Isothermal aging characteristics of Sn–Pb micro solder bumps

The shear strength of the under bump metallurgy (UBM) structure in both the high-melting solder bump and low-melting solder bump after aging were evaluated. Scanning electron microscopy and transmission electron microscopy were examined in the intermetallic compounds (IMCs) and bump joint profiles at the interface between solder and UBM. In 900 h aging experiments, the maximum shear strength of Sn–97wt.%Pb and Sn–37wt.%Pb decreased by 25% and 20%, respectively. The growth of Cu₆Sn₅ and Cu₃Sn was ascertained by the aging treatment. The crack path changes from the interior of a solder to the IMC interface. Compare with the Cu–Sn IMC, the amount of Ni–Sn IMC was small. The Ni layer is considered as the diffusion barrier.     

A Study on the Thermal Reliability of Cu/SnAg Double-Bump Flip-Chip Assemblies on Organic Substrates

The Cu/SnAg double-bump structure is a promising candidate for fine-pitch flip-chip applications. In this study, the interfacial reactions of Cu (60 μm)/SnAg (20 μm) double-bump flip chip assemblies with a 100 μm pitch were investigated. Two types of thermal treatments, multiple reflows and thermal aging, were performed to evaluate the thermal reliability of Cu/SnAg flip-chip assemblies on organic printed circuit boards (PCBs). After these thermal treatments, the resulting intermetallic compounds (IMCs) were identified with scanning electron microscopy (SEM), and the contact resistance was measured using a daisy-chain and a four-point Kelvin structure. Several types of intermetallic compounds form at the Cu column/SnAg solder interface and the SnAg solder/Ni pad interface. In the case of flip-chip samples reflowed at 250°C and 280°C, Cu₆Sn₅ and (Cu, Ni)₆Sn₅ IMCs were found at the Cu/SnAg and SnAg/Ni interfaces, respectively. In addition, an abnormal Ag₃Sn phase was detected inside the SnAg solder. However, no changes were found in the electrical contact resistance in spite of severe IMC formation in the SnAg solder after five reflows. In thermally aged flip-chip samples, Cu₆Sn₅ and Cu₃Sn IMCs were found at the Cu/SnAg interface, and (Cu, Ni)₆Sn₅ IMCs were found at the SnAg/Ni interface. However, Ag₃Sn IMCs were not observed, even for longer aging times and higher temperatures. The growth of Cu₃Sn IMCs at the Cu/SnAg interface was found to lead to the formation of Kirkendall voids inside the Cu₃Sn IMCs and linked voids within the Cu₃Sn/Cu column interfaces. These voids became more evident when the aging time and temperature increased. The contact resistance was found to be nearly unchanged after 2000 h at 125°C, but increases slightly at 150°C, and a number of Cu/SnAg joints failed after 2000 h. This failure was caused by a reduction in the contact area due to the formation of Kirkendall and linked voids at the Cu column/Cu₃Sn IMC interface.     

Interfacial Reaction Effect on Electrical Reliability of Cu Pillar/Sn Bumps

Thermal annealing and electromigration (EM) tests were performed with Cu pillar/Sn bumps to understand the growth mechanism of intermetallic compounds (IMCs). Annealing tests were carried out at both 100°C and 150°C. At 150°C, EM tests were performed using a current density of 3.5 × 10⁴ A/cm². The electrical failure mechanism of the Cu pillar/Sn bumps was also investigated. Cu₃Sn formed and grew at the Cu pillar/Cu₆Sn₅ interface with increasing annealing and current-stressing times. The growth mechanism of the total (Cu₆Sn₅ + Cu₃Sn) IMC changed when the Sn phase in the Cu pillar/Sn bump was exhausted. The time required for complete consumption of the Sn phase was shorter during the EM test than in the annealing test. Both IMC growth and phase transition from Cu₆Sn₅ to Cu₃Sn had little impact on the electrical resistance of the whole interconnect system during current stressing. Electrical open failure in the Al interconnect near the chip-side Cu pillar edge implies that the Cu pillar/Sn bump has excellent electrical reliability compared with the conventional solder bump.     

