The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si₃N₄/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni_1−x,Cu_x)₃Sn₄ intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni_1−x,Cu_x)₃Sn₄ IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu_1−y,Ni_y)₆Sn₅ IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu_1−y,Ni_y)₆Sn₅ IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 10¹⁶−10¹⁷ atoms/cm²sec in both the eutectic Sn-Ag and Sn-Pb systems.     

Characterization of the growth of intermetallic interfacial layers of Sn-Ag and Sn-Pb eutectic solders and their composite solders on Cu substrate during isothermal long-term aging

Single shear lap joints were made with four different solders, Sn-Pb and Sn-Ag eutectic solders, and their composites containing about 20 vol.% in-situ Cu6Sn5 intermetallic phases about 3–8 micrometers in diameter. Two sets of experiments were performed: In the first set, all of the above four solder joints were aged at 150°C for periods ranging to 5000 h and the intermetallic growth was monitored periodically. In the second set, each of the above four solder joints was aged at five different temperatures for 4000 h. The interfacial layers between solders and the Cu substrate were examined using optical and scanning electron microscopy. The growth kinetics of intermetallic interfacial layers formed between solder and Cu substrate was characterized. The effect of in-situ Cu₆Sn₅ intermetallic phases on the growth rate is discussed. The growth rate of the intermetallic layers in the eutectic Sn-Pb composite was slower for the first 150 h as compared to the eutectic Sn-Pb non-composite. The growth rate of the intermetallic layers were similar for both the eutectic Sn-Ag and eutectic Sn-Ag composite throughout the aging duration. The activation energies for Cu₆Sn₅ layer growth for the eutectic Sn-Pb and Sn-Ag solder joints are evaluated to be 111 kJ/mol and 116 kJ/mol, respectively. The eutectic Sn-Pb and Sn-Ag composite solder joints exhibit higher activation energies of 161 kJ/mol and 203 kJ/mol.     

Microstructure characterization of SnAgCu solder bearing Ce for electronic packaging

The creep-rupture lives of Sn3.8Ag0.7Cu and Sn3.8Ag0.7Cu0.03Ce lead-free solder joints for electronic packaging were investigated, respectively. And the relationship between creep behavior and intermetallic compound (IMC: Ag₃Sn, Cu₆Sn₅, CeSn₃) particles in SnAgCu/SnAgCuCe solder joints has been obtained. Meanwhile, rare earth Ce concentration gradient and retardation effect of Ce on the IMC layer have been observed at the solder/Cu interface. Moreover, aging reaction of Sn and Cu, and the effect mechanism of rare earth Ce on two IMCs (Cu₆Sn₅ and Cu₃Sn) are reported.     

Scanning electron microscope in-situ investigation of fracture behavior in 96.5Sn3.5Ag lead-free solder

In-situ tensile tests of as-cast 96.5Sn3.5Ag eutectic solder were performed under the scanning electron microscope (SEM) using different strain rates at room temperature, and various crack initiation and propagation behavior was observed on the specimen surface. It was found that, due to the existence of Ag₃Sn intermetallic particles and the special microstructure of β-Sn phases in Sn3.5Ag solder, grain boundary sliding (GBS) was no longer the dominant mechanism for this Pb-free solder. In the lower strain rate regime, accompanied by partial intragranular cracks, intergranular fracture along the grain boundaries in Sn-Ag eutectic structure or along the interphase boundaries between Sn-rich dendrites and Sn-Ag eutectic phases occurred primarily for the Sn3.5Ag solder in the early tensile stage. However, significant plastic deformation was observed in large areas for the specimens tested at higher strain rates, and cracks propagated in a transgranular manner across the Sn dendrites and Sn-Ag eutectic structure.     

Activation energies of intermetallic growth of Sn-Ag eutectic solder on copper substrates

Intermetallic phases formed along a Sn-Ag eutectic solder/Cu interface during solid-state aging have been characterized and the activation energies of Cu₃Sn and Cu₆Sn₅ growth have been calculated. Diffusion couples consisting of Cu/ 96.5Sn-3.5Ag/Cu were aged at 110 to 208°C for 0 to 32 days. After aging, the Cu/ solder interfaces were examined using scanning electron microscopy and energy dispersive x-ray spectroscopy. The growth rate constants for each intermetallic layer were calculated assuming a simple parabolic diffusion-controlled growth model. The activation energy for Cu₃Sn growth is 0.73 eV/atom and the activa-tion energy for Cu₆Sn₅ growth is 1.11 eV/atom.     

