Intermetallic reactions in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes

The intermetallic compounds (IMCs) formed during the reflow and aging of Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes were investigated. After reflow, the thickness of (Cu, Ni, Au)₆Sn₅ interfacial IMCs in Sn3Ag0.5Cu0.06Ni0.01Ge was similar to that in the Sn3Ag0.5Cu specimen. The interiors of the solder balls in both packages contained Ag₃Sn precipitates and brick-shaped AuSn₄ IMCs. After aging at 150°C, the growth thickness of the interfacial (Ni, Cu, Au)₃Sn₄ intermetallic layers and the consumption of the Ni surface-finished layer on Cu the pads in Sn3Ag0.5Cu0.06Ni0.01Ge solder joints were both slightly less than those in Sn3Ag0.5Cu. In addition, a coarsening phenomenon for AuSn₄ IMCs could be observed in the solder matrix of Sn3Ag0.5Cu, yet this phenomenon did not occur in the case of Sn3Ag0.5Cu0.06Ni0.01Ge. Ball shear tests revealed that the reflowed Sn3Ag0.5Cu0.06Ni0.01Ge packages possessed bonding strengths similar to those of the Sn3Ag0.5Cu. However, aging treatment caused the ball shear strength in the Sn3Ag0.5Cu packages to degrade more than that in the Sn3Ag0.5Cu0.06Ni0.01Ge packages.     

Intermetallic reactions in reflowed and aged Sn-9Zn solder ball grid array packages with Au/Ni/Cu and Ag/Cu pads

During the reflowing of Sn-9Zn solder ball grid array (BGA) packages with Au/Ni/Cu and Ag/Cu pads, the surface-finished Au and Ag film dissolved rapidly and reacted with the Sn-9Zn solder to form a γ₃-AuZn₄/γ-Au₇Zn₁₈ intermetallic double layer and ε-AgZn₆ intermetallic scallops, respectively. The growth of γ₃-AuZn₄ is prompted by further aging at 100°C through the reaction of γ-Au₇Zn₁₈ with the Zn atoms dissolved from the Zn-rich precipitates embedded in the β-Sn matrix of Sn-9Zn solder BGA with Au/Ni/Cu pads. No intermetallic compounds can be observed at the solder/pad interface of the Sn-9Zn BGA specimens aged at 100°C. However, after aging at 150°C, a Ni₄Zn₂₁ intermetallic layer is formed at the interface between Sn-9Zn solder and Ni/Cu pads. Aging the immersion Ag packages at 100°C and 150°C caused a γ-Cu₅Zn₈ intermetallic layer to appear between ε-AgZn₆ intermetallics and the Cu pad. The scallop-shaped ε-AgZn₆ intermetallics were found to detach from the γ-Cu₅Zn₈ layer and float into the solder ball. Accompanied with the intermetallic reactions during the aging process of reflowed Sn-9Zn solder BGA packages with Au/Ni/Cu and Ag/Cu pads, their ball shear strengths degrade from 8.6 N and 4.8 N to about 7.2 N and 2.9 N, respectively.     

Intermetallic reactions in Sn-3.5Ag solder ball grid array packages with Ag/Cu and Au/Ni/Cu pads

During the reflow process of Sn-3.5Ag solder ball grid array (BGA) packages with Ag/Cu and Au/Ni/Cu pads, Ag and Au thin films dissolve rapidly into the liquid solder, and the Cu and Ni layers react with the Sn-3.5Ag solder to form Cu₆Sn₅ and Ni₃Sn₄ intermetallic compounds at the solder/pad interfaces, respectively. The Cu₆Sn₅ intermetallic compounds also appear as clusters in the solder matrix of Ag surface-finished packages accompanied by Ag₃Sn dispersions. In the solder matrix of Au/Ni surface-finished specimens, Ag₃Sn and AuSn₄ intermetallics can be observed, and their coarsening coincides progressively with the aging process. The interfacial Cu₆Sn₅ and Ni₃Sn₄ intermetallic layers grow by a diffusion-controlled mechanism after aging at 100 and 150°C. Ball shear strengths of the reflowed Sn-3.5Ag packages with both surface finishes are similar, displaying the same degradation tendencies as a result of the aging effect.     