Interfacial Reactions and Joint Strengths of Sn-<Emphasis Type="Italic">x</Emphasis>Zn Solders with Immersion Ag UBM

The solder joint microstructures of immersion Ag with Sn-xZn (x = 0 wt.%, 1 wt.%, 5 wt.%, and 9 wt.%) solders were analyzed and correlated with their drop impact reliability. Addition of 1 wt.% Zn to Sn did not change the interface microstructure and was only marginally effective. In comparison, the addition of 5 wt.% or 9 wt.% Zn formed layers of AgZn₃/Ag₅Zn₈ at the solder joint interface, which increased drop reliability significantly. Under extensive aging, Ag-Zn intermetallic compounds (IMCs) transformed into Cu₅Zn₈ and Ag₃Sn, and the drop impact resistance at the solder joints deteriorated up to a point. The beneficial role of Zn on immersion Ag pads was ascribed to the formation of Ag-Zn IMC layers, which were fairly resistant to the drop impact, and to the suppression of the brittle Cu₆Sn₅ phase at the joint interface.     

High temperature reliability and interfacial reaction of eutectic Sn–0.7Cu/Ni solder joints during isothermal aging

The interfacial reactions and growth kinetics of intermetallic compound (IMC) layers formed between Sn–0.7Cu (wt.%) solder and Au/Ni/Cu substrate were investigated at aging temperatures of 185 and 200 °C for aging times of up to 60 days. After reflow, the IMC formed at the interface was (Cu, Ni)₆Sn₅. After aging at 185 °C for 3 days and at 200 °C for 1 day, two IMCs of (Cu, Ni)₆Sn₅ and (Ni, Cu)₃Sn₄ were observed. The growth of the (Ni, Cu)₃Sn₄ IMC consumed the (Cu, Ni)₆Sn₅ IMC at an aging temperature of 200 °C due to the restriction of supply of Cu atoms from the solder to interface. After aging at 200 °C for 60 days, the Ni layer of the substrate was completely consumed in many parts of the sample, at which point a Cu₃Sn IMC was formed. In the ball shear test, the shear strength decreased with increasing aging temperature and time. Until the aging at 185 °C for 15 days and at 200 °C for 3 days, fractures occurred in the bulk solder. After prolonged aging treatment, fractures partially occurred at the (Cu, Ni)₆Sn₅ + Au/solder interface for aging at 185 °C and at the (Ni, Cu)₃Sn₄/Ni interface for aging at 200 °C, respectively. Consequently, thick IMC layer and thermal loading history significantly affected the integrity of the Sn–0.7Cu/Ni BGA joints.     

Effects of fourth alloying additive on microstructures and tensile properties of Sn–Ag–Cu alloy and joints with Cu

The effects of the fourth elements, i.e., Fe, Ni, Co, Mn and Ti, on microstructural features, undercooling characteristics, and monotonic tensile properties of Sn–3 wt.%Ag–0.5 wt.%Cu lead-free solder were investigated. All quaternary alloys basically form third intermetallic compounds in addition to fine Ag₃Sn and Cu₆Sn₅ and exhibit improved solder structure. The precipitates of Sn–3Ag–0.5Cu (–0.1 wt.%X; X=Ni, Ti and Mn) alloy are very fine comparing with the other alloys. The effective elements for suppressing undercooling in solidification are Ti, Mn, Co and Ni. All quaternary bulk alloys exhibit similar or slightly larger tensile strengths; especially Mn and Ni can improve elongation without degrading strength. The interfacial phases of Sn–3Ag–0.5Cu (–0.1 wt.%X; X=Fe, Mn and Ti)/Cu joints are typical Cu₆Sn₅ scallops. Sn–3Ag–0.5Cu (–0.1 wt.%X; X=Ni and Co)/Cu joints form very fine Sn–Cu–Ni and Sn–Cu–Co scallops at interface. The Cu/Sn–3Ag–0.5Cu–0.1Ni/Cu joint exhibits improved tensile strength prior to thermal aging at 125 and 150 °C. The fracture surface of Cu/Sn–3Ag–0.5Cu/Cu joint exhibits mixture of ductile and brittle fractures, while Cu/Sn–3Ag–0.5Cu (–0.1X; X=Ni and Co)/Cu joints exhibit only brittle fracture at interface. The Sn–3Ag–0.5Cu–0.1Ni alloy is more reliable solder alloy with improved properties for all tests in the present work.     

