Effect of a high-temperature pre-bake treatment on whisker formation under various thermal and humidity conditions for electrodeposited tin films on copper substrates

The effect of high-temperature pre-bake treatment on whisker formation was studied under various thermal and/or humidity and plating conditions for thin tin films on thick copper substrates. The pre-bake treatment was performed at 180 °C for 1 h. In tests conducted at 85 °C/85% relative humidity and ambient atmosphere, whisker formation was suppressed considerably when a pre-bake treatment was applied. After the pre-bake treatment, Cu₃Sn intermetallic compounds were formed at the tin-copper interface. Cu₃Sn IMCs play an important role in the formation of regular-shaped Cu₆Sn₅. Cu₃Sn IMCs were also formed after temperature cycling and under conditions of 85 °C/85% RH. Irregular-shaped Cu₆Sn₅ IMCs were formed under all test conditions except for pre-baked samples in ambient atmosphere. A pre-bake treatment at 180 °C is advantageous for the inhibition of whisker formation and allows for planar and regular-shaped Cu₃Sn to be produced.     

Effect of bismuth on the growth kinetics of intermetallic compounds in Sn-3.5Ag solder joints: A growth kinetic model

The effect on the growth kinetics of the intermetallic compounds (IMCs) in solder/Cu joints, caused by adding Bi to eutectic Sn-3.5Ag solder alloy, was examined at the aging temperatures of 150°C and 180°C. The Cu₆Sn₅ layer growth was significantly enhanced, but the Cu₃Sn layer growth was slightly retarded by the addition of Bi, resulting in significant growth enhancement of the total (Cu₆Sn₅+Cu₃Sn) IMC layer with increasing Bi addition. The IMC layer growth in the Bi-containing solder joints was accompanied by the accumulation of Bi ahead of the Cu₆Sn₅ layer that resulted in the formation of a liquid layer at the Cu₆Sn₅/solder interface. A kinetic model was developed for the planar growth of the Cu₆Sn₅ and Cu₃Sn layers in the solder joints, accounting for the existence of interfacial reaction barriers. Predictions from the kinetic model showed that the experimental results could be well explained by the hypothesis that the formation of a Bi-rich liquid layer at the Cu₆Sn₅/solder interface reduces the interfacial reaction barrier at the interface.     

Microstructure evolution in Cu pillar/eutectic SnPb solder system during isothermal annealing

The reaction between Cu pillar and eutectic SnPb solder during isothermal annealing was studied systematically. Intermetallic compounds (IMCs), such as Cu₆Sn₅ and Cu₃Sn, were formed in between Cu and SnThe parabolic rate law was observed on IMC formation, which indicated that the growth of IMCs was controlled by atomic diffusion (a diffusion-limited process). Annealing at 165 °C for 160 h decreased the growth rate of Cu₆Sn₅, and at the same time increased the growth rate of Cu₃Sn. This was when Sn in solder was exhausted completely. The activation energies for the growth of Cu₃Sn and Cu₆Sn₅ were measured to be 1.77 eV and 0.72 eV, respectively. The Kirkendall void that formed at the interface between Cu pillar and solder obeyed the parabolic rate law. The growth rate of the Kirkendall void increased when the Sn in solder was consumed in its entirety.     

Growth Behavior of Intermetallic Compounds at SnAgCu/Ni and Cu Interfaces

The growth behavior of reaction-formed intermetallic compounds (IMCs) at Sn3.5Ag0.5Cu/Ni and Cu interfaces under thermal-shear cycling conditions was investigated. The results show that the morphology of (Cu _x Ni_1–x )₆Sn₅ and Cu₆Sn₅ IMCs formed both at Sn3.5Ag0.5Cu/Ni and Cu interfaces gradually changed from scallop-like to chunk-like, and different IMC thicknesses developed with increasing thermal-shear cycling time. Furthermore, Cu₆Sn₅ IMC growth rate at the Sn3.5Ag0.5Cu/Cu interface was higher than that of (Cu _x Ni_1–x )₆Sn₅ IMC under thermal-shear cycling. Compared to isothermal aging, thermal-shear cycling led to only one Cu₆Sn₅ layer at the interface between SnAgCu solder and Cu substrate after 720 cycles. Moreover, Ag₃Sn IMC was dispersed uniformly in the solder after reflow. The planar Ag₃Sn formed near the interface changed remarkably and merged together to large platelets with increasing cycles. The mechanism of formation of Cu₆Sn₅, (Cu _x Ni_1–x )₆Sn₅ and Ag₃Sn IMCs during thermal-shear cycling process was investigated.     