Influence of microstructure on fatigue crack growth behavior of Sn-Ag solder interfaces

The relationship between microstructure and fatigue crack growth behavior was examined at Sn-Ag solder interfaces on copper and electroless-nickel metallizations. On copper metallization, the solder interface was lined with a coarse Ag₃Sn intermetallic phase in addition to the Cu₆Sn₅ intermetallic and the adjacent solder alloy contained nodular Ag₃Sn phase. This interfacial microstructure was shown to result in inferior fatigue resistance, with the fatigue crack path following the interfacial Ag₃Sn intermetallic phase. In contrast, the solder interface on the electroless-nickel metallization was covered with a thin layer of Ni₃Sn₄ intermetallic phase, and the solder microstructure was composed of fine needles of Ag₃Sn phase dispersed in the Sn-rich matrix. This solder interface was found to be significantly more resistant to fatigue than the copper/Sn-Ag solder interface.     

Microstructural evolution in the Sn-Cu-Ni and Pb-Sn solder joints with Cu and Pt-Ag metallized Al2O3 substrate

The growth mechanism of intermetallics between solders and metallized substrates, after thermal aging, are investigated. The solders used in this study are unleaded Sn-Cu-Ni solder and eutectic Pb-Sn solder. The Pt-Ag/Al₂O₃, Cu block and the electroless Cu/Pt-Ag/Al₂O₃ are employed as the metallized substrates. Microstructure evolution of the interfacial morphology, elemental, and phase distribution are probed with the aid of electron-probe microanalyzer (EPMA) and x-ray diffractometry. Two kinds of intermetallics, Cu₃Sn and Cu₆Sn₅, are formed at the solder/Cu interface. However, for the solder/Pt-Ag system, only Ag₃Sn is observed at the interface. The thickness of Cu₃Sn, Cu₆Sn₅, and Ag₃Sn compound layers for all solder/metallized substrate systems shows at t^0.5 dependence at 100, 125, 150 and 170 C. According to the calculated activation energy and diffusion constant, the growth rate of Cu₃Sn and Cu₆Sn₅ intermetallics in the electroless Cumetallized substrate is relatively higher than that for Cu block one at the range of 100 C to 170 C. However, the growth rate of Cu₆Sn₅ and Ag₃Sn is reduced in the Sn-Cu-Ni solder with respect to the eutectic Pb-Sn solder. On the other hand, the Sn-Cu-Ni solder system exhibits a thicker Cu₃Sn intermetallic layer than the eutectic Pb-Sn solder after various aging times at 100 C. The thickness of Cu3Sn in the eutectic Pb-Sn solder is, however, thicker than that for Sn-Cu-Ni solder at 170 C.     

Creep deformation behavior in eutectic Sn-Ag solder joints using a novel mapping technique

Creep deformation behavior was measured for 60–100 μm thick solder joints. The solder joints investigated consisted of: (a) non-composite solder joints made with eutectic Sn-Ag solder, and (b) composite solder joints with eutectic Sn-Ag solder containing 20 vol. %, 5 μm diameter in-situ Cu₆Sn₅ intermetallic reinforcements. All creep testing in this study was carried out at room temperature. Qualitative and quantitative assessment of creep deformation was characterized on the solder joints. Creep deformation was analyzed using a novel mapping technique where a geometrical-regular line pattern was etched over the entire solder joint using excimer laser ablation. During creep, the laser-ablation (LA) pattern becomes distorted due to deformation in the solder joint. By imaging the distortion of laser-ablation patterns using the SEM, actual deformation mapping for the entire solder joint is revealed. The technique involves sequential optical/digital imaging of the deformation versus time history during creep. By tracing and recording the deformation of the LA patterns on the solder over intervals of time, local creep data are obtained in many locations in the joint. This analysis enables global and localized creep shear strains and strain rate to be determined.     

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.     

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.     

Effects of self-aligned electroplating Cu pillar/Sn-xAg bump on dense Al lines for chip-to-package connection

Self-aligned electroplating is applied to form the Cu pillar/Sn-Ag bump for semiconductor device packaging, while passivation SiN cracks are usually observed at the bump edge on the bump of the array (BOA). In this paper, the simulation method was used to investigate the mechanism of SiN cracks and then, the bump process was optimized to improve the mechanical properties of the Cu pillar/Sn-Ag bump. It was found that higher reflow rounds could improve the shear strength due to the large degree of contact between the rugged scallop-like shape of the Cu₆Sn₅ and the Sn-Ag solder. The fracture plane cleaved between the Sn-Ag and Cu₆Sn₅ interface is consistent with the simulation results. The hardness of the Sn‒Ag solder is proportional to the reflow rounds, and the amount of Ag₃Sn phase precipitation within the Sn-Ag solder contributes to the hardness value. In contrast, the disadvantage is that thermal residual stress could deteriorate the SiN crack, especially for a BOA structure The study concludes that an optimal bump process, including Sn-2%Ag solders at 260 °C for 30 s, could obtain a high shear strength and appropriate solder hardness without passivated SiN cracking.     

