A numerical method for predicting intermetallic layer thickness developed during the formation of solder joints

A numerical, method has been developed for calculating the thickness of intermetallic layers formed in substrate-solder systems during the soldering process. As input, the method requires the temperature-time profile for the soldering process and the isothermal liquid state growth rate parameters for the growth of the intermetallic layer. These usually consist of a growth constant, k_o, and an activation energy, Q. The method allows one to predict the thickness of a layer at any time during the soldering process. As such, it can be used in industrial solder processing to enhance the reliability and lifetime of solder joints by allowing control of the thickness of intermetallic layers. The validity of the method is demonstrated for intermetallic growth between copper and 62Sn-36Pb-2Ag solder. The kinetic parameters for the chosen model system were experimentally determined and isothermal intermetallic layer growth between molten solder and copper was found to follow a t^0.25 dependence on time t. The growth rate increased with increasing temperature according to an Arrhenius dependence in the temperature range 187 to 258°C with Q = 7.04 kJ/mol and k_o = 7.75 μm/min^0.25.     

Substrate Dissolution and Shear Properties of the Joints between Bi-Ag Alloys and Cu Substrates for High-Temperature Soldering Applications

The present study investigated interfacial reactions between Cu substrates and Bi-Ag alloys during soldering. Without forming intermetallic compounds (IMCs), the molten solder grooved and further penetrated along the grain boundaries (GBs) of the Cu substrate. An increase in Ag content enhanced GB grooving, raised the dissolution rate and also the amount of dissolved Cu in molten Bi. A stoichiometric Cu-Bi phase formed isothermally in liquid solders and considerably affected the Cu dissolution kinetics. The results also show that Bi-Ag/Cu joints possessed a better shear strength than the Pb-Sn/Cu, which implies that mechanical bonding by grain-boundary grooves was strong enough to withstand shear deformation.     

Interdiffusion analysis of the soldering reactions in Sn-3.5Ag/Cu couples

Extensive microstructural and kinetic studies on the formation and growth of the intermetallics of Sn-rich solder/Cu couples have been reported. However, experimental data on the interdiffusion mechanisms during soldering reactions are limited and in conflict. The interdiffusion processes for soldering of Sn-3.5Ag alloy/Cu couples were investigated by using the Cr-evaporated surface as a reference line. At the beginning of soldering, Cu was observed to outdiffuse to the molten Sn−3.5Ag alloy until saturation, and the Sn−Ag solder dissolved with Cu collapsed below the reference line. As a result, the scallop-shaped Cu₆Sn₅ intermetallic compound was formed at the newly-formed Sn−Ag−Cu solder/Cu interface below the original Cu surface. When the soldered joint was reflowed at the lower temperature to suppress the Cu dissolution, the Cu₆Sn₅/Cu interface moved into the Cu substrate. Therefore, Sn is the dominant diffusing species for the intermetallic formation during the soldering process, although the extensive Cu dissolution occurs at the early stage of soldering.     

Study of interfacial reactions between Sn3.5Ag0.5Cu composite alloys and Cu substrate

For development of a lead-free composite solder for advance electrical components, lead-free Sn3.5Ag0.5Cu solder was produced by mechanically mixing 0.5 wt.% TiO₂ nanopowder with Sn3.5Ag0.5Cu solder. The morphology and growth kinetics of the intermetallic compounds that formed during the soldering reactions between Sn3.5Ag0.5Cu solder with intermixed TiO₂ nanopowder and Cu substrates at various temperatures ranging from 250 to 325 °C were investigated. A scanning electron microscope (SEM) was used to quantify the interfacial microstructure at each processing condition. The thickness of interfacial intermetallic layers was quantitatively evaluated from SEM micrographs using imaging software. Experimental results show that a discontinuous layer of scallop-shaped Cu-Sn intermetallic compounds formed during the soldering. Kinetics analysis shows that the growth of such interfacial Cu-Sn intermetallic compounds is diffusion controlled with an activation energy of 67.72 kJ/mol.     

