic paste prevented Cu nanoparticles from oxidation. However, 8% phenolic resin led to an increase of electrical resistivity due to the insulating property of phenolic resin, and a decrease of shear strength due to the hindrance to sintering between the nanoparticles.     

Electromigration Reliability and Morphologies of Cu Pillar Flip-Chip Solder Joints with Cu Substrate Pad Metallization

The Cu pillar is a thick underbump metallurgy (UBM) structure developed to alleviate current crowding in a flip-chip solder joint under operating conditions. We present in this work an examination of the electromigration reliability and morphologies of Cu pillar flip-chip solder joints formed by joining Ti/Cu/Ni UBM with largely elongated ∼62 μm Cu onto Cu substrate pad metallization using the Sn-3Ag-0.5Cu solder alloy. Three test conditions that controlled average current densities in solder joints and ambient temperatures were considered: 10 kA/cm² at 150°C, 10 kA/cm² at 160°C, and 15 kA/cm² at 125°C. Electromigration reliability of this particular solder joint turns out to be greatly enhanced compared to a conventional solder joint with a thin-film-stack UBM. Cross-sectional examinations of solder joints upon failure indicate that cracks formed in (Cu,Ni)₆Sn₅ or Cu₆Sn₅ intermetallic compounds (IMCs) near the cathode side of the solder joint. Moreover, the ~52-μm-thick Sn-Ag-Cu solder after long-term current stressing has turned into a combination of ~80% Cu-Ni-Sn IMC and ~20% Sn-rich phases, which appeared in the form of large aggregates that in general were distributed on the cathode side of the solder joint.     

Morphological transition of interfacial Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> grains at the Sn-3.5Ag/Ni joint

The transition in morphology of Ni₃Sn₄ grains that formed at the interface between liquid Sn-3.5Ag (numbers are in wt.% unless specified otherwise) solder and Ni substrate has been observed at 250–650°C. The morphological transition of Ni₃Sn₄ is due to the decrease of entropy of formation of the Ni₃Sn₄ phase and has been explained well by the change of Jackson’s parameter with temperature. According to the variation of solder joint strength with temperature, it decreased rapidly between 350°C and 450°C, where the thickness of the Ni₃Sn₄ intermetallic compound (IMC) layer was around 6.5 μm. However, the solder joint strength decreased slowly with an increase of soldering time without a significant drop, although the thickness of the IMC was larger than 6.5 μm. The notable drop of solder joint strength and the fracture mode transition with increase of soldering temperature appears to come from excessive lateral growth of IMC grains between 350°C and 450°C.     

Morphology and Growth of Intermetallics at the Interface of Sn-based Solders and Cu with Different Surface Finishes

Several types of surface finishes have been applied on Cu substrates in an effort to facilitate bonding and improve the reliability of lead-free solder joints. In the current research, the effects of printed circuit board surface finishes on the reliability of the solder joints were investigated by examining the morphology and growth behavior of the intermetallic compounds (IMCs) between Sn-based solders and different surface finishes on Cu. Three types of Cu substrates with different surface finishes were fabricated in this study: organic solderability preservative (OSP)/Cu, Ni/Cu, and electroless nickel immersion gold (ENIG)/Cu. Sn-3.5Ag and Sn-3.0Ag-0.5Cu were used as the solders. In the experiment, the solder joint specimens were aged isothermally at 150°C for up to 1000 h. Experimental results revealed that the OSP surface finish promoted the interdiffusion between Cu and Sn during soldering. The composition and morphology of the IMC layer at the solder/Ni/Cu interface were sensitive to the Cu concentration in the solder. Meanwhile, the solder joints with different morphological features of the IMCs exhibited significant differences in shear strengths. The Au-containing ENIG surface finish affected the shear strength of the solder joint significantly at the initial stage of isothermal aging.     

Residual-mechanical behavior of thermomechanically fatigued Sn-Ag based solder joints

Thermomechanical fatigue (TMF) due to the mismatch in coefficients of thermal expansion between solder and substrate gradually degrades the mechanical properties of electronic solder joints during service. This study investigated the role of TMF on the residual-mechanical behavior of solder joints made with eutectic Sn-Ag solder and Sn-Ag solder with Cu or Ni additions. The TMF tests were carried out between −15°C and +150°C with a ramp rate of 25°C/min for the heating segment and 7°C/min for the cooling segment. The hold times were 20 min at the high extreme and 300 min at the low extreme. Residual shear strength was found to drop significantly during the first 250 TMF cycles, although it did remain relatively constant between 250 and 1000 cycles. Alloying elements were found to affect the residual creep strength of solder joints after TMF.     