Mechanical Characterization of Lead-Free Sn-Ag-Cu Solder Joints by High-Temperature Nanoindentation

The reliability of Pb-free solder joints is controlled by their microstructural constituents. Therefore, knowledge of the solder microconstituents’ mechanical properties as a function of temperature is required. Sn-Ag-Cu lead-free solder alloy contains three phases: a Sn-rich phase, and the intermetallic compounds (IMCs) Cu₆Sn₅ and Ag₃Sn. Typically, the Sn-rich phase is surrounded by a eutectic mixture of β-Sn, Cu₆Sn₅, and Ag₃Sn. In this paper, we report on the Young’s modulus and hardness of the Cu₆Sn₅ and Cu₃Sn IMCs, the β-Sn phase, and the eutectic compound, as measured by nanoindentation at elevated temperatures. For both the β-Sn phase and the eutectic compound, the hardness and Young’s modulus exhibited strong temperature dependence. In the case of the intermetallics, this temperature dependence is observed for Cu₆Sn₅, but the mechanical properties of Cu₃Sn are more stable up to 200°C.     

Microstructure, thermal analysis and hardness of a Sn–Ag–Cu–1 wt% nano-TiO2 composite solder on flexible ball grid array substrates

Sn-Ag-Cu composite solders reinforced with nano-sized, nonreacting, noncoarsening 1 wt% TiO₂ particles were prepared by mechanically dispersing TiO₂ nano-particles into Sn-Ag-Cu solder powder and the interfacial morphology of the solder and flexible BGA substrates were characterized metallographically. At their interfaces, different types of scallop-shaped intermetallic compound layers such as Cu₆Sn₅ for a Ag metallized Cu pad and Sn-Cu-Ni for a Au/Ni and Ni metallized Cu pad, were found in plain Sn-Ag-Cu solder joints and solder joints containing 1 wt% TiO₂ nano-particles. In addition, the intermetallic compound layer thicknesses increased substantially with the number of reflow cycles. In the solder ball region, Ag₃Sn, Cu₆Sn₅ and AuSn₄ IMC particles were found to be uniformly distributed in the β-Sn matrix. However, after the addition of TiO₂ nano-particles, Ag₃Sn, AuSn₄ and Cu₆Sn₅ IMC particles appeared with a fine microstructure and retarded the growth rate of IMC layers at their interfaces. The Sn-Ag-Cu solder joints containing 1 wt% TiO₂ nano-particles consistently displayed a higher hardness than that of the plain Sn-Ag-Cu solder joints as a function of the number of reflow cycles due to the well-controlled fine microstructure and homogeneous distribution of TiO₂ nano-particles which gave a second phase dispersion strengthening mechanism.     

The effect of soldering process variables on the microstructure and mechanical properties of eutectic Sn-Ag/Cu solder joints

Fundamental understanding of the relationship among process, microstructure, and mechanical properties is essential to solder alloy design, soldering process development, and joint reliability prediction and optimization. This research focused on the process-structure-property relationship in eutectic Sn-Ag/Cu solder joints. As a Pb-free alternative, eutectic Sn-Ag solder offers enhanced mechanical properties, good wettability on Cu and Cu alloys, and the potential for a broader range of application compared to eutectic Sn-Pb solder. The relationship between soldering process parameters (soldering temperature, reflow time, and cooling rate) and joint microstructure was studied systemati-cally. Microhardness, tensile shear strength, and shear creep strength were measured and the relationship between the joint microstructures and mechani-cal properties was determined. Based on these results, low soldering tempera-tures, fast cooling rates, and short reflow times are suggested for producing joints with the best shear strength, ductility, and creep resistance.     

Interfacial reaction between multicomponent lead-free solders and Ag,Cu, Ni,and Pd substrates

The interfacial reaction between two prototype multicomponent lead-free solders, Sn-3.4Ag-1Bi-0.7Cu-4In and Sn-3.4Ag-3Bi-0.7Cu-4In (mass%), and Ag, Cu, Ni, and Pd substrates are studied at 250°C and 150°C. The microstructural characterization of the solder bumps is carried out by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis. Ambient temperature, isotropic elastic properties (bulk, shear, and Young’s moduli and Poisson’s ratio) of these solders along with eutectic Sn-Ag, Sn-Bi, and Sn-Zn solders are measured. The isotropic elastic moduli of multicomponent solders are very similar to the eutectic Sn-Ag solder. The measured solubility of the base metal in liquid solders at 250°C agrees very well with the solubility limits reported in assessed Sn-X (X=Ag, Cu, Ni, Pd) phase diagrams. The measured contact angles were generally less than 15° on Cu and Pd substrates, while they were between 25° and 30° on Ag and Ni substrates. The observed intermediate phases in Ag/solder couples were Ag₃Sn after reflow at 250°C and Ag₃Sn and ζ (Ag-Sn) after solid-state aging at 150°C. In Cu/solder and Ni/solder couples, the interfacial phases were Cu₆Sn₅ and (Cu,Ni)₆Sn₅, respectively. In Pd/solder couples, only PdSn₄ after 60-sec reflow, while both PdSn₄ and PdSn₃ after 300-sec reflow, were observed.     