Characterizing metallurgical reaction of Sn3.0Ag0.5Cu composite solder by mechanical alloying with electroless Ni-P/Cu under-bump metallization after various reflow cycles

Electroless Ni-P/Cu under-bump metallization (UBM) is widely used in electronics packaging. The Sn3.0Ag0.5Cu lead-free composite solder pastes were produced by a mechanical alloying (MA) process doped with Cu₆Sn₅ nanoparticles. In this study, the detailed interfacial reaction of Sn3.0Ag0.5Cu composite solders with EN(P)/Cu UBM was investigated after reflow. A field-emission scanning electron microscope (FESEM) was employed to analyze the interfacial morphology and microstructure evolution. The intermetallic compounds (IMCs) formed at the interface between the Sn3.0Ag0.5Cu composite solders and EN(P)/Cu UBM after one and three reflows were mainly (Ni_1−x,Cu_x)₃Sn₄ and (Cu_1−y,Ni_y)₆Sn₅. However, only (Ni_1−x,Cu_x)₃Sn₄ IMC was observed after five reflows. The elemental distribution near the interfacial region was evaluated by an electron probe microanalyzer (EPMA) as well as field-emission electron probe microanalyzer (FE-EPMA). Based on the observation and characterization by FESEM, a EPMA, and an FE-EPMA, the reaction mechanism of interfacial phase transformation between Sn3.0Ag0.5Cu composite solders and EN(P)/Cu UBM after various reflow cycles was discussed and proposed.     

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.     

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.     

Abnormal growth of tin whiskers in a Sn3Ag0.5Cu0.5Ce solder ball grid array package

It has been discovered for the first time that Sn whiskers appeared in Sn3Ag0.5Cu0.5Ce solder joints of ball grid array (BGA) packages after storage at room temperature (natural aging) for less than 3 days and they grew at a high rate of 2.9 ?/sec. In one particular case, whiskers even formed after 1 day of storage at an extremely high growth rate of 8.6 ?/sec. Experimental investigations showed that a number of CeSn₃ clusters existed in the Sn3Ag0.5Cu0.5Ce solder matrix after the reflow process. Further natural aging in air for several days caused the CeSn₃ phases to oxidize rapidly, from which many Sn whiskers sprouted and grew to a length of hundreds of micrometers. The most commonly observed whiskers have been long fiber-shaped ones of 0.1 μm to 0.3 μm in diameter (type I), while short whiskers larger than 1 μm in diameter can also be found (type II). Here in our case, the surface oxide of the CeSn₃ phase possessed a higher content of Ce than of Sn, which implied that a Ce-depleted region (nearly of pure Sn) was left beneath the oxide layer. The abnormal whisker growth was attributed to the compressive stress squeezing the Sn atoms in the Ce-depleted region of CeSn₃ phase out of the oxide layer.     

Phase identification and growth kinetics of the intermetallic compounds formed during in-49Sn/Cu soldering reactions

For the application of In-49Sn solder in bonding recycled-sputtering targets to Cu back plates, the intermetallic compounds formed at the In-49Sn/Cu interface are investigated. Scanning electron microscopy (SEM) observations show that the interfacial intermetallics consist of a planar layer preceded by an elongated scalloped structure. Electron-probe microanalyzer analyses indicate that the chemical compositions of the planar layer and the scalloped structure are Cu_74.8In_12.2Sn_13.0 and Cu_56.2In_20.1Sn_23.7, respectively, which correspond to the ε-Cu₃(In,Sn) and η-Cu₆(In,Sn)₅ phases. Kinetics analyses show that the growth of both intermetallic compounds is diffusion controlled. The activation energies for the growth of η- and ε-intermetallics are calculated to be 28.9 kJ/mol and 186.1 kJ/mol. Furthermore, the formation mechanism of intermetallic compounds during the In-49Sn/Cu soldering reaction is clarified by marking the original interface with a Ta-thin film. Wetting tests are also performed, which reveal that the contact angles of liquid In-49Sn drops on Cu substrates decline to an equilibrium value of 25°C.     

Intermetallics Evolution in Sn-3.5Ag Based Lead-Free Solder Matrix on an OSP Cu Finish