Electromigration-Induced Interfacial Reactions in Cu/Sn/Electroless Ni-P Solder Interconnects

The effect of electromigration (EM) on the interfacial reaction in a line-type Cu/Sn/Ni-P/Al/Ni-P/Sn/Cu interconnect was investigated at 150°C under 5.0 × 10³ A/cm². When Cu atoms were under downwind diffusion, EM enhanced the cross-solder diffusion of Cu atoms to the opposite Ni-P/Sn (anode) interface compared with the aging case, resulting in the transformation of interfacial intermetallic compound (IMC) from Ni₃Sn₄ into (Cu,Ni)₆Sn₅. However, at the Sn/Cu (cathode) interface, the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.2 wt.% Ni) and Cu₃Sn. When Ni atoms were under downwind diffusion, only a very small quantity of Ni atoms diffused to the opposite Cu/Sn (anode) interface and the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.6 wt.% Ni) and Cu₃Sn. EM significantly accelerated the dissolution of Ni atoms from the Ni-P and the interfacial Ni₃Sn₄ compared with the aging case, resulting in fast growth of Ni₃P and Ni₂SnP, disappearance of interfacial Ni₃Sn₄, and congregation of large (Ni,Cu)₃Sn₄ particles in the Sn solder matrix. The growth kinetics of Ni₃P and Ni₂SnP were significantly accelerated after the interfacial Ni₃Sn₄ IMC completely dissolved into the solder, but still followed the t ^1/2 law.     

Interfacial Reaction of Sn and Cu-<Emphasis Type="Italic">x</Emphasis>Zn Substrates After Reflow and Thermal Aging

Zn additions to Cu under bump metallurgy (UBM) in solder joints were the subject of this study. An alternative design was implemented to fabricate pure Sn as the solder and Cu-xZn (x = 15 wt.% and 30 wt.%) as the UBM to form the reaction couple. As the Zn content increased from 15 wt.% to 30 wt.% in the Sn/Cu-Zn system, growth of both Cu₃Sn and Cu₆Sn₅ was suppressed. In addition, no Kirkendall voids were observed at the interface in either Sn/Cu-Zn couple during heat treatment. After 40-day aging, different multilayered phases of [Cu₆Sn₅/Cu₃Sn/Cu(Zn)] and [Cu₆Sn₅/Cu(Zn,Sn)/CuZn] formed at the interface of [Sn/Cu-15Zn] and [Sn/Cu-30Zn] couples, respectively. The growth mechanism of intermetallic compounds (IMCs) during aging is discussed on the basis of the composition variation in the joint assembly with the aid of electron-microscopic characterization and the Sn-Cu-Zn ternary phase diagram. According to these analyses of interfacial morphology and IMC formation in the Sn/Cu-Zn system, Cu-Zn is a potential UBM for retarding Cu pad consumption in solder joints.     

Experimental investigation of the failure mechanism of Cu–Sn intermetallic compounds in SAC solder joints

A detailed experimental study on the fracture mechanism of Cu–Sn intermetallic compounds (IMCs) in the Pb-free solder was presented in this paper. The growth behaviors of the Cu₆Sn₅ and Cu₃Sn IMCs were inspected and the respective evolution pattern of their microstructures was investigated. Then, a detailed fractographic analysis on brittle fractured solder joints was conducted after the high speed ball pull test. The fracture locations in the Cu–Sn IMC layers during different periods of aging process were identified. The fracture modes of Cu₆Sn₅ and Cu₃Sn were determined as well. Afterwards, the fracture energies of different Cu–Sn IMC materials were directly compared using the Charpy impact test with a specially designed specimen. It was found that the grain boundary of Cu₃Sn is the weakest link in the Cu–Sn IMC system. Finally, based on these three parts of study, a mechanism to explain the thermal degradation of Cu–Sn IMCs was proposed.     