The formation and growth of intermetallics in composite solder

The formation and growth of intermetallics at the solder/substrate interface are factors affecting the solderability and reliability of electronic solder joints. This study was performed to better understand the diffusion behavior and microstructural evolution of Cu−Sn intermetallics at the composite solder/copper substrate interface for eutectic solder and solder alloys containing particle additions of Cu, Cu₃Sn, Cu₆Sn₅, Ag, Au, and Ni. Annealing temperatures of 110 to 160°C were used with aging times of 0 to 64 days. The copper-containing composite solders generally formed thinner Cu₆Sn₅ layers, but thicker Cu₃Sn layers than were formed by the eutectic solder alone. These copper-containing additions, therefore, resulted in increased activation energies for Cu₆Sn₅ formation and decreased activation energies for Cu₃Sn formation as compared to the eutectic solder. The activation energy for Cu₃Sn formation decreased relative to eutectic solder for silver and gold composite solders even though less Cu₃Sn was formed at the substrate interface. Nickel and palladium drastically reduced the Cu₃Sn thickness and increased the Cu₆Sn₅ thickness. However, the Cu₆Sn₅ contained a substantial volume fraction of voids close to the copper substrate. We propose two mechanisms to explain the effects of the copper-containing and silver particles on the kinetics of intermetallic formation. First, the particles act as tin-sinks which remove tin from the solder and decrease the amount of tin available for reaction at the solder/substrate interface. Second, the particles reduce the cross-sectional area available for tin diffusion, which also reduces the amount of tin available at the interface for reaction.     

Microstructural effect on the creep strength of a Sn-3.5%Ag solder alloy

The effect of microstructure obtained by rapid or slow solidification and cooling of a Sn-3.5%Ag lead-free solder alloy on the creep strength has been investigated. The rapidly cooled alloy showed that the microstructure consisted of the primarily crystallized Sn phase and the quasi-eutectic phase, where fine Ag₃Sn particles dispersed in the Sn matrix. In the slowly cooled alloy, large platelets of Ag₃Sn were formed sparsely in the Sn matrix. A difference of about 2.5 orders of magnitude in the cooling rate translates to about 1.5 orders of magnitude in the creep-rupture time. Accordingly, fine particle dispersion of Ag₃Sn is considered to be very beneficial for the restraining of creep deformation, that is, for the decreasing of creep rate of the Sn-3.5%Ag alloy, compared with the effect of large platelets of Ag₃Sn sparsely formed in the Sn matrix.     

The nanoindentation characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> intermetallic compounds in the solder bump

In general, formation and growth of intermetallic compounds (IMCs) play a major role in the reliability of the solder joint in electronics packaging and assembly. The formation of Cu-Sn or Ni-Sn IMCs have been observed at the interface of Sn-rich solders reacted with Cu or Ni substrates. In this study, a nanoindentation technique was employed to investigate nanohardness and reduced elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ IMCs in the solder joints. The Sn-3.5Ag and Sn-37Pb solder pastes were placed on a Cu/Ti/Si substrate and Ni foil then annealed at 240°C to fabricate solder joints. In Sn-3.5Ag joints, the magnitude of the hardness of the IMCs was in the order Ni₃Sn₄>Cu₆Sn₅>Cu₃Sn, and the elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ were 125 GPa, 136 GPa, and 142 GPa, respectively. In addition, the elastic modulus of the Cu₆Sn₅ IMC in the Sn-37Pb joint was similar to that for the bulk Cu₆Sn₅ specimen but less than that in the Sn-3.5Ag joint. This might be attributed to the strengthening effect of the dissolved Ag atoms in the Cu₆Sn₅ IMC to enhance the elastic modulus in the Sn-3.5Ag/Cu joint.     

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.     

Investigation of intermetallic compounds (IMCs) in electrochemically stripped solder joints with SEM

In this work we compare the microstructures of intermetallic compounds (IMCs) in electrochemically stripped solder joints created by two different soldering methods (vapor phase soldering (VPS), and selective laser soldering with a CO₂ laser). After the selective removal of the Sn phase with amperometry, the microstructure and structural composition of the IMC can be revealed in a detailed way, which is unlike any other previously published methods. The differences between the IMC microstructures of the technologically different solder joints were analyzed with optical microscopy and scanning electron microscopy (SEM). Energy dispersive spectroscopy (EDS) measurements were utilized to identify the different intermetallic phases (Ag₃Sn, Cu₆Sn₅). Significant differences were observed in the IMC structures of solder joints prepared by different technologies.