Inhibition of Whisker Growth on the Surface of Sn-3Ag-0.5Cu-0.5Ce Solder Alloyed with Zn

Solder alloys doped with rare-earth elements have been reported to show many beneficial effects. However, tin whiskers have been observed to appear on the surface of Sn-3Ag-0.5Cu-0.5Ce solder joints after air exposure for short periods. Such a phenomenon of abnormal whisker growth may significantly degrade the reliability of electronic packaging. The present study shows that the tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder. The inhibition effect on the whisker growth is correlated to the refining of (Ce_0.9Zn_0.1)Sn₃ intermetallics in this Sn-3Ag-0.5Cu-0.5Ce-0.5Zn alloy.     

Effects of Ce Addition on the Microstructure and Mechanical Properties of Sn-58Bi Solder Joints

The effects of a rare-earth element on the microstructure, mechanical properties, and whisker growth of Sn-58Bi alloys and solder joints in ball grid array (BGA) packages with Ag/Cu pads have been investigated. Mechanical testing indicated that the elongation of Sn-58Bi alloys doped with Ce increased significantly, and the tensile strength decreased slightly, in compar- ison with undoped Sn-58Bi. In addition, the growth of both fiber- and hillock-shaped tin whiskers on the surface of Sn-58Bi-0.5Ce was retarded in the case of Sn-3Ag-0.5Cu-0.5Ce alloys. The growth of interfacial intermetallic compounds (IMC) in Sn-58Bi-0.5Ce solder joints was slower than that in Sn-58Bi because the activity of Ce atoms at the interface of the Cu₆Sn₅ IMC/solder was reduced. The reflowed Sn-58Bi and Sn-58Bi-0.5Ce BGA packages with Ag/Cu pads had a ball shear strength of 7.91 N and 7.64 N, which decreased to about 7.13 N and 6.87 N after aging at 100°C for 1000 h, respectively. The reflowed and aged solder joints fractured across the solder balls with ductile characteristics after ball shear tests.     

Oxidation-Induced Whisker Growth on the Surface of Sn-6.6(La,Ce) Alloy

During solidification of rare-earth (RE)-containing Sn-6.6(La, Ce) alloys, (La_0.93Ce_0.07)Sn₃ intermetallic clusters form in the near β-Sn matrix. These (La_0.93Ce_0.07)Sn₃ intermetallics oxidize predominately after air storage at room temperature for short time periods. Accompanying the oxidation reaction, tin sprouts appear on the outer surface of the intermetallic clusters. Increasing the storage time at room temperature leads to the formation of thread-like tin whiskers. In specimens stored at 150°C in an air furnace, only a small amount of tin sprouts can be found in the interior regions of the oxidized (La_0.93Ce_0.07)Sn₃ intermetallics. However, many coarse tin hillocks formed around the intermetallic clusters. The driving force for whisker growth is the compressive stress induced by the volume expansion of (La_0.93 Ce_0.07)Sn₃, which extrudes the tin atoms released by the oxidation reaction of these RE intermetallics. In addition, the huge compressive stress accumulated by the volume expansion of the drastically oxidized RE intermetallics during 150°C air storage extrudes the Sn-6.6(La, Ce) matrix around the RE oxides to form the coarse hillocks.     

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.     

Interfacial Reactions of Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Cu (<Emphasis Type="Italic">x</Emphasis> = 1, 4, 7, 10) Solders with Ni Substrates

This study investigates the effects of various reaction times and Cu contents on the interfacial reactions between Sn-9Zn-xCu alloys and Ni substrates. After aging at 255°C for 1 h to 3 h, the Ni₅Zn₂₁ and Cu₅Zn₈ phases formed at the interface of Sn-9Zn/Ni and Sn-9Zn-1wt.%Cu/Ni couples, respectively. The (Ni,Zn)₃Sn₄ phase was found in the Sn-9Zn-4wt.%Cu/Ni couple, and the (Cu,Ni)₆Sn₅ and Cu₆Sn₅ phases formed, respectively, in the Sn-9Zn-7wt.%Cu/Ni and Sn-9Zn-10wt.%Cu/Ni couples. As the reaction time was increased from 5 h to 24 h, the (Cu₅Zn₈ + Ni₅Zn₂₁) phases replaced the Cu₅Zn₈ phase to form in the Sn-9Zn-1wt.%Cu/Ni couple; the (Ni,Zn)₃Sn₄ phase formed in the Sn-9Zn-4wt.%Cu/Ni couple, and (CuZn + Cu₆Sn₅) formed in the Sn-9Zn-10wt.%Cu alloys. Experimental results indicate that intermetallic compound (IMC) formation in Sn-9Zn-xCu/Ni couples changes dramatically with reaction time and Cu content. The Sn-Zn-Ni, Sn-Cu-Ni, and Sn-Zn-Cu ternary isothermal sections greatly help us to understand the IMC evolutions in the Sn-9Zn-xCu/Ni couples.     