Microstructure-based modeling of the ageing effect on the deformation behavior of the eutectic micro-constituent in SnAgCu lead-free solder

The eutectic micro-constituent in SnAgCu solder governs the deformation behavior of the joint as it shows better deformation resistance than the Sn dendrites and occupies a high volume percentage of the whole solder. The main scope of this study is to develop a three-dimensional (3-D) homogenization model taking into account the microstructural evolution in the eutectic micro-constituent of SnAgCu solder in order to simulate the change in mechanical behavior of the joint caused by isothermal ageing. For this purpose, 3-D configurations of Ag₃Sn and Cu₆Sn₅ intermetallic compounds (IMCs) in near-eutectic SnAgCu solder are visualized in the as-soldered condition and after ageing by focused ion beam/scanning electron microscopy tomography. The tomographic images are used to generate feature-preserving finite element meshes of the actual microstructures. The representative volume element size and constitutive behavior of the eutectic mixture in the two conditions are determined by a numerical homogenization procedure. The results show a considerable reduction in the yield stress level of the eutectic micro-constituent after ageing of the solder joint. It is shown that the increase in the inter-particle spacing and decrease in the aspect ratio of IMCs due to ageing cause a significant change in the strain distribution in the tin matrix, which leads to a lower contribution of IMCs in load-sharing and yield strength of aged solder. The elastic–plastic properties of as-soldered and aged eutectic mixtures are determined by nanoindentation. The results of homogenization are validated through comparison with experimental results and prediction of the dislocation detachment theory.     

Annealing effects on the intermetallic compound formation of cold sprayed Ni,Al coatings

The annealing of Ni and Al coatings under various conditions on substrates fabricated by a cold gas dynamic spray process (CDSP) were investigated. The powder particles were accelerated through a standard De Laval-type nozzle with air used as the main carrying gas. The coatings were annealed at 450–550 °C in either argon or air atmospheres for 4 h. In the case of Ni coatings during annealing both in argon and air atmospheres, intermetallic compound layers such as Al₃Ni and Al₃Ni₂ were observed at the interfaces between the Ni coating and Al substrate. Also, the intermetallic layer formation of Al₃Ni and Al₃Ni₂ at the interfaces depended on the solid-state diffusion and the annealing temperature. The intermetallic compound AlNi was obtained at the interface of Al coating on a Ni substrate by low-temperature annealing under the melting temperature.     

Effects of in situ nickel particle addition on the microstructure and microhardness of Sn–Ag solder

Abstract

In this study, various amounts of Ni particles were added in situ to Sn–3·5 wt-%Ag lead free solder to form new composite solders. Copper substrates were then dipped into these solders and aged at 150°C for 0, 25, 225, or 1000 h. The microstructure and microhardness of the as solidified solder and the aged solder/copper couples were investigated. Experimental results revealed that the addition of Ni particles increased the microhardness of the composite solder. Ni additions of less than 3 wt-% yielded a microstructure of β-Sn grains surrounded by a eutectic mixture of Ag₃Sn and a Sn rich matrix. An intermetallic compound of Ni₃Sn₄ particles was dispersed throughout the eutectic. For 5 wt-%Ni addition, the Ni₃Sn₄ phase and the remaining Ni particles were agglomerated. In the case of copper substrate dipped with a thick layer of composite solder, water quenched and then aged at 150°C, the induced (Ni, Cu)₃Sn₄ particles coarsened and agglomerated. Additionally, the intermetallic (Cu, Ni)₆Sn₅ compound layer formed at the solder/Cu interface thickened with increasing Ni content.     

Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu₆Sn₅ and Cu₃Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu₆Sn₅ and Cu₃Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.     

The effect of tin and nitrogen on liquid phase sintering of Al–Cu–Mg–Si alloys

Alloys of Al–3.8Cu–1Mg, Al–3.8Cu–1Mg–0.7Si, Al–3.8Cu–1Mg–0.1Sn and Al–3.8Cu–1Mg–0.7Si–0.1Sn were made using elemental powders and conventional press-and-sinter powder metallurgy techniques. The sintering of these alloys was studied at 590 °C under atmospheres of nitrogen or argon using a horizontally aligned, push-rod dilatometer. Sintered samples were characterized using scanning electron microscopy and positron annihilation lifetime spectroscopy. Under argon, shrinkage occurs in a single stage and the shrinkage rate decays monotonically over time. Sintering shrinkage under nitrogen occurs in three distinct stages and the rate increases over time. Tin decreases shrinkage under argon but activates shrinkage under nitrogen. Positron spectroscopy indicates that the presence of tin does not alter the vacancy concentration in the sintered alloys, suggesting that tin does not bind preferentially to vacancies in the aluminum matrix in these AlCuMgSi alloys. Rather, it appears that tin may limit the formation of aluminum nitride on specific surfaces.     