Effects of microstructural evolution and intermetallic layer growth on shear strength of ball-grid-array Sn-Cu solder joints

The shear strength of ball-grid-array (BGA) solder joints on Cu bond pads was studied for Sn-Cu solder containing 0, 1.5, and 2.5 wt.% Cu, focusing on the effect of the microstructural changes of the bulk solder and the growth of intermetallic (IMC) layers during soldering at 270°C and aging at 150°C. The Cu additions in Sn solder enhanced both the IMC layer growth and the solder/IMC interface roughness during soldering but had insignificant effects during aging. Rapid Cu dissolution from the pad during reflow soldering resulted in a fine dispersion of Cu₆Sn₅ particles throughout the bulk solder in as-soldered joints even for the case of pure Sn solder, giving rise to a precipitation hardening of the bulk solder. The increased strength of the bulk solder caused the fracture mode of as-soldered joints to shift from the bulk solder to the solder/IMC layer as the IMC layer grew over a critical thickness about 1.2 m for all solders. The bulk solder strength decreased rapidly as the fine Cu₆Sn₅ precipitates coarsened during aging. As a consequence, regardless of the IMC layer thickness and the Cu content of the solders, the shear strength of BGA solder joints degraded significantly after 1 day of aging at 150°C and the shear fracture of aged joints occurred in the bulk solder. This suggests that small additions of Cu in Sn-based solders have an insignificant effect on the shear strength of BGA solderjoints, especially during system use at high temperatures.     

Phase field simulations of intermetallic compound growth during soldering reactions

Phase field simulations of the microstructural evolution of the intermetallic compound (IMC) layer formed during isothermal soldering reactions between Sn-Cu solder alloys and a Cu substrate are presented. The simulation accounts for the fast grain boundary (GB) diffusion in the IMC layer, the concurrent IMC grain coarsening along with the IMC layer growth, and the dissolution of Cu from the substrate and IMC layer. The simulation results support the previous suggestions that the growth kinetics of the IMC layer during soldering is predominantly governed by the fast GB diffusion and the concurrent coarsening rate of the IMC grains. The IMC grain coarsening is initiated by a competitive growth of the IMC grains at the solder/IMC interface. It is also shown that the dissolution of Cu into an unsaturated solder reduces the coarsening rate of the IMC grains, consequently decreasing the temporal growth exponent of the IMC layer.     

Reactions of lead-free solders with CuNi metallizations

We have done experimental research on the dissolution rate and intermetallic growth on Cu, Ni, and CuNi-alloy substrates as a function of time and Cu/Ni ratio of the substrate. Reactions that occur when CuNi metallizations are soldered with lead-free solders were investigated. The experiments were performed using Sn-3.5Ag and Sn-3.8Ag-0.7Cu solders and different CuNi alloys. To determine the rate of dissolution of the substrate material into the solder, CuNi foils of different concentrations were immersed in Sn-3.5Ag and Sn-3.8Ag-0.7Cu solder baths for soldering times ranging from 15 sec to 5 min at 250°C. In addition, reflows of solder balls were made on top of bulk substrates to study the reaction when there is a practically infinite amount of CuNi available compared to the amount of solder. Thin film experiments were also done, where Ni containing under bump metallizations (UBMs) were fabricated and reflowed with eutectic SnAg solder balls. The nickel slows down the dissolution of the UBM into the solder and the formation of intermetallics during reflow compared to Cu metallizations. The solder/UBM interfaces were analyzed with SEM to find out how Ni concentration affects the reaction, and how much Ni is needed to obtain a sufficiently slow reaction rate.     

Characteristics of the Sn-Pb eutectic solder bump formed via fluxless laser reflow soldering

In an attempt to develop a fluxless reflow solder bumping process, the effects of processing variables, which include energy input rate and time, and the shape of solder disk on the microstructure of the solder/Cu pad interface and the shear strength of the joints were investigated. It was demonstrated that a proper combination of the variables could lead to the formation of a spherical solder bump with shear strength comparable to that formed via the conventional reflow soldering process. In addition, the kinetics of Cu pad dissolution into the solder during laser heating was modeled numerically to elucidate intermetallic formation mechanism at the solder/Cu pad interface. Jointly appointed by CAAM at POSTECH     

