Microstructure, solderability, and growth of intermetallic compounds of Sn-Ag-Cu-RE lead-free solder alloys

The near-eutectic Sn-3.5 wt.% Ag-0.7 wt.% Cu (Sn-3.5Ag-0.7Cu) alloy was doped with rare earth (RE) elements of primarily Ce and La of 0.05–0.25 wt.% to form Sn-3.5Ag-0.7Cu-xRE solder alloys. The aim of this research was to investigate the effect of the addition of RE elements on the microstructure and solderability of this alloy. Sn-3.5Ag-0.7Cu-xRE solders were soldered on copper coupons. The thickness of the intermetallic layer (IML) formed between the solder and Cu substrate just after soldering, as well as after thermal aging at 170°C up to 1000 h, was investigated. It was found that, due to the addition of the RE elements, the size of the Sn grains was reduced. In particular, the addition of 0.1wt.%RE to the Sn-3.5Ag-0.7Cu solder improved the wetting behavior. Besides, the IML growth during thermal aging was inhibited.     

The effect of Ag content on the formation of Ag3Sn plates in Sn-Ag-Cu lead-free solder

The formation of Ag₃Sn plates in the Sn-Ag-Cu lead-free solder joints for two different Ag content solder balls was investigated in wafer level chip scale packages (WLCSPs). After an appropriate surface mount technology reflow process on a printed circuit board, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging, or 1,000 cycles thermal cycling test (TCT). Sequentially, the cross-sectional analysis was scrutinized using a scanning electron microscope/energy dispersive spectrometer (SEM/EDX) to observe the metallurgical evolution of the amount of the Ag₃Sn plates at the interface and the solder bulk itself. Pull and shear tests were also performed on samples. It was found that the interfacial intermetallic compound (IMC) thickness, the overall IMC area, and the numbers of Ag₃Sn plates increase with increasing HTS and TCT cycles. The amount of large Ag₃Sn plates found in the Sn-4.0Ag-0.5 Cu solder balls is much greater than that found in the Sn-2.6Ag-0.5Cu solder balls; however, no significant difference was found in the joint strength between two different Ag content solder joints.     

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.     

Effect of thermal cycling on the growth of intermetallic compounds at the Sn-Zn-Bi-In-P lead-free solder/Cu interface

The low-temperature Sn-9Zn-1.5Bi-0.5In-0.01P lead-free solder alloy is used to investigate the intermetallic compounds (IMCs) formed between solder and Cu substrates during thermal cycling. Metallographic observation, scanning electron microscopy, transmission electron microscopy, and electron diffraction analysis are used to study the IMCs. The γ-Cu₅Zn₈ IMC is found at the Sn-9Zn-1.5Bi-0.5In-0.01P/Cu interface. The IMC grows slowly during thermal cycling. The fatigue life of the Sn-9Zn-1.5Bi-0.5In-0.01P solder joint is longer than that of Pb-Sn eutectic solder joint because the IMC thickness of the latter is much greater than that of the former. Thermodynamic and diffusivity calculations can explain the formation of γ-Cu₅Zn₈ instead of Cu-Sn IMCs. The growth of IMC layer is caused by the diffusion of Cu and Zn elements. The diffusion coefficient of Zn in the Cu₅Zn₈ layer is determined to be 1.10×10⁻¹² cm²/sec. A Zn-rich layer is found at the interface, which can prevent the formation of the more brittle Cu-Sn IMCs, slow down the growth of the IMC layer, and consequently enhance the fatigue life of the solder joint.     

Interfacial reaction between 42Sn-58Bi solder and electroless Ni-P/immersion Au under bump metallurgy during aging

The interfacial reaction between 42Sn-58Bi solder (in wt.% unless specified otherwise) and electroless Ni-P/immersion Au was investigated before and after thermal aging, with a focus on the formation and growth of an intermetallic compound layer, consumption of under bump metallurgy (UBM), and bump shear strength. The immersion Au layer with thicknesses of 0 μm (bare Ni), 0.1 μm, and 1 μm was plated on a 5-μm-thick layer of electroless Ni-P (with 14–15 at.% P). The 42Sn-58Bi solder balls were then fabricated on three different UBM structures by using screen printing and pre-reflow. A Ni₃Sn₄ layer formed at the joint interface after the pre-reflow for all three UBM structures. On aging at 125°C, a quaternary phase, identified as Sn₇₇Ni₁₅Bi₆Au₂, was observed above the Ni₃Sn₄ layer in the UBM structures that contain Au. The thick Sn₇₇Ni₁₅Bi₆Au₂ layer degraded the integrity of the solder joint, and the shear strength of the solder bump was about 40% less than the nonaged joints.     

Diffusion behavior of Cu in Cu/electroless Ni and Cu/electroless Ni/Sn-37Pb solder joints in flip chip technology

For Cu pads used as under bump metallization (UBM) in flip chip technology, the diffusion behavior of Cu in the metallization layer is an important issue. In this study, isothermal interdiffusion experiments were performed at 240°C for different times with solid-solid and liquid-solid diffusion couples assembled in Cu/electroless-Ni (Ni-10 wt.% P) and Cu/electroless Ni (Ni-10 wt.% P)/ Sn-37Pb joints. The diffusion structure and concentration profiles were examined by scanning electron microscopy and electron microprobe analysis. The interdiffusion fluxes of Cu, Ni and P were calculated from the concentration profiles with the aid of Matano plane evaluation. The values of J_Cu, J_Ni, and J_P decreased with increasing annealing time. The average effective interdiffusion coefficients on the order of 10⁻¹⁴ cm²/s were also evaluated within the diffusion zone. The amounts of Cu dissolved in the intermetallic compounds (IMCs) Ni₃Sn₄ and Ni₃P that precipitate after annealing the Cu/electroless Ni/Sn-37Pb joints were about 0.25 at.% and 0.5 at.%, respectively. For the short period of annealing, it appears that the presence of electroless Ni (EN) with the Sn-Pb soldering reaction assisted the diffusion of Cu through the EN layer.     