Microstructural evolution of intermetallic compounds in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn and 1.5In)/Cu solder joints during liquid aging

In this paper, the microstructural evolution of IMCs in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn, 1.5In)/Cu solder joints and their growth mechanisms during liquid aging were investigated by microstructural observations and phase analysis. The results show that two-phase (Ni₃Sn₄ and Cu₆Sn) IMC layers formed in Sn–3.5Ag–0.75Ni/Cu solder joints during their initial liquid aging stage (in the first 8 min). While after a long period of liquid aging, due to the phase transformation of the IMC layer (from Ni₃Sn₄ and Cu₆Sn phases to a (Cu, Ni)₆Sn₅ phase), the rate of growth of the IMC layer in Sn–3.5Ag–0.75Ni/Cu solder joints decreased. The two Cu₆Sn₅ and Cu₅Zn₈ phases formed in Sn–3.5Ag–1.0Zn/Cu solder joints during the initial liquid aging stage and the rate of growth of the IMC layers is close to that of the IMC layer in Sn–3.5Ag/Cu solder joints. However, the phase transformation of the two phases into a Cu–Zn–Sn phase speeded up the growth of the IMC layer. The addition of In to Sn–3.5Ag solder alloy resulted in Cu₆(Sn_x,In_1?x)₅ phase which speeded up the growth of the IMC layer in Sn–3.5Ag–1.5In/Cu solder joint.     

Phase equilibria of the Au–Sn–Zn ternary system and interfacial reactions in Sn–Zn/Au couples

Phase equilibria of the Au–Sn–Zn ternary system and interfacial reactions between Sn–Zn alloys and Au were experimentally investigated at 160 °C. Experimental results reveal that no equilibrium-stated ternary phases were found and the ternary element solubility in the binary phase is insignificant. When the Zn content was less than 3 wt% in the Sn–Zn alloy, only the Au–Sn binary intermetallic compounds (IMCs), such as AuSn, AuSn₂ and AuSn₄ phases, were formed at the Sn–Zn/Au interface. When the Zn content in Sn–Zn alloys was greater than 7 wt%, the AuZn, AuZn₂ and Au₃Zn₇ phases were formed in the Sn–Zn/Au couples at 160 °C. However, both Sn–Zn and Au–Zn IMCs, and the Au–Zn–Sn ternary IMC (T phase) were observed between Au and the Sn–Zn alloys with 3–5 wt% added Zn. This T phase might be the metastable phase. The evolution of IMCs in the Sn–Zn/Au couples is very sensitive to the Zn content in Sn–Zn alloys.     

Pb-free solders for flip-chip interconnects

A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag₃Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni₃Sn₄ formed and on copper, Cu₆Sn₅Cu₃Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu. Editor’s Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/Frear-0106.html For more information, contact D.R. Frear, Interconnect Systems Laboratories, Motorola, Tempe, AZ 85284; (480) 413-6655; fax (480) 413-4511; e-mail darrel.frear@motorola.com.     

Effects of sulfide-forming element additions on the Kirkendall void formation and drop impact reliability of Cu/Sn–3.5Ag solder joints

Ternary Pb-free solders, Sn–3.5Ag–X, containing 0.5 wt.% of Zn, Mn and Cr, were reacted with Cu UBM, which was electroplated using SPS additive. Characteristics of Cu–Sn IMCs and Kirkendall void formation at the Cu/Sn–3.5Ag solder joints were significantly affected by the third element, and the potency to suppress Kirkendall voids at the solder joint increased in the order of Cr, Mn, Zn, which was indeed the order of the drop reliability improvement. From the AES analyses, it was suggested that the sulfide-forming elements in the solder diffused into the Cu UBM and reduced the segregation of S atoms to the Cu/Cu₃Sn interface by scavenging S, which led to the suppression of Kirkendall void nucleation at the Cu/Cu₃Sn interface and the drop reliability improvement. In the case of the Zn-containing solder joint, Cu₃Sn phase, known to be a host of Kirkendall voids, did not form at all even after extended aging treatments. The magnitude of the tensile stress at the Cu₃Sn/Cu interface which drove the Kirkendall void growth was estimated to be 10–100 MPa.     

Morphology and growth kinetics of Ag3Sn during soldering reaction between liquid Sn and an Ag substrate

For the soldering of recycled Ag sputtering targets, the interfacial reaction between liquid Sn and an Ag substrate at temperatures ranging from 250 –425°C has been investigated. Experimental results show that a scallop-shaped layer of Ag₃Sn intermetallic compounds formed during the soldering reaction. Kinetics analysis indicated that the growth of such interfacial Ag₃Sn intermetallic compounds is diffusion-controlled with activation energy of 70.3kJ/mol. During the reaction, the Ag substrate dissolves into the molten Sn solder and causes the appearance of needle-shaped Ag₃Sn precipitates in the Sn matrix.     