Depressing effect of 0.2wt.%Zn addition into Sn-3.0Ag-0.5Cu solder alloy on the intermetallic growth with Cu substrate during isothermal aging

The formation and growth of intermetallic compounds (IMCs) in lead-free solder joints, during soldering or subsequent aging, have a significant effect on the thermal and mechanical behavior of solder joints. In this study, the effects of a 0.2wt.%Zn addition into Sn-3.0Ag-0.5Cu (SAC) lead-free solder alloys on the growth of IMCs with Cu substrates during soldering and subsequent isothermal aging were investigated. During soldering, it was found that a 0.2wt.%Zn addition did not contribute to forming the IMC, which was verified as the same phase structure as the IMC for Sn-3.0Ag-0.5Cu/Cu. However, during solid-state isothermal aging, the IMC growth was remarkably depressed by the 0.2 wt.% Zn addition in the SAC solder matrix, and this effect tended to be more prominent at higher aging temperature. The activation energy for the overall IMC growth was determined as 61.460 and 106.903 kJ/mol for Sn-Ag-Cu/Cu and Sn-Ag-Cu-0.2Zn/Cu, respectively. The reduced diffusion coefficient was confirmed for the 0.2Zn-containing solder/Cu system. Also, thermodynamic analysis showed the reduced driving force for the Cu₆Sn₅ IMC with the addition of Zn. These may provide the evidence to demonstrate the depressing effect of IMC growth due to the 0.2wt.%Zn addition in the Sn-Ag-Cu solder matrix.     

Copper substrate dissolution in eutectic Sn-Ag solder and its effect on microstructure

The dissolution of Cu into molten Sn-3.8at.%Ag (Sn-3.5wt.%Ag) solder and its effect on microstructure were studied by light microscopy, scanning microscopy, and x-ray microanalysis. X-ray microanalysis of the average Cu content of samples soldered under various conditions showed that the amount of Cu dissolved during soldering increased with increasing soldering temperature and time and that the rate of dissolution could be described by a Nernst-Brunner equation. Microstructurally it was found that the volume fractions of primary β(Sn) dendrites and η-phase dendrites increase with increasing soldering temperature and time. The microstructural changes can be explained using Sn-Ag-Cu phase equilibrium data. A numerical method was developed for calculating the amount of Cu dissolved under non-isothermal conditions, which describes dissolution reasonably well.     

Wetting and Soldering Behavior of Eutectic Au-Ge Alloy on Cu and Ni Substrates

Au-Ge-based alloys are interesting as novel high-temperature lead-free solders because of their low melting point, good thermal and electrical conductivity, and high corrosion resistance. In the present work, the wetting and soldering behavior of the eutectic Au-28Ge (at.%) alloy on Cu and Ni substrates have been investigated. Good wetting on both substrates with final contact angles of 13° to 14° was observed. In addition, solder joints with bond shear strength of 30 MPa to 35 MPa could be produced under controlled conditions. Cu substrates exhibit pronounced dissolution into the Au-Ge filler metal. On Ni substrates, the NiGe intermetallic compound was formed at the filler/substrate interface, which prevents dissolution of Ni into the solder. Using thin filler metal foils (25 μm), complete consumption of Ge in the reaction at the Ni interface was observed, leading to the formation of an almost pure Au layer in the soldering zone.     

Kinetics of intermetallic formation at Sn-37Pb/Cu interface during reflow soldering

The kinetics of the intermetallic layer formation at Sn-37wt.%Pb solder/Cu pad interface during reflow soldering were studied. The growth kinetics were analyzed theoretically by assuming that the mass flux of Cu through channels between scalloplike grains primarily contributes to the growth. Rate-controlling steps considered for the mass flux were the Cu dissolution from the bottom of the channels, diffusion through the channel, and the formation reaction of the intermetallic layer. These results indicated that a transition in the growth rate observed around 120–150 sec of reflow time may be associated with transition of the rate-controlling step from the Cu dissolution to the Cu diffusion through the channel.     