Drop impact reliability of Sn–1.0Ag–0.5Cu BGA interconnects with different mounting methods

The poor drop-shock resistance of near-eutectic Sn–Ag–Cu (SAC) solder interconnects drives the research and application low-Ag SAC solder alloys, especially for Sn–1.0Ag–0.5Cu (SAC105). In this work, by dynamic four-point bend testing, we investigate the drop impact reliability of SAC105 alloy ball grid array (BGA) interconnects with two different surface mounting methods: near-eutectic solder paste printing and flux dipping. The results indicate that the flux dipping method improves the interconnects failure strain by 44.7% over paste printing. Further mechanism studies show the fine interfacial intermetallic compounds (IMCs) at the printed circuit board side and a reduced Ag content inside solder bulk are the main beneficial factors overcoming other negative factors. The flux dipping SAC105 BGA solder joints possess fine Cu₆Sn₅ IMCs at the interface of solder/Cu pads, which increases the bonding strength between the solder/IMCs and the fracture resistance of the IMC grains themselves. Short soldering time of flux dipping joints above the solder alloy liquidus mitigates the growth of interfacial IMCs in size. In addition, a reduced Ag content in flux dipping joint bulk causes a low hardness and high compliance, thus increasing fracture resistance under higher-strain rate conditions.     

Reliability of Au-Ge and Au-Si Eutectic Solder Alloys for High-Temperature Electronics

High-temperature electronics will facilitate deeper drilling, accessing harder-to-reach fossil fuels in oil and gas industry. A key requirement is reliability under harsh conditions for a minimum continuous operating time of 500?h at 300°C. Eutectic solder alloys are generally favored due to their excellent fatigue resistance. Performance of Au-Ge and Au-Si eutectic solder alloys at 300°C up to 500?h has been evaluated. Nanoindentation results confirm the loss of strength of Au-Ge and Au-Si eutectic solder alloys during thermal aging at 300°C, as a result of grain coarsening. However, the pace at which the Au-Ge eutectic alloy loses its strength is much slower when compared with Au-Si eutectic alloy. The interfacial reactions between these eutectic solder alloys and the underbump metallization (UBM), i.e., electroless nickel immersion gold (ENIG) UBM and Cu/Au UBM, have been extensively studied. Spalling of Au₃Cu intermetallic compound is observed at the interface between Au-Ge eutectic solder and the Cu/Au UBM, when aged at 300°C for 500?h, while the consumption of ENIG UBM is nominal. Unlike the Au-Si solder joint, hot ball shear testing at high temperature confirmed that the Au-Ge joint on ENIG UBM, when aged at 300°C for 500?h, could still comply with the minimum qualifying bump shear strength based on the UBM dimension used in this work. Thus, it has been determined that, among these two binary eutectic alloys, Au-Ge eutectic alloy could fulfill the minimum requirement specified by the oil and gas exploration industry.     

Influence of Joining Conditions on Bonding Strength of Joints: Efficacy of Low-Temperature Bonding Using Cu Nanoparticle Paste

We investigated a new low-temperature bonding process utilizing Cu nanoparticle paste without addition of sintering promoter. Joint bonding strengths above 30 MPa were achieved even at a low bonding temperature of 250ºC. We attribute the higher bonding strengths of joints fabricated using the vacuum preheating process to the rapid progression of Cu nanoparticle sintering due to the activated nanoparticle surface at lower temperatures. The increase in bonding strength depended on the applied pressure, in addition to the bonding temperature. The formation of a dimple-like morphology was confirmed in the ductile fracture area. This indicated that the joint bonded strongly with the bonding layer, in agreement with the results of bonding tests carried out on strongly bonded joints. The bonding ability of the joints obtained using Cu nanoparticle paste could be improved by controlling the joint fabrication conditions.     

Shear and Pull Testing of Sn-3.0Ag-0.5Cu Solder with Ti/Ni(V)/Cu Underbump Metallization During Aging

Ti/Ni(V)/Cu underbump metallization (UBM) is widely used in flip-chip technology today. The advantages of Ti/Ni(V)/Cu UBM are a low reaction rate with solder and the lack of a magnetic effect during sputtering. Sn atoms diffuse into the Ni(V) layer to form a Sn-rich phase, the so-called Sn-patch, during reflow and aging. In this study, the relationship between interfacial reaction and mechanical properties of the solder joints with Ti/Ni(V)/Cu UBM was evaluated. Sn-3.0Ag-0.5Cu solder was reflowed on sputtered Ti/Ni(V)/Cu UBM, and then the reflowed samples were aged at 125°C and 200°C, respectively. (Cu,Ni)₆Sn₅ was formed and grew gradually at the interface of the solder joints during aging at 125°C. The Sn-patch replaced the Ni(V) layer, and (Ni,Cu)₃Sn₄ was thus formed between (Cu,Ni)₆Sn₅ and the Sn-patch at 200°C. The Sn-patch, composed of Ni and V₂Sn₃ after reflow, was transformed to V₂Sn₃ and amorphous Sn during aging. Shear and pull tests were applied to evaluate the solder joints under various heat treatments. The shear force of the solder joints remained at 421 mN, yet the pull force decreased after aging at 125°C. Both the shear and pull forces of the solder joints decreased during aging at 200°C. The effects of aging temperature on the mechanical properties of solder joint were investigated and discussed.     