Numerical and experimental analysis of the Sn3.5Ag0.75Cu solder joint reliability under thermal cycling

The Sn3.5Ag0.75Cu (SAC) solder joint reliability under thermal cycling was investigated by experiment and finite element method (FEM) analysis. SAC solder balls were reflowed on three Au metallization thicknesses, which are 0.1, 0.9, and 4.0 μm, respectively, by laser soldering. Little Cu–Ni–Au–Sn intermetallic compound (IMC) was formed at the interface of solder joints with 0.1 μm Au metallization even after 1000 thermal cycles. The morphology of AuSn₄ IMC with a small amount of Ni and Cu changed gradually from needle- to chunky-type for the solder joints with 0.9 μm Au metallization during thermal cycling. For solder joints with 4 μm Au metallization, the interfacial morphology between AuSn₄ and solder bulk became smoother, and AuSn₄ grew at the expense of AuSn and AuSn₂. The cracks mainly occurred through solder near the interface of solder/IMC on the component side for solder joints with 0.1 μm Au metallization after thermal shock, and the failure was characterized by intergranular cracking. The cracks of solder joints with 0.9 μm Au metallization were also observed at the same location, but the crack was not so significant. Only micro-cracks were found on the AuSn₄ IMC surface for solder joints with 4.0 μm Au metallization. The responses of stress and strain were investigated with nonlinear FEM, and the results correlated well with the experimental results.     

Effects of Surface Finishes and Current Stressing on Interfacial Reaction Characteristics of Sn-3.0Ag-0.5Cu Solder Bumps

The effects of surface finishes on the in situ interfacial reaction characteristics of ball grid array (BGA) Sn-3.0Ag-0.5Cu lead-free solder bumps were investigated under annealing and electromigration (EM) test conditions of 130°C to 175°C with 5.0 × 10³ A/cm². During reflow and annealing, (Cu,Ni)₆Sn₅ intermetallic compound (IMC) formed at the interface of electroless nickel immersion gold (ENIG) finish. In the case of both immersion Sn and organic solderability preservative (OSP) finishes, Cu₆Sn₅ and Cu₃Sn IMCs formed. Overall, the IMC growth velocity of ENIG was much lower than that of the other finishes. The activation energies of total IMCs were found to be 0.52 eV for ENIG, 0.78 eV for immersion Sn, and 0.72 eV for OSP. The ENIG finish appeared to present an effective diffusion barrier between the Cu substrate and the solder, which leads to better EM reliability in comparison with Cu-based pad systems. The failure mechanisms were explored in detail via in situ EM tests.     

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.     

The formation and growth of intermetallic compounds and shear strength at Sn–Zn solder/Au–Ni–Cu interfaces

The microstructures and shear strength of the interface between Sn–Zn lead-free solders and Au/Ni/Cu interface under thermal aging conditions was investigated. The intermetallic compounds (IMCs) at the interface between Sn–Zn solders and Au/Ni/Cu interface were analyzed by field emission scanning electron microscopy and transmission electron microscopy. The results showed the decrease in the shear strength of the interface with aging time and temperature. The solder ball with highly activated flux had about 8.2% increased shear strength than that with BGA/CSP flux. Imperfect wetting and many voids were observed in the fracture surface of the latter flux. The decreased shear strength was influenced by IMC growth and Zn grain coarsening. In the solder layer, Zn reacted with Au and then was transformed to the β-AuZn compound. Although AuZn grew first, three diffusion layers of γ-Ni₅Zn₂₁ compounds were formed after aging for 600 h at 150 °C. The layers divided by Ni₅Zn₂₁ (1), (2), and (3) were formed with the thickness of 0.7 μm, 4 μm, and 2 μm, respectively.     