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.     

Electrochemical Properties of Joints Formed Between Sn-9Zn-1.5Ag-1Bi Alloys and Cu Substrates in a 3.5 wt.% NaCl Solution

The electrochemical properties of the joints formed between Sn-9Zn-1.5Ag-1Bi alloys and Cu substrates in a 3.5 wt.% NaCl solution have been investigated by potentiodynamic polarization, X-ray diffraction, and scanning electron microscopy. For the Sn-9Zn-1.5Ag-1Bi/Cu joints in a 3.5 wt.% NaCl solution, corrosion current (I _corr), corrosion potential (E _corr) and corrosion resistance (R _p) are 2.46 × 10⁻⁶ A/cm², −1.18 V, and 7.54 × 10³ Ωcm², respectively. Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn are formed at the interface between the Sn-9Zn-1.5Ag-xBi solder alloy and Cu substrate. The corrosion products of ZnCl₂, SnCl₂ and ZnO are formed at the Sn-9Zn-1.5Ag-xBi/Cu joints after polarization in a 3.5 wt.% NaCl solution. Pits are also formed on the surface of the solder alloys.     

Intermetallic compounds and adhesion strength between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder and unfluxed Cu substrate

The intermetallic compounds (IMCs) formed at the interface between the Sn-9Zn-1.5Ag-0.5Bi lead-free solder alloy and unfluxed Cu substrate have been investigated by x-ray diffraction, optical microscopy, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The melting point and melting range of the Sn-9Zn-1.5Ag-0.5Bi solder alloy are determined as 195.9°C and 10°C, respectively, by differential scanning calorimetry (DSC). Cu₆Sn₅ and Cu₅Zn₈ IMCs are formed between the Sn-9Zn-1.5Ag-0.5Bi/unfluxed Cu substrate wetted at 250°C for 10 sec. The interfacial adhesion strength changes from 10.27±0.68 MPa to 8.58±0.59 MPa when soldering time varies from 10 sec to 30 sec at 250°C.     

Intermetallic compounds formed during the reflow and aging of Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder ball grid array packages

After reflow of Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder balls on Au/Ni surface finishes in ball grid array (BGA) packages, scallop-shaped intermetallic compounds (Cu_0.70Ni_0.28Au_0.02)₆Sn₅ (IM1a) and (Cu_0.76Ni_0.24)₆(Sn_0.86In_0.14)₅ (IM1b), respectively, appear at the interfaces. Aging at 100°C and 150°C for Sn-3.8Ag-0.7Cu results in the formation of a new intermetallic phase (Cu_0.70Ni_0.14Au_0.16)₆Sn₅ (IM2a) ahead of the former IM1a intermetallics. The growth of the newly appeared intermetallic compound, IM2a, is governed by a parabolic relation with an increase in aging time, with a slight diminution of the former IM1a intermetallics. After prolonged aging at 150°C, the IM2a intermetallics partially spall off and float into the solder matrix. Throughout the aging of Sn-20In-2Ag-.5Cu solder joints at 75°C and 115°C, partial spalling of the IM1b interfacial intermetallics induces a very slow increase in thickness. During aging at 115°C for 700 h through 1,000 h, the spalled IM1b intermetallics in the solder matrix migrate back to the interfaces and join with the IM1b interfacial intermetallics to react with the Ni layers of the Au/Ni surface finishes, resulting in the formation and rapid growth of a new (Ni_0.85Cu_0.15)(Sn_0.71In_0.29)₂ intermetallic layer (IM2b). From ball shear tests, the strengths of the Sn-3.8Ag-0.7Cu and Sn-20In-2Ag-0.5Cu solder joints after reflow are ascertained to be 10.4 N and 5.4 N, respectively, which drop to lower values after aging. An erratum to this article is available at .     

