Effect of reaction time on mechanical strength of the interface formed between the Sn-Zn(-Bi) solder and the Au/Ni/Cu bond pad

In this work, the shear strengths and the interfacial reactions of Sn-9Zn, Sn-8Zn-1Bi, and Sn-8Zn-3Bi (wt.%) solders with Au/Ni/Cu ball grid array (BGA) pad metallization were systematically investigated after extended reflows. Zn-containing Pb-free solder alloys were kept in molten condition (240°C) on the Au/electrolytic Ni/Cu bond pads for different time periods ranging from 1 min. to 60 min. to render the ultimate interfacial reaction and to observe the consecutive shear strength. After the shear test, fracture surfaces were investigated by scanning electron microscopy equipped with an energy dispersive x-ray spectrometer. Cross-sectional studies of the interfaces were also conducted to correlate with the fracture surfaces. The solder ball shear load for all the solders during extended reflow increased with the increase of reflow time up to a certain stage and then decreased. It was found that the formation of thick Ni-Zn intermetallic compound (IMC) layers at the solder interface of the Au/electrolytic Ni/Cu bond pad with Sn-Zn(-Bi) alloys deteriorated the mechanical strength of the joints. It was also noticed that the Ni-Zn IMC layer was larger in the Sn-Zn solder system than that in the other two Bi-containing solder systems.     

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.     

Intermetallic reactions in Sn-8Zn-20In solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflow process of Sn-8Zn-20In solder joints in the ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the Au and Ag thin films react with liquid solder to form γ₃-AuZn₄/γ-Au₇Zn₁₈ and ε-AgZn₆ intermetallics, respectively. The γ₃/γ intermetallic layer is prone to floating away from the solder/Ni interface, and the appearance of any interfacial intermetallics cannot be observed in the Au/Ni surface finished Sn-8Zn-20In packages during further aging treatments at 75°C and 115°C. In contrast, ε-CuZn₅/γ-Cu₅Zn₈ intermetallics are formed at the aged Sn-8Zn-20In/Cu interface of the immersion Ag BGA packages. Bonding strengths of 3.8N and 4.0N are found in the reflowed Sn-8Zn-20In solder joints with Au/Ni/Cu and Ag/Cu pads, respectively. Aging at 75°C and 115°C gives slight increases of ball shear strength for both cases.     

Properties of quad flat package joints using Sn-Zn-Bi solder with varying lead-plating materials

The effects of plating materials (Sn-10Pb, Sn-3.5Ag, Sn-3Bi, Sn-0.7Cu, and Au/Pd/Ni) on Cu leads on quad flat package (QFP) joints using a Sn-8Zn-3Bi solder were investigated. The joints with Sn-3.5Ag plating and Sn-8Zn-3Bi solder had the slowest growth rate of interfacial reaction layers and the highest strength. The Ag dissolution into the interfacial reaction layers causes this increased strength. The Sn-Ag plating is the best plating material for Cu leads among the five kinds of plating using Sn-8Zn-3Bi solder.     

Interfacial reaction studies on lead (Pb)-free solder alloys

Recently, the research and development activities for replacing Pb-containing solders with Pb-free solders have been intensified due to both competitive market pressures and environmental issues. As a result of these activities, a few promising candidate solder alloys have been identified, mainly, Sn-based alloys. A key issue affecting the integrity and reliability of solder joints is the interfacial reactions between a molten solder and surface finishes in the solder joint structures. In this paper, a fundamental study of the interfacial reactions between several Pb-free candidate solders and surface finishes commonly used in printed-circuit cards is reported. The Pb-free solders investigated include Sn-3.5 Ag, Sn-3.8 Ag-0.7 Cu, and Sn-3.5 Ag-3.0 Bi. The surface finishes investigated include Cu, Au/Ni(P), Au/Pd/Ni(P), and Au/Ni (electroplated). The reaction kinetics of the dissolution of surface finishes and intermetallic compound growth have been measured as a function of reflow temperature and time. The intermetallic compounds formed during reflow reactions have been identified by SEM with energy dispersive x-ray spectroscopy.     