Comparative study of the dissolution kinetics of electrolytic Ni and electroless Ni–P by the molten Sn3.5Ag0.5Cu solder alloy

Lead-free solders have high Sn content and high melting temperature, which often cause excessive interfacial reactions at the interface. Sn3.5Ag0.5Cu lead-free solder alloy has been used to identify its interfacial reactions with two-metal layer flexible substrates. In this paper we investigate the dissolution kinetics of Sn3.5Ag0.5Cu solder on electrolytic Ni/electroless NiP layer. It is found that during 1 min of reflow electroless NiP layer dissolves slightly lower than the electrolytic Ni due to the barrier layer formation between the intermetallic compounds (IMCs) and electroless NiP layer. Faster nucleation of IMCs on the electrolytic Ni layer is proposed as the main reason for higher initial dissolution. The appearance of P-rich Ni layer acts as a diffusion barrier layer between the solder and electroless NiP layer, which decreases the dissolution rate and IMCs growth rate than that of the electrolytic Ni layer, but weaken the interface and reduces the ball shear strength and reliability. After acquiring certain thickness P-rich Ni layer breaks and increases the diffusion rate of Sn and as a consequence both the IMCs growth rate and dissolution rate also increases. It is found that 3 μm thick electroless NiP layer cannot protect the Cu layer for more than 120 min at 250 °C. In electrolytic Ni shear strength does not change significantly and lower dissolution rate and more protective for Cu layer during long time molten reaction.     

Dissolution behavior of Cu and Ag substrates in molten solders

This study investigated the dissolution behavior of Cu and Ag substrates in molten Sn, Sn-3.5Ag, Sn-4.0Ag-0.5Cu, Sn-8.6Zn and Sn-8.55Zn-0.5Ag-0.1Al-0.5Ga lead-free solders as well as in Sn-37Pb solder for comparison at 300, 350, and 400°C. Results show that Sn-Zn alloys have a substantially lower dissolution rate of both Cu and Ag substrates than the other solders. Differences in interfacial intermetallic compounds formed during reaction and the morphology of these compounds strongly affected the substrate dissolution behavior. Soldering temperature and the corresponding solubility limit of the substrate elements in the liquid solder also played important roles in the interfacial morphology and dissolution rate of substrate.     

Influence of Cu addition to interface microstructure between Sn-Ag solder and Au/Ni-6P plating

The formation and growth of intermetallics at the interface between Sn-Ag-(Cu) alloy balls and Au/Ni-6P plating were experimentally examined as a function of soldering period. Joint strengths were also evaluated by a ball pull test. For the joint with Sn-3.5Ag, the primary reaction product of Ni₃Sn₄ exhibits growth and shrinkage in thickness repeatedly with a passage of reaction time up to 30 min, while the Ni₃SnP reaction layer monotonously increases its thickness without fluctuation. In the cases of the joints with Cu bearing solder, Sn-3Ag-0.5Cu and Sn-3.5Ag-0.8Cu, a single η-(Cu,Ni)₆Sn₅ interface layer grows by fast Cu segregation from liquid solder to the interface layer on soldering. For all the soldered joints, a P-rich layer appears at the surface region of a Ni-6P plating layer by Ni depletion to form those intermetallic compounds at interfaces. The growth rate of a P-rich layer for Sn-3.5Ag is faster by about 4–8 times than those of the Sn-Ag-Cu. The presence of Cu in solder enhances the formation of the Cu₆Sn₅ intermetallic layer at the interface resulting in prevention of Ni diffusion to liquid solder. For all the soldered joints, coarsened reaction interfaces decrease the joint strengths.     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Reaction of Sn-3.5Ag-0.7Cu-xSb solder with Cu metallization during reflow soldering