Selective formation of intermetallic compounds in Sn-20In-0.8Cu ball grid array solder joints with Au/Ni surface finishes

After Sn-20In-0.8Cu solder balls are reflowed on a ball grid array (BGA) substrate (substrate A) with an Au/Ni surface finish, scallop-shaped intermetallic compounds with a composition of 0.83[Cu₆(Sn_0.87In_0.13)₅] + 0.17[Ni₃(Sn_0.87In_0.13)₄] are formed at the solder/pad interface. The distribution of the intermetallics is not altered by gravity or by multiple reflows of the solder joints. As another substrate (substrate B) is further attached onto the primary reflowed BGA assembly to form a sandwich structure subjected to subsequent multiple reflows, the Cu₆(Sn_0.87In_0.13)₅ interfacial intermetallic scallops remain still on the side of substrate A while many Au(In_0.91Sn_0.09)₂ intermetallics of cubic shape appear near the solder/Ni interface on the side of substrate B. When the Sn-20In-0.8Cu solder balls are assembled simultaneously in between two substrates (A and B), Au(In_0.91Sn_0.09)₂ intermetallic cubes of equal proportion are observed to form on both sides of the assembly. In summarizing the results, it is proposed that the diffusion of Cu atoms in the Sn-20In-0.8Cu solder toward the Ni layers after Au thin-film dissolution on Au/Ni surface finishes led to the formation of Cu₆(Sn_0.87Zn_0.17)₅ intermetallic compounds, which prevailed over the gravitational effect so that no intermetallic sedimentation in the liquid solder would occur. The appearance of Au(In_0.91Sn_0.09)₂ at the Ni/Sn-20In-0.8Cu interfaces was hindered by the preferential formation of Cu₆(Sn_0.87Zn_0.17)₅ until the Cu atoms in the Sn-20In-0.8Cu solder matrix were consumed to a lower content via the attachment of a second substrate to the assembly.     

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.     

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.     

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-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.     

Investigation of Dissolution Behavior of Metallic Substrates and Intermetallic Compound in Molten Lead-free Solders

This study investigates the dissolution behavior of the metallic substrates Cu and Ag and the intermetallic compound (IMC)-Ag₃Sn in molten Sn, Sn-3.0Ag-0.5Cu, Sn-58Bi and Sn-9Zn (in wt.%) at 300, 270 and 240°C. The dissolution rates of both Cu and Ag in molten solder follow the order Sn > Sn-3.0Ag-0.5Cu >Sn-58Bi > Sn-9Zn. Planar Cu₃Sn and scalloped Cu₆Sn₅ phases in Cu/solders and the scalloped Ag₃Sn phase in Ag/solders are observed at the metallic substrate/solder interface. The dissolution mechanism is controlled by grain boundary diffusion. The planar Cu₅Zn₈ layer formed in the Sn-9Zn/Cu systems. AgZn₃, Ag5Zn₈ and AgZn phases are found in the Sn-9Zn/Ag system and the dissolution mechanism is controlled by lattice diffusion. Massive Ag₃Sn phases dissolved into the solders and formed during solidification processes in the Ag₃Sn/Sn or Sn-3.0Ag-0.5Cu systems. AgZn₃ and Ag₅Zn₈ phases are formed at the Sn-9Zn/Ag₃Sn interface. Zn atoms diffuse through Ag-Zn IMCs to form (Ag, Zn)Sn₄ and Sn-rich regions between Ag₅Zn₈ and Ag₃Sn.     

Morphology of intermetallic compounds formed between lead-free Sn-Zn based solders and Cu substrates

The morphologies of intermetallic compounds formed between Sn-Zn based solders and Cu substrates were investigated in this study. The investigated solders were Sn-9Zn, Sn-8.55Zn-0.45Al, and Sn-8.55Zn-0.45Al-0.5Ag. The experimental results indicated that the Sn-9Zn solder formed Cu₅Zn₈ and CuZn₅ compounds on the Cu substrate, while the Al-containing solders formed the Al_4.2Cu_3.2Zn_0.7 compound. The addition of Ag to the Sn-8.55Zn-0.45Al solder resulted in the formation of the AgZn₃ compound at the interface between the Al_4.2Cu_3.2Zn_0.7 compound and the solder. Furthermore, it was found that the cooling rate of the specimen after soldering had an effect on the quantity of AgZn₃ compound formed at the interface. The AgZn₃ compound formed with an air-cooling condition exhibited a rougher surface and larger size than with a water-quenched condition. It was believed that the formation of the AgZn₃ compound at the interface occurs through heterogenous nucleation during solidification.     