The Inhibition of Tin Whiskers on the Surface of Sn-8Zn-3Bi-0.5Ce Solders

Through the refinement of the (Ce, Zn)Sn₃ intermetallic phase, the formation of tin whiskers, previously observed on the surface of a Sn-3Ag-0.5Cu-0.5Ce solder, was prevented in a Sn-9Zn-0.5Ce alloy. However, whisker growth can still occur on the surface of Sn-8Zn-3Bi-0.5Ce solder after air storage at room temperature and at 150 °C due to the formation of large (Ce, Zn)Sn₃ intermetallic clusters. Further experiments showed that decreasing the Bi-content in this Sn-8Zn-0.5Ce alloy to 1 and 2 wt.% can recover the beneficial effects of Zn additions on the refinement of the (Ce, Zn)Sn₃ phase and obviously reduce the appearance of tin whiskers. In addition, alloying the Sn-8Zn-3Bi-0.5Ce solder with 0.5 wt.% Ge, which increases the oxidation resistance of the (Ce, Zn)Sn₃ intermetallic clusters, can also effectively inhibit tin whisker growth.     

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag (0 wt.%-1 wt.%) to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds (IMCs) formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the glutinosity and fluidity of Sn-9Zn-(0.5, 1)Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics (Cu₅Zn₈). The peripheral AgZn₃, nodular on the Cu₅Zn₈ IMCs layer, is likely to be generated by a peritectic reaction L + γ-Ag₅Zn₈ → ɛ-AgZn₃ and the following crystallization of AgZn₃.     

Dissolution and interfacial reaction of Nb in contact with the molten 52In–48Sn solder

The dissolution and interfacial reaction of Nb in contact with the molten 52In–48Sn solder has been investigated in the temperature range 192–260 °C for periods ranging up to 1 year. Intermetallic compounds (IMCs) grow at the interface between the Nb and the solder, after a latency time required for Nb to diffuse in the solder, and these have been identified by X-ray diffraction as NbSn₂ hexagonal platelet crystals, with a highly preferred orientation. The crystal sizes have been found to follow a log-normal distribution and crystal growth begins first at the corners of the substrate, followed by the edges and then finally in the centre. The Nb/solder system is unusual in that the IMC growth is several orders of magnitude slower than observed in other solder–substrate systems, and the limiting size of the IMC layer actually decreases with increasing temperature. A model explaining these observations is presented where the IMC nucleation and growth are controlled by diffusion of Nb atoms in the liquid solder. Low meta-stable concentration of Nb at the interface, a critical supersaturated concentration of Nb very close to the meta-stable concentration required before the IMC can grow and negligible solid state diffusion in the IMC are identified as the key factors responsible for the observed kinetics of dissolution and interfacial reaction.     

Sn-Ag-Cu and Sn-Cu solders: Interfacial reactions with platinum

The interfacial reaction and intermetallic formation at the interface between tin solders containing a small amount of copper with platinum were investigated in this study. Sn-0.7Cu and Sn-1.7Cu solders were reacted with platinum by dipping Pt/Ti/Si specimens into the molten solder at 260°C. Sn-3.8Ag-0.7Cu solder was reacted with platinum by reflowing solder paste on a Pt/Ti/Si substrate at 250°C. PtSn₄ intermetallic formed in all specimens while Cu₆Sn₅ interfacial intermetallic was not observed at the solder/platinum interfaces in any specimens. A parabolic relationship existed between the thickness of the Pt-Sn intermetallic and reaction time, which indicates the intermetallic formation in the solder/platinum interface is diffusion controlled. For more information, contact Young-Ho Kim, Hanyang University, Department of Materials Engineering, Seoul, 133-791, Korea; e-mail kimyh@hanyang.ac.kr.     

Effect of Zn addition in Sn-rich alloys on interfacial reaction with Au foils

To restrain the formation of AuSnx intermetallic components （IMCs） in solder joints, Zn was added into Sn-rich solders. The solder joints were fabricated by a laser reflow soldering method, and then they were aged at 125 ℃. The results show that the total thickness of AuSnx IMCs at the interface of pure Sn solder and Au foils reaches about 54 μm under the condition of 600 h aging. In Sn-1.5Zn solder joints, however, formation of AuSn4 IMCs is restrained greatly. As the content of Zn in the solder is increased to 3.5%（mass fraction）, no AuSn4 IMC is observed at the interface. Au-Zn phases form beside AuSn2 and AuSn IMCs layers. As for Sn-9.0Zn solder joints, Au-Zn and Au-Zn-Sn phases and few AuSnx IMCs form at the interface. Moreover, total thickness of the phases and IMCs is far less than that ofAuSnx IMCs in the pure Sn solder joints.