Mechanical properties of intermetallic compounds associated with Pb-free solder joints using nanoindentation

Mechanical properties of intermetallic compound (IMC) phases in Pb-free solder joints were obtained using nanoindentation testing (NIT). The elastic modulus and hardness were determined for IMC phases associated with insitu FeSn particle reinforced and mechanically added, Cu particle-reinforced, composite solder joints. The IMC layers that formed around Cu particle reinforcement and at the Cu substrate/solder matrix interface were probed with NIT. Moduli and hardness values obtained by NIT revealed were noticeably higher for Cu-rich Cu₃Sn than those of Cu₆Sn₅. The Ag₃Sn platelets that formed during reflow were also examined for eutectic Sn-Ag solder column joints. The indentation modulus of Ag₃Sn platelets was significantly lower than that of FeSn, SnCuNi, and CuSn IMCs. Indentation creep properties were assessed in localized microstructure regions of the as-cast, eutectic Sn-Ag solder. The stress exponent, n, associated with secondary creep differed widely depending on the microstructure feature probed by the indenter tip.     

Effect of thermal aging on the interfacial structure of SnAgCu solder joints on Cu

Interfacial structure plays a great role in solder joint reliability. In solder joints on Cu, not only is Kirkendall voiding at the solder/Cu interface a concern, but also the growth of interfacial Cu–Sn intermetallic compounds (IMCs). In this work, evolution of microstructure in the interfacial region was studied after thermal aging at 100–150 °C for up to 1000 h. Special effort was made during sample preparation to reveal details of the interfacial structure. Thickness of the interfacial phases was digitally measured and the activation energy was deduced for the growth of Cu₃Sn. Kirkendall voids formed at the Cu/Cu₃Sn interface as well as within the Cu₃Sn layer. The thickness of Cu₃Sn significantly increased with aging time, but that of Cu₆Sn₅ changed a little. The interfacial Cu₃Sn layer was found growing at the expense of Cu₆Sn₅. Evolution of the interfacial structure during thermal aging is discussed.     

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.     

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.     

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.     

High-Temperature Resistant Intermetallic Compound Joints for Si Chips and Cu Substrates

A thin-film joining method utilizing evaporated films as the joining material was newly developed for power semiconductor die attachment. When the evaporated films are completely transformed into intermetallic compounds (IMCs) with high melting points, the joint can exhibit the required high-temperature strength. In this study, a joint consisting of Cu₆Sn₅, (Ag,Cu)₃Sn, and Cu₃Sn IMCs was achieved at 573 K after 30 s. Results of nanoindentation tests revealed the hardness and elastic moduli of each IMC. In accelerated tests, a high-temperature strength of at least 15 MPa was shown for 3.6 Ms at 423 K or 500 cycles between 223 K and 403 K. These results suggest that the IMC joint has great potential as a die-attach material.     

Improvement in high-temperature degradation by isotropic conductive adhesives including Ag–Sn alloy fillers

The reliability evaluation of Cu and Sn/Ni joined with isotropic conductive adhesives (ICAs) including Ag–Sn alloy fillers with or without Ag plating instead of Ag fillers was examined using tensile tests, electrical resistivity tests and microstructural observations. For an ICA, including Ag–Sn alloy fillers added to Sn–58wt%Bi fillers, the tensile strength was found to improve, but the electrical resistivity worsened with 150 °C heat exposure. An ICA, including, Ag–Sn alloy fillers with Ag plating, was able to maintain electrical resistivity after being subjected to 150 °C heat exposure. The Ag plating on the Ag–Sn fillers reacted with the Sn in the Ag–Sn fillers, leading to the joining of the fillers with each other though metallurgical connections, and the transformation of Ag into Ag₃Sn within a 1-h curing time at 150 °C, since the Ag plating was microscopic and active. After heat exposure, the Sn distributed itself along the substrate/ICA interface by the diffusion of Sn though the connected fillers, and Cu₃Sn formed at the Cu/ICA interface, in contrast with the Ag–Sn alloy fillers without Ag plating.