Interfacial microstructure and shear strength of Ag nano particle doped Sn-9Zn solder in ball grid array packages

Sn-9Zn solder joints containing Ag nano particles were prepared by mechanically mixing Ag nano particles (0.3, 0.5 and 1 wt%) with Sn-9Zn solder paste. In the monolithic Sn-Zn solder joints, scallop-shaped AuZn₃ intermetallic compound layers were found at their interfaces. However, after the addition of Ag nano particles, an additional uniform AgZn₃ intermetallic compound layer well adhered to the top surface of the AuZn₃ intermetallic compound layer was found. In addition, in the solder ball region, fine spherical-shaped AgZn₃ intermetallic compound particles were observed as well as Zn-rich and β-Sn phases. With the addition of Ag nano particles, the shear strengths consistently increased with an increase in the Ag nano particle content due to the uniform distribution of fine AgZn₃ intermetallic compound particles. The shear strength of monolithic Sn-Zn and 1 wt% Ag nano particle content Sn-Zn solder joints after one reflow cycle were about 42.1 MPa and 48.9 MPa, respectively, while their shear strengths after eight reflow cycles were about 39.0 MPa and 48.4 MPa, respectively. The AgZn₃ IMCs were found to be uniformly distributed in the β-Sn phase for Ag particle doped Sn-9Zn composite solder joints, which result in an increase in the tensile strength, due to a second phase dispersion strengthening mechanism. The fracture surface of monolithic Sn-Zn solder exhibited a brittle fracture mode with a smooth surface while Sn-Zn solder joints containing Ag nano particles showed a typical ductile failure with very rough dimpled surfaces.     

Interfacial Reactions of Sn-3.5Ag-<Emphasis Type="Italic">x</Emphasis>Zn Solders and Cu Substrate During Liquid-State Aging

The effects of Zn (1 wt.%, 3 wt.%, and 7 wt.%) additions to Sn-3.5Ag solder and various reaction times on the interfacial reactions between Sn-3.5Ag-xZn solders and Cu substrates a during liquid-state aging were investigated in this study. The composition and morphological evolution of interfacial intermetallic compounds (IMCs) changed significantly with the Zn concentration and reaction time. For the Sn-3.5Ag-1Zn/Cu couple, CuZn and Cu₆Sn₅ phases formed at the interface. With increasing aging time, the Cu₆Sn₅ IMC layer grew thicker, while the CuZn IMC layer drifted into the solder and decomposed gradually. Cu₅Zn₈ and Ag₅Zn₈ phases formed at the interfaces of Sn-3.5Ag-3Zn/Cu and Sn-3.5Ag-7Zn/Cu couples. With increasing reaction time, the Cu₅Zn₈ layer grew and Cu atoms diffused from the substrate to the solder, which transformed the Ag₅Zn₈ to (Cu,Ag)₅Zn₈. The Cu₆Sn₅ layer that formed between the Cu₅Zn₈ layer and Cu was much thinner at the Sn-3.5Ag-7Zn/Cu interface than at the Sn-3.5Ag-3Zn/Cu interface. Additionally, we measured the thickness of interfacial IMC layers and found that 3 wt.% Zn addition to the solder was the most effective for suppressing IMC growth at the interfaces.     

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.     

Evaluation of Diffusion Barrier Between Lead-Free Solder Systems and Thermoelectric Materials

The intermetallic compound SnTe rapidly formed at interfaces between p-type bismuth telluride (Bi_0.5Sb_1.5Te₃) thermoelectric materials and lead-free solders. The intermetallic compound influences the mechanical properties of the joints and the reliability of the thermoelectric modules. Various lead-free solder alloys, Sn-3.5Ag, Sn-3Ag-0.5Cu, Sn-0.7Cu, and Sn-2.5Ag-2Ni, were used to investigate the interfacial reactions. The results thus obtained show that Ag and Cu preferentially diffused into the Te-rich phase in Bi_0.5Sb_1.5Te₃, so layers of Ag-Te and Cu-Te compounds could not form an effective diffusion barrier. Electroless nickel-phosphorus was plated at the interfaces to serve as a diffusion barrier, and the (Cu,Ni)₆Sn₅ compound formed instead of SnTe. Furthermore, the intermetallic compound NiTe formed between nickel- phosphorus and Bi_0.5Sb_1.5Te₃ and also served as a diffusion barrier. A plot of thickness as a function of annealing time yielded the growth kinetics of the intermetallic compounds in the thermoelectric material systems. The activation energy for the growth of the NiTe intermetallic compound is 111 kJ/mol.