Reliability of adhesion strength of the Sn-9Zn-1.5Ag-0.5Bi/Cu during isothermal aging

The reliability of adhesion strength of the Sn-9Zn-1.5Ag-0.5Bi/Cu during isothermal aging has been investigated. Due to the growth and decomposition of the intermetallic compound (IMC), the adhesion strength varies with aging at 150°C from 100, 400, and 700–1,000 h as wetted at 250°C for 60 sec. The IMC layers are determined at the Sn-9Zn-1.5Ag-0.5Bi/Cu interface by an x-ray diffractometer (XRD), an optical microscope (OM), a scanning electron microscope (SEM), an energy-dispersive spectroscope (EDS), and a transmission electron microscope (TEM). The adhesion strength has been investigated by the pull-off test. The results show that the Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn IMCs are identified at the Sn-9Zn-1.5Ag-0.5Bi/Cu interface as aging. The adhesion strengths are 12.44±0.58, 8.57±0.43, 5.50±0.78, 4.32±0.78, and 3.32±0.43 MPa for aging times of 0 h, 100 h, 400 h, 700 h, and 1,000 h, respectively.     

Effect of reflow and thermal aging on the microstructure and microhardness of Sn-3.7Ag-xBi solder alloys

This work investigates the effect of reflow and the thermal aging process on the microstructural evolution and microhardness of five types of Sn-Ag based lead-free solder alloys: Sn-3.7Ag, Sn-3.7Ag-1Bi, Sn-3.7Ag-2Bi, Sn-3.7Ag-3Bi, and Sn-3.7Ag-4Bi. The microhardness and microstructure of the solders for different cooling rates after reflow at 250°C and different thermal aging durations at 150°C for air-cooled samples have been studied. The effect of Bi is discussed based on the experimental results. It was found that the microhardness increases with increasing Bi addition to Sn-3.7Ag solder regardless of reflow or thermal aging process. Scanning electron microscopy images show the formation of Ag₃Sn particles, Sn-rich phases, and precipitation of Bi-rich phases in different solders. The increase of microhardness with Bi addition is due to the solution strengthening and precipitation strengthening provided by Bi in the solder. The trend of decrease in microhardness with increasing duration of thermal aging was observed.     

Numerical prediction of fraction of eutectic phase in Sn−Ag−Cu soldring using the phase-field method

A combination of macroscale solidification simulation and phase-field calculation is employed to predict the volume fraction of the eutectic phase in Sn-4.0 mass% Ag-XCu solder alloys (X=0.5–1.1 mass%). The solidification simulation incorporates the cooling rate in the phase-field simulation. We assume the residual liquid solidifies as eutectic phase when the driving force for the nucleation of Cu₆Sn₅ amounts to a critical value, which is determined based on the experimental data. Though the calculation results depend on the experimental data, the obtained fractions are about 40% for 0.5 mass% Cu and more than 90% for 1.1 mass% Cu alloy, which shows good agreement with the experimental data.     

elemental redistribution and interfacial reaction mechanism for the flip chip Sn-3.0Ag-(0.5 or 1.5)Cu solder bump with Al/Ni(V)/Cu under-Bump metallization during aging

In flip chip technology, Al/Ni(V)/Cu under-bump metallization (UBM) is currently applicable for Pb-free solder, and Sn−Ag−Cu solder is a promising candidate to replace the conventional Sn−Pb solder. In this study, Sn-3.0Ag-(0.5 or 1.5)Cu solder bumps with Al/Ni(V)/Cu UBM after assembly and aging at 150°C were employed to investigate the elemental redistribution, and reaction mechanism between solders and UBMs. During assembly, the Cu layer in the Sn-3.0Ag-0.5Cu joint was completely dissolved into solders, while Ni(V) layer was dissolved and reacted with solders to form (Cu_1−y,Ni_y)₆Sn₅ intermetallic compound (IMC). The (Cu_1−y,Ni_y)₆Sn₅ IMC gradually grew with the rate constant of 4.63 × 10⁻⁸ cm/sec^0.5 before 500 h aging had passed. After 500 h aging, the (Cu_1−y,Ni_y)₆Sn₅ IMC dissolved with aging time. In contrast, for the Sn-3.0Ag-1.5Cu joint, only fractions of Cu layer were dissolved during assembly, and the remaining Cu layer reacted with solders to form Cu₆Sn₅ IMC. It was revealed that Ni in the Ni(V) layer was incorporated into the Cu₆Sn₅ IMC through slow solid-state diffusion, with most of the Ni(V) layer preserved. During the period of 2,000 h aging, the growth rate constant of (Cu_1−y,Ni_y)₆Sn₅ IMC was down to 1.74 × 10⁻⁸ cm/sec^0.5 in, the Sn-3.0Ag-1.5Cu joints. On the basis of metallurgical interaction, IMC morphology evolution, growth behavior of IMC, and Sn−Ag−Cu ternary isotherm, the interfacial reaction mechanism between Sn-3.0Ag-(0.5 or 1.5)Cu solder bump and Al/Ni(V)/Cu UBM was discussed and proposed.