The 0.2Co + 0.1Ni dual additives were used to dope a Sn-3.5Ag solder matrix to modify the alloy microstructure and the solder joint on an organic solderability preservative (OSP) Cu pad. The refined microstructure of the Sn-3.5Ag-0.2Co-0.1Ni solder alloy or the reduced β-Sn size was attributed to the depressed undercooling achieved by the Co-Ni addition. After soldering on the OSP Cu pad, a large Ag₃Sn plate was formed at the Sn-3.5Ag/OSP solder joint, whereas it was absent at the Sn-3.5Ag-0.2Co-0.1Ni/OSP solder joints. With isothermal aging at 150°C, large Ag₃Sn plates formed at the Sn-3.5Ag/OSP solder joint were still observed. A coarsened and dispersed Ag₃Sn phase was found in the solder joints with Co-Ni additions as well. Compared to Cu₆Sn₅, the (Co,Ni)Sn₂ intermetallic compound showed much lower microhardness values. However, (Co,Ni)Sn₂ hardness was comparable to that of the Ag₃Sn phase. Pull strength testing of Sn-3.5Ag-0.2Co-0.1Ni/OSP revealed slightly lower values than for Sn-3.5Ag/OSP during aging. Such results are thought be due to the phase transformation of (Co,Ni)Sn₂ to (Cu,Co,Ni)₆Sn₅.     

Sn3.8Ag0.7Cu和Sn37Pb焊点界面显微结构研究

利用扫描电子显微镜（SEM）和透射电子显微镜（TEM）研究了Sn3.8Ag0.7Cu（Sn37Pb）/Cu焊点在时效过程中的界面金属间化合物（IMC）形貌和成份。结果表明：150℃高温时效50、100、200、500h后,Sn3.8Ag0.7Cu（Sn37Pb）/Cu焊点界面IMC尺寸和厚度增加明显,IMC颗粒间的沟槽越来越小。50h时效后界面出现双层IMC结构,靠近焊料的上层为Cu6Sn5,邻近基板的下层为Cu3Sn。之后利用透射电镜观察了Sn37Pb/Ni和Sn3.8Ag0.7Cu/Ni样品焊点界面,结果显示,焊点界面清晰,IMC晶粒明显。     

电迁移对Sn3.0Ag0.5Cu无铅焊点剪切强度的影响

通过热风回流焊制备了Cu/Sn3.0Ag0.5Cu/Cu对接互连焊点,测试了未通电及6.5 A直流电下通电36 h和48 h后焊点的剪切强度.结果表明,电迁移显著地降低了焊点的剪切强度,电迁移36 h使剪切抗力降低约30%,电迁移48 h降低约50%.SEM观察断口和界面形貌表明,界面金属间化合物增厚使断裂由韧性向脆性...     

Mechanisms for interfacial reactions between liquid Sn-3.5Ag solders and cu substrates

Intermetallic compounds formed during the soldering reactions between Sn-3.5Ag and Cu at temperatures ranging from 250°C to 375°C are investigated. The results indicate that scallop-shaped η-Cu₆(Sn_0.933 Ag_0.007)₅ intermetallics grow from the Sn-3.5Ag/Cu interface toward the solder matrix accompanied by Cu dissolution. Following prolonged or higher temperature reactions, ɛ-Cu₃ (Sn_0.996 Ag_0.004) intermetallic layers appear behind the Cu₆(Sn_0.933 Ag_0.007)₅ scallops. The growth of these interfacial intermetallics is governed by a kinetic relation: ΔX=tⁿ, where the n values for η and ɛ intermetallics are 0.75 and 0.96, respectively. The mechanisms for such nonparabolic growth of interfacial intermetallics during the liquid/solid reactions between Sn-3.5Ag solders and Cu substrates are probed.     

Solid-state annealing behavior of two high-Pb solders, 95Pb5Sn and 90Pb10Sn,on Cu under bump metallurgy

The solid-state annealing behavior of two high-lead solders, 95Pb5Sn and 90Pb10Sn (in wt.%), was examined. After reflow, Cu₃Sn intermetallics formed on the Cu under bump metallurgy (UBM) for both solder alloys. However, solidstate annealing produced significantly different reaction morphologies for the two solder compositions. The Cu₃Sn intermetallics spalled off faster at higher temperatures in the 95Pb5Sn solder. In the case of 90Pb10Sn solder, the Cu₃Sn intermetallics continued to grow even after 1500 h at 170°C. The difference was explained by a two-step phenomenon—Sn diffusion from the bulk solder region to the solder/Cu₃Sn interface (J_Sn), and subsequent intermetallic formation (I_Cu3Sn) by interdiffusion of Cu and Sn. For 95Pb5Sn, the relation, J_Sn < I_Cu3Sn was postulated because of insufficient supply of Sn. The relation, J_Sn > I_Cu3Sn was suggested for the continuous intermetallic growth of the 90Pb10Sn solder. Although a small difference was expected between the two quantities in both solder alloys, the difference in the solid-state annealing behavior was dramatic.     