Interfacial microstructure and strength of lead-free Sn-Zn-RE BGA solder bumps

Rare earth (RE) elements, primarily La and Ce, were doped in Sn-Zn solder to improve its properties such as wettability. The interfacial microstructure evolution and shear strength of the Sn-9Zn and Sn-9Zn-0.5RE (in wt%) solder bumps on Au/Ni/Cu under bump metallization (UBM) in a ball grid array (BGA) were investigated after thermal aging at 150 /spl deg/C for up to 1000 h. In the as-reflowed Sn-9Zn solder bump, AuSn/sub 4/ intermetallic compounds (IMCs) and Au-Zn circular IMCs formed close to the solder/UBM interface, together with the formation of a Ni-Zn-Sn ternary IMC layer of about 1 /spl mu/m in thickness. In contrast, in the as-reflowed Sn-9Zn-0.5RE solder bump, a spalled layer of Au-Zn was formed above the Ni layer. Sn-Ce-La and Sn-Zn-Ce-La phases were found near the interface at positions near the surface of the solder ball. Upon thermal aging at 150 /spl deg/C, the concentration of Zn in the Ni-Zn-Sn ternary layer of Sn-9Zn increased with aging time. For Sn-9Zn-0.5RE, the Au-Zn layer began to dissolve after 500 h of thermal aging. The shear strength of the Sn-9Zn ball was decreased after the addition of RE elements, although it was still higher than that of the Sn-37Pb and Sn-36Pb-2Ag Pb-bearing solders. The fracture mode of the Sn-9Zn system was changed from ductile to partly brittle after adding the RE elements. This is mainly due to the presence of the brittle Au-Zn layer.     

Comparison of electroplated eutectic Bi/Sn and Pb/Sn solder bumpson various UBM systems

The effect of a reflow process and under bump metallurgy (UBM) systems on the growth of intermetallic compounds (IMC) of the 57Bi/43Sn and 37Pb/63Sn solder bump/UBM interfaces was investigated. The selected UBM systems were sputtered Al/Ti/Cu, sputtered Al/NiV/Cu, Al/electroless Ni/immersion Au, and Al/Ti/electroless Cu. An alloy electroplating method was used for the solder bumping process. The microstructure and composition of intermetallic compound (IMC) phases and their morphologies were examined using scanning electron microscopy and X-ray diffraction. The Cu₆Sn₅ η'-phase IMC appeared on all Cu containing UBM cases with Pb/Sn and Bi/Sn solders and the Cu ₃Sn ϵ-phase was detected only with Pb/Sn solder bumps. The Ni₃Sn₄ IMC was found to be the main IMC phase between Ni and solder. The Ni₃Sn secondary IMC was also detected on the electroless Ni UBM with PbSn solder after ten times reflow. Through the bump shear test, Al/NiV/Cu, Al/elNi/Au, and Al/Ti/elCu UBMs showed good stability with Bi/Sn and Pb/Sn solder in terms of metallurgical aspects     

Interfacial reaction and microstructural evolution for electroplated Ni and electroless Ni in the under bump metallurgy with 42Sn58Bi solder during annealing

In the present study, several under bump metallization (UBM) schemes using either electroplated Ni or electroless Ni (EN) as the solderable layer are investigated. The EN and electroplated Ni are first deposited on Cu/Al₂O₃ substrates, followed by electroplating of thin gold coatings. Joints of 42Sn-58Bi/Au/EN/Cu/Al₂O₃ and 42Sn-58Bi/Au/Ni/Cu/Al₂O₃ are annealed at 145 C and 185CC for 30–180 minutes to investigate the interfacial reaction between the solder and metallized substrates. For 42Sn-58Bi/Au/Ni-5.5wt.%P/Cu/Al₂O₃, 42Sn-58Bi/Au/Ni-12.1wt.%P/Cu/Al₂O₃, and 42Sn-58Bi/Au/Ni/CU/Al₂O₃ joints annealed at 145 C, only Ni₃Sn₄ intermetallic compound (IMC) formed at the solder/EN interace. When annealed at an elevated temperature of 185 C, plate-like Ni₃Sn₄ IMC forms at the solder/Ni-5.5wt.%P interface, while a trace of (Ni, Cu)₃Sn₄ IMC is observed at the solder/Ni-12.1wt.%P interface and within the solder region. For the electroplated Ni-based multi-metallization substrate, the Ni₃Sn₄ IMC is present at the solder/Ni interface during annealing at 185 C for a short period of time. In the 42Sn-58Bi/Au/EN/Cu/Al₂O₃ joint, the EN spalls off the EN layer and migrates into the solder region when annealed at 185 C. The interface of the solder/electroplating Ni becomes saw-toothed as the annealing temperature is raised to 185 C. In addition, an enrichment of phosphorus is observed at the interface of the Ni-Sn IMC and EN.     