Influence of Bonding Temperature and Applied Load on the Bonding Integrity and Optical Performance of Face-Down Bonded Ridge-Waveguide Lasers

The effects of bonding temperature and applied load on the mechanical integrity of 80Au-20Sn solder joints and the optical performance of laser diodes (LDs) are presented. Insufficient solder wetting at 280°C and poor joint integrity at an applied load below 0.196 MPa resulted in solder failure during die shear test. As the bonding temperature and applied load increased, the joint integrity and the optical performance improved. Shear testing further showed fracture in the LD due to the high mechanical strength of 80Au-20Sn solder and good adhesion properties of the solder joint. Microstructure studies showed good metallurgical stability with little interfacial intermetallic compound (IMC) formed. However, beyond an applied load of 0.523 MPa, the LD performances degraded due to modification of the bandgap energy in the active region. From our experimentation, a bonding window with good bonding integrity and high optical performance was, nevertheless, achieved.     

Electromigration in Line-Type Cu/Sn-Bi/Cu Solder Joints

In this study, the different electromigration (EM) behaviors of eutectic Sn-Bi solder in the solid and molten states were clarified using line-type Cu/Sn-Bi/Cu solder joints. When the eutectic Sn-Bi solder was in the solid state during the EM test, a Bi-rich layer formed at the anode side while a Sn-rich band formed at the cathode side, and the intermetallic compound (IMC) at the cathode side was thicker than that at the anode side. The growth of the Bi-rich layer exhibited a linear dependence on the time of stressing. While the actual temperature of the solder joint increased to 140°C and the solder was in a molten state or partially molten state, two separate Bi-rich layers formed at the anode side and a great many Cu₆Sn₅ IMC precipitates formed between the two Bi-rich layers. Also, the IMC layer at the cathode side was thinner than that at the anode side. With a current-crowding-reduced structure, the products of diffusivity and effective charge number of Bi in the eutectic Cu/Sn-Bi/Cu solder joints stressed with current density of 5 × 10³ A/cm² at 35°C, 55°C, and 75°C were calculated.     

Controlling intermetallic compound growth in SnAgCu/Ni-P solder joints by nanosized Cu6Sn5 addition

Nanosized Cu₆Sn₅ dispersoids were incorporated into Sn and Ag powders and milled together to form Sn-3Ag-0.5Cu composite solders by a mechanical alloying process. The aim of this study was to investigate the interfacial reaction between SnAgCu composite solder and electroless Ni-P/Cu UBM after heating for 15 min. at 240°C. The growth of the IMCs formed at the composite solder/EN interface was retarded as compared to the commercial Sn3Ag0.5Cu solder joints. With the aid of the elemental distribution by x-ray color mapping in electron probe microanalysis (EPMA), it was revealed that the SnAgCu composite solder exhibited a refined structure. It is proposed that the Cu₆Sn₅ additives were pinned on the grain boundary of Sn after heat treatment, which thus retarded the movement of Cu toward the solder/EN interface to form interfacial compounds. In addition, wetting is an essential prerequisite for soldering to ensure good bonding between solder and substrate. It was demonstrated that the contact angles of composite solder paste was <25°, and good wettability was thus assured.     

Interfacial reaction study on a solder joint with Sn-4Ag-0.5Cu solder ball and Sn-7Zn-Al (30 ppm) solder paste in a lead-free wafer level chip scale package

The interfacial reactions of solder joints between the Sn-4Ag-0.5Cu solder ball and the Sn-7Zn-Al (30 ppm) presoldered paste were investigated in a wafer level chip scale package (WLCSP). After appropriate surface mount technology (SMT) reflow process on the printed circuit board (PCB) with organic solderability preservative (Cu/OSP) and Cu/Ni/Au surface finish, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging. Sequentially, the cross-sectional analysis is scrutinized using a scanning electron microscope (SEM)/energy-dispersive spectrometer (EDS) and energy probe microanalysis (EPMA) to observe the metallurgical evolution in the interface and solder buck itself. It was found that Zn-enriched intermetallic compounds (IMCs) without Sn were formed and migrated from the presolder paste region into the solder after reflow and 150°C HTS test.