Interfacial microstructure between Sn-3Ag-xBi alloy and Cu substrate with or without electrolytic Ni plating

The microstructure of the interfacial phase of Sn-3Ag-xBi alloy on a Cu substrate with or without electrolytic Ni plating was evaluated. Bismuth additions into Sn-Ag alloys do not affect interfacial phase formations. Without plating, η-Cu₆Sn₅/ε-Cu₃Sn interfacial phases developed as reaction products in the as-soldered condition. The η-phase Cu₆Sn₅ with a hexagonal close-packed structure grows about 1-μm scallops. The ε-phase Cu₃Sn with an orthorhombic structure forms with small 100-nm grains between η-Cu₆Sn₅ and Cu. For Ni plating, a Ni₃Sn₄ layer of monoclinic structure formed as the primary reaction product, and a thin η-Ni₃Sn₂ layer of hexagonal close-packed structure forms between the Ni₃Sn₄ and Ni layer. In the Ni layer, Ni-Sn compound particles of nanosize distribute by Sn diffusion into Ni. On the total thickness of interfacial reaction layers, Sn-3Ag-6Bi joints are thicker by about 0.9 μm for the joint without Ni plating and 0.18 μm for the joint with Ni plating than Sn-3Ag joints, respectively. The thickening of interfacial reaction layers can affect the mechanical properties of strength and fatigue resistance.     

回流次数对Sn3.8Ag0.7Cu-xNi/Ni焊点的影响

研究了复合无铅焊料Sn3.8Ag0.7Cu-xNi(x=0.5,1.0,2.0)与Au/Ni/Cu焊盘在不同回流次数下形成的焊点的性能.结果表明,Ni颗粒增强的复合焊料具有良好的润湿性能,熔点小于222℃;X为0.5的焊料界面IMC由针状(CuNi)6Sn5演化为双层IMC,即多面体状化合物(CuNi)6Sn5和回飞棒...     

Effects of Co Alloying and Size on Solidification and Interfacial Reactions in Sn-57 wt.%Bi-(Co)/Cu Couples

Solidification and interfacial reactions in Sn-57 wt.%Bi-(Co)/Cu couples are investigated. The addition of 0.05 wt.% Co and 0.5 wt.% Co and changes between 2 g and 20 mg solder sizes have no significant effects on the undercooling of Sn-57 wt.%Bi solders. Both η-Cu₆Sn₅ and ε-Cu₃Sn phases are formed in Sn-57 wt.%Bi/Cu couples reacted at 80°C, 100°C, and 100°C, whereas only η-Cu₆Sn₅ is formed at 160°C. The formation of ε-Cu₃Sn is suppressed and only η-Cu₆Sn₅ is found in the couple with 0.05 wt.% Co and 0.5 wt.% Co addition in Sn-57 wt.%Bi solder. Both the growth rate of η-Cu₆Sn₅ and the dissolution rate of the Cu substrate increase with Co addition. The morphology of η-Cu₆Sn₅ is also altered with Co addition, becoming a porous structure with solder trapped in the voids.     

镧对Sn3.5Ag0.5Cu钎料组织性能影响

运用莱卡显微镜、扫描电镜和能谱分析等手段,研究了稀土元素La的添加量对Sn3.5Ag0.5Cu钎料及其与Cu基体焊接后微观组织及性能的影响。结果表明:添加不同含量的稀土La均能使钎料及其与Cu基体焊接后组织与性能得到改善,其中以w(La)达到0.05%时为最优,显微硬度及剪切强度分别提高14%和10.7%。键参数函数计算结果表明La具有"亲Sn"倾向,可细化钎料组织,降低IMC(界面金属间化合物)的长大驱动力。     

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.     

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.     

Interfacial microstructure and bonding strength of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder BGA packages with immersion Ag surface finish

Although it has been verified that tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder, no detailed studies have been conducted on interfacial reactions and mechanical properties of Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with an immersion Ag surface finish. The intermetallic compounds formed during the reflow and aging of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder ball grid array (BGA) packages were investigated. Because more heterogeneous nucleation sites, provided by CeSn₃ intermetallics and Zn atoms, formed in the Sn-3Ag-0.5Cu-0.5Ce-xZn solder matrix, and Cu and Zn have a stronger affinity than Cu and Sn, the Cu-Sn intermetallics growth in Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with Ag/Cu pads was suppressed. The 0.2% Zn addition for inhibiting rapid whisker growth in RE-doped Sn-Ag-Cu solder joints is more appropriate than 0.5 wt.% additions, as excess Zn addition causes poor oxidation resistance and inferior bonding strength.