Effect of Cr additions on interfacial reaction between the Sn-Zn-Bi solder and Cu/electroplated Ni substrates

Intermetallic compounds (IMCs) growth on the Sn-8Zn-3Bi (-Cr) solder joints with Cu and electroplated Ni substrates was investigated after aging at 150 °C. It was found that the IMCs were the Cu₅Zn₈ and Ni₅Zn₂₁ at the solder/Cu and solder/Ni interface, respectively. The IMCs growth rate at the Sn-8Zn-3Bi-Cr/Cu and Ni interface was slower than that at Sn-8Zn-3Bi/Cu interface (about 1/2 times) and Sn-8Zn-3Bi/Ni interface (about 1/4 times) during aging. The reason may be that Cr reacts with Zn and forms the Sn-Zn-Cr phase which block the diffusion of Zn atom to the interface and slow down the IMCs growth rate.     

Compound formation for electroplated Ni and electroless Ni in the under-bump metallurgy with Sn-58Bi solder during aging

The Ni-based under-bump metallurgies (UBMs) are of interest because they have a slower reaction rate with Sn-rich solders compared to Cu-based UBMs. In this study, several UBM schemes using Ni as the diffusion barrier are investigated. Joints of Sn-58Bi/Au/electroless nickel (EN)/Cu/Al₂O₃ and Sn-58Bi/Au/electroplated nickel/Cu/Al₂O₃ were aged at 110°C and 130°C for 1–25 days to study the interfacial reaction and microstructural evolution. The Sn-Bi solder reacts with the Ni-based multimetallization and forms the ternary Sn-Ni-Bi intermetallic compound (IMC) during aging at 110°C. Compositions of ternary IMC were (78–80)at.%Sn-(12–16)at.%Ni-(5–8)at.%Bi in joints of Sn-58Bi/Au/Ni-5.5wt.%P/Cu, Sn-58Bi/Au/Ni-12wt.%P/Cu, and Sn-58Bi/Au/Ni/Cu. Elevated aging at 130°C accelerates the IMC growth rate and results in the formation of (Ni,Cu)₃Sn₄ and (Cu,Ni)₆Sn₅ adjacent to the ternary Sn-Ni-Bi IMC for the Sn-58Bi/Au/Ni-12wt.%P/Cu and Sn-58Bi/Au/Ni/Cu joints, respectively. The Cu content in the (Cu,Ni)₆Sn₅ IMC is six times that in (Ni,Cu)₃Sn₄. Electroplated Ni fails to prevent Cu diffusion toward the Ni/solder interface as compared to EN-based joints. Cracks are observed in the Sn-58Bi/Au/Ni-5.5wt.%P/Cu/Al₂O₃ joint aged at 130°C for 25 days. It is more favorable to employ Ni-12wt.%P for the Sn-58Bi/Au/EN/Cu joint. Electroless nickel, with the higher P content of 12 wt.%, is a more effective diffusion barrier during aging. In addition, P enrichment occurs near the interface of the EN/solder, and the degree of P enrichment is enhanced with aging time. The Au(Sn,Bi)₄, with pyramidal and cubic shape, is observed in the Sn-58Bi/Au/Ni/Cu/Al₂O₃ joint.     

The interfacial reaction between Sn-Zn-Ag-Ga-Al solders and metallized Cu substrates

The interfacial interaction between the Sn-8.55Zn-0.5Ag-0.5Ga-0.1Al solder and three kinds of metallized substrates (Cu, Cu/Au, and Cu/Ni-P/Au) does not form the Cu-Sn intermetallic compound (IMC). Continuous Cu-Zn and discontinuous Ag-Zn interfacial IMC layers formed between the Cu and Sn-Zn-Ag-Ga-Al solder, while Cu-Zn and Au-Al-Zn IMCs formed on the Cu/Au substrate. Only the Au-Al-Zn IMC formed at the interface when the electroless Ni-P deposit was the diffusion barrier between Cu and the Au surface layer.     