The influence of Sb on the growth kinetics of intermetallic compound (IMC) and chemical reaction between Sn-3.5Ag-0.7Cu-xSb (x=0, 0.2, 0.5, 1.0, 1.5, and 2.0) lead-free solder and Cu during reflow soldering is investigated in this study. Scanning electron microscope (SEM) is used to measure the thickness and grain size of the intermetallic layer and observe the microstructural evolution of solder joints. Results show that both thickness and grain size of IMC decrease once Sb is added into the Sn-Ag-Cu solder system, and have a significant drop at the composition of about 1.0 wt%. Beyond this composition, the thickness and grain size of IMC increase slightly. The growth exponents for both IMC layers and grains are determined by curve-fitting to study the growth kinetics of IMC in wetting reaction. The results reveal that the growth exponents of IMC range from 0.32 to 0.35, and those of IMC grains range from 0.28 to 0.32, which suggests that the growth of IMC is controlled through combined kinetic processes of atomic interdiffusion, interfacial reaction, and grain ripening. These data also show that Sn-3.5Ag-0.7Cu with about 1.0 wt% Sb solder system exhibits the smallest growth rate and gives the most prominent effect in retarding IMC growth and refining IMC grain size. Based on the phase diagram analysis and the observation of the microstructural evolution of the solder joints, a heterogeneous nucleation mechanism for retarding the IMC growth due to Sb addition is proposed.     

Properties of Sn3.8Ag0.7Cu Solder Alloy with Trace Rare Earth Element Y Additions

In the current research, trace rare earth (RE) element Y was incorporated into a promising lead-free solder, Sn3.8Ag0.7Cu, in an effort to improve the comprehensive properties of Sn3.8Ag0.7Cu solder. The range of Y content in Sn3.8Ag0.7Cu solder alloys varied from 0 wt.% to 1.0 wt.%. As an illustration of the advantage of Y doping, the melting temperature, wettability, mechanical properties, and microstructures of Sn3.8Ag0.7CuY solder were studied. Trace Y additions had little influence on the melting behavior, but the solder showed better wettability and mechanical properties, as well as finer microstructures, than found in Y-free Sn3.8Ag0.7Cu solder. The Sn3.8Ag0.7Cu0.15Y solder alloy exhibited the best comprehensive properties compared to other solders with different Y content. Furthermore, interfacial and microstructural studies were conducted on Sn3.8Ag0.7Cu0.15Y solder alloys, and notable changes in microstructure were found compared to the Y-free alloy. The thickness of an intermetallic compound layer (IML) was decreased during soldering, and the growth of the IML was suppressed during aging. At the same time, the growth of intermetallic compounds (IMCs) inside the solder was reduced. In particular, some bigger IMC plates were replaced by fine, granular IMCs.     

Effect of substrate metallization on interfacial reactions and reliability of Sn-Zn-Bi solder joints

The scope of this paper covers a comprehensive study of the lead-free Sn-Zn-Bi solder system, on Cu, electrolytic Ni/Au and electroless Ni(P)/Au surface finishes. This includes a study of the shear properties, intermetallic compounds at the substrate-ball interface and dissolution of the under bump metallization. The Sn-8Zn-3Bi (wt.%) solder/Cu system exhibited a low shear load with thick IMCs formation at the interface. The dissolution of the Cu layer in the Sn-Zn-3Bi solder is higher than that of the other two Ni metallizations. It was found that the formation of a thick Ni-Zn intermetallic compound (IMC) layer at the solder interface of the electrolytic Ni bond pad reduced the mechanical strength of the joints during high temperature long time liquid state annealing. The solder ball shear-load for the Ni(P) system during extended reflow increased with an increase of reflow time. No spalling was noticed at the interface of the Sn-Zn-3Bi solder/Ni(P) system. Sn-8Zn-3Bi solder with electroless Ni(P) metallization appeared as a good combination in soldering technology.     

The formation of Cu3Sn intermetallic on the reaction of cu with 95Pb-5Sn solder

This study characterizes the interfacial reactions that occur when Cu is soldered with 95 Pb-5Sn solder. A continuous layer of Cu₃Sn ε phase forms during the soldering process. Previous studies suggest that the intermetallic layer spalls off during soldering. However, the present work shows that the intermetallic layer is intact after soldering and that any spalling observed is due to improper polishing. A new polishing technique was developed to preserve the intermetallic layer. The Cu³Sn has a fine columnar grain structure that is very brittle. Both intergranular and transgranular fracture modes are observed. The size of the intermetallic layer is dependent upon the length of time the solder is molten. The rate of formation of e phase was measured and used to determine an activation energy for diffusion of Sn in 95Pb-5Sn of 13 kcal/mol.