Interfacial microstructure evolution in Pb-free solder systems

The Sn-3.5Ag and Sn-3.0Ag-0.5Cu ball-grid-array solder balls bonded onto Ni/Au metallization exhibited different interfacial morphology after both wetting and solid-state reactions. In contrast to the eutectic-SnPb solder system, both Pb-free systems showed higher solder-ball shear strength after annealing. Reprecipitation of Au as (Au,Ni)Sn₄ at the interface, as shown in the eutectic-SnPb solder system, was not observed in both Pb-free solder systems. Instead, Ni₃Sn₄ and Cu-Sn-Ni-Au intermetallic compounds (IMCs) were found in the SnAg and SnAgCu systems, respectively. In the SnAgCu system, a thick, acicular-Cu-Sn-Ni IMC formed after wetting, but a faceted-Cu-Sn-Ni-Au phase was found with longer annealing. The growth of this interfacial phase in the Sn-3.0Ag-0.5Cu solder system was also slightly inhibited by the addition of Cu, with a formation energy of about 200 kJ/mol.     

Studies of the mechanical and electrical properties of lead-free solder joints

The mechanical and electrical properties of several Pb-free solder joints have been investigated including the interfacial reactions, namely, the thickness and morphology of the intermetallic layers, which are correlated with the shear strength of the solder joint as well as its electrical resistance. A model joint was made by joining two “L-shaped” copper coupons with three Pb-free solders, Sn-3.5Ag (SA), Sn-3.8Ag-0.7Cu (SAC), and Sn-3.5Ag-3Bi (SAB) (all in wt.%), and combined with two surface finishes, Cu and Ni(P)/Au. The thickness and morphology of the intermetallic compounds (IMCs) formed at the interface were affected by solder composition, solder volume, and surface finish. The mechanical and electrical properties of Pb-free solder joints were evaluated and correlated with their interfacial reactions. The microstructure of the solder joints was also investigated to understand the electrical and mechanical characteristics of the Pb-free solder joints.     

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.     

Interfacial reaction and joint reliability of fine-pitch flip-chip solder bump using stencil printing method

This study was focused on the formation and reliability evaluation of solder joints with different diameters and pitches for flip chip applications. We investigated the interfacial reaction and shear strength between two different solders (Sn-37Pb and Sn-3.0Ag-0.5Cu, in wt.%) and ENIG (Electroless Nickel Immersion Gold) UBM (Under Bump Metallurgy) during multiple reflow. Firstly, we formed the flip chip solder bumps on the Ti/Cu/ENIG metallized Si wafer using a stencil printing method. After reflow, the average solder bump diameters were about 130, 160 and 190 μm, respectively. After multiple reflows, Ni₃Sn₄ intermetallic compound (IMC) layer formed at the Sn-37Pb solder/ENIG UBM interface. On the other hand, in the case of Sn-3.0Ag-0.5Cu solder, (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄ IMCs were formed at the interface. The shear force of the Pb-free Sn-3.0Ag-0.5Cu flip chip solder bump was higher than that of the conventional Sn-37Pb flip chip solder bump.     

回流焊对SnAgCuBi/Cu焊点IMC及剪切强度的影响

利用金相显微镜和扫描电镜对多次回流焊后的Sn-0.3Ag-0.7Cu-xBi/Cu焊点IMC和剪切断口形貌进行了观察和分析。结果表明:Bi的加入提高了接头剪切强度,且随着Bi含量的增加而增加,当w(Bi)为4.5%时达最大值45.07MPa,同时Bi的加入有效抑制了焊点IMC的增长。经过5次回流焊后,未加入Bi的焊点剪切强度由24.55MPa下降到20.82MPa,而加入w(Bi)为3.0%的焊点剪切强度由35.95MPa下降到32.46MPa。     

Interfacial reactions and shear strengths between Sn-Ag-based Pb-free solder balls and Au/EN/Cu metallization

The morphological and compositional evolutions of intermetallic compounds (IMCs) formed at three Pb-free solder/electroless Ni-P interface were investigated with respect to the solder compositions and reflow times. The three Pb-free solder alloys were Sn3.5Ag, Sn3.5Ag0.75Cu, and Sn3Ag6Bi2In (in wt.%). After reflow reaction, three distinctive layers, Ni₃Sn₄ (or Ni-Cu-Sn for Sn3.5Ag0.75Cu solder), NiSnP, and Ni₃P, were formed on the electroless Ni-P layer in all the solder alloys. For the Sn3.5Ag0.75Cu solder, with increasing reflow time, the interfacial intermetallics switched from (Cu,Ni)₆Sn₅ to (Cu,Ni)₆Sn₅+(Ni,Cu)₃Sn₄, and then to (Ni,Cu)₃Sn₄ IMCs. The degree of IMC spalling for the Sn3.5Ag0.75Cu solder joint was more than that of other solders. In the cases of the Sn3.5Ag and Sn3Ag6Bi2In solder joints, the growth rate of the Ni₃P layer was similar because these two type solder joints had a similar interfacial reaction. On the other hand, for the Sn3.5Ag0.75Cu solder, the thickness of the Ni₃P and Ni-Sn-P layers depended on the degree of IMC spalling. Also, the shear strength showed various characteristics depending on the solder alloys and reflow times. The fractures mainly occurred at the interfaces of Ni₃Sn₄/Ni-Sn-P and solder/Ni₃Sn₄.     

Reaction characteristics of the In-15Pb-5Ag solder with a Au/Ni/Cu pad and their effects on mechanical properties

Reaction characteristics of the In-15Pb-5Ag (wt.%) solder with a Au/Ni/Cu pad during reflow soldering and aging treatment were examined. Interfacial reaction during reflow resulted in either an AuIn₂ or Ni₂₈In₇₂ layer, depending on reflow time. The AuIn₂ layer became thinner and disappeared from the interface, and only the Ni₂₈In₇₂ layer grew with the progress of aging treatment at 130°C. Based on those observations, the dissolution rate of the Au top layer was estimated, and the behavior of the AuIn₂ layer during reflow and aging treatment was discussed. In addition, peak shear load and fracture energy of the solder bump were measured as a function of reflow time and aging treatment. The results were compared with those measured with the Sn-37Pb solder bump.     

SnAgCu系钎料的合金组织和力学性能

研究了Cu含量对SnAgCu系钎料合金显微组织及其与化学镀Ni基板钎焊接头力学性能的影响。结果表明:高Cu含量SnAgCu合金会产生较多的(CuxNi1-x)6Sn5金属间化合物,从而减少镀Ni层的消耗,进一步提高钎焊接头的剪切强度。与Sn-3.0Ag-0.3Cu相比,Sn-3.0Ag-1.0Cu钎焊接头剪切强度提高了6.78%。经过150℃时效1000h后,界面Ni3(P,Sn)层的增长率从Sn-3.0Ag-0.3Cu合金的约66%降低到Sn-3.0Ag-1.0Cu合金的约40%。     

Intermetallic Reactions in Sn-0.4Co-0.7Cu Solder BGA Packages with an ENIG Surface Finish

As-cast Sn-0.4Co-0.7Cu solder contains both (Cu_0.98Co_0.02)₆Sn₅ and (Co_0.85Cu_0.15) Sn₃ intermetallic phases in the matrix. After reflowing, the Au thin film in the electroless Ni/immersion Au (ENIG) surface-finished Sn-0.4Co-0.7Cu solder ball grid array (BGA) packages dissolved rapidly into the solder matrix to form AuSn₄ intermetallics, and a thin layer of (Cu_0.57Ni_0.35Au_0.08)₆Sn₅ intermetallic compound appeared at the solder/pad interface, growing very slowly during aging at 100°C. Increasing the aging temperature to 150°C caused the formation of a new intermetallic layer, (Ni_0.79Cu_0.21)₃Sn₄, at the (Cu_0.57Ni_0.35Au_0.08)₆Sn₅/Ni interface. The reflowed Sn-0.4Co-0.7Cu BGA packages have a ball shear strength of 6.8 N, which decreases to about 5.7 N and 5.5 N after aging at 100°C and 150°C, respectively. The reflowed and aged solder joints fractured across the solder balls with ductile characteristics in ball shear tests.