Intermetallic Cu6Sn5 Research Articles

The Effect of Multiple Solder Reflows on the Formation of Cu6Sn5 Intermetallics and the Decomposition of SnAg3.0Cu0.5 Solder Joints in the Framework of Rework and Reuse of MLCC Components

The Effect of Multiple Solder Reflows on the Formation of Cu6Sn5 Intermetallics and the Decomposition of SnAg3.0Cu0.5 Solder Joints in the Framework of Rework and Reuse of MLCC Components

Effects of CuO nanoparticles on SAC composite solder joints: Microstructural and DFT study

In this paper, novel application possibilities of CuO nanoparticles were investigated in SAC0307 solder alloy for composite soldering purposes. CuO nanoparticles in 0.25 and 0.5 wt% were mixed into the solder paste to produce composite solder joints. Solder joints were manufactured using standard surface mounting technology from different solder pastes. The solder joints were loaded in an 85 °C/85RH% temperature and humidity test for 4000 h. It was found that the CuO composite solder joints showed improved mechanical quality due to the microstructural refinement, which was studied using scanning electron microscopy (SEM) and focused ion beam (FIB) analysis. On the other hand, the corrosion resistance of CuO joints decreased, as they suffered localized corrosion extensively, which produced longer and more Sn whiskers on their surface than on the reference SAC0307. Density functional theory (DFT) calculations proved that CuO can bond to Sn, but CuO is not chemically inert in the solder bulk. CuO can start a cyclic reaction with the dispersed Cu6Sn5 intermetallics, which produces SnO2 in the solder bulk, ultimately enhancing corrosion. Therefore, CuO nanoparticles are suggested to be applied only in non-corrosive environments, such as space applications.

Metal deposited nanoparticles as “bridge materials” for lead-free solder nanocomposites

An influence of carbon nanotubes and carbon nanospheres coated by Au–Pd and Pt on the microstructure of solder/copper joints at room temperature and after aging at sub-zero temperature. The carbon nanosized admixtures were mixed with ternary Sn3.0Ag0.5Cu matrix to prepare a composite solder. The microstructure of the solder joints between the nanocomposite solders and a copper substrate was studied by scanning electron microscopy. It was found that minor (0.05 wt. %) admixtures of both the carbon nanospheres and nanotubes increase the shear strength of the solder joints and reduce the growth rate of the intermetallic Cu6Sn5 layer, formed at the interface between solder and copper. This effect may be related to the adsorption of nanoinclusions on the grain surface during the solidification process. Comparative analysis suggests that exposure for 2 months at 253 K does not lead to deterioration of such an important mechanical characteristic of the solder joint as shear strength, indicating the possibility of using these nanocomposite solders in microelectronic equipment even at temperatures below 0 ℃.

Electrochemical formation of Sn films on copper by overpotential and underpotential electrodeposition in deep eutectic solvents

The electrodeposition process of tin films on copper electrodes in ethaline and reline deep eutectic solvents (DES) was studied in the 303 – 353 K range. Voltammetric data indicate the presence of underpotential and overpotential electrodeposition processes. While the former occurs under surface-reaction control, the latter proceeds under mass transport control. Electrochemical impedance spectroscopy shows two capacitive contributions during the underpotential process and a single capacitive contribution at high frequencies and a Warburg contribution at low frequencies, when the electrodeposition process takes place in the overpotential region. Tin deposits obtained in ethaline exhibit blunt particles with ordered structures whereas in reline facetted particles with no preferential order are observed as electrodeposition time is increased. The electrocrystallization mechanism under overpotential conditions in ethaline and reline corresponds to an instantaneous nucleation and a 3D growth process. For underpotential conditions in ethaline, an instantaneous nucleation and 2D growth coupled to an adsorption process occurs. XRD spectra shows the formation of Cu3Sn and Cu6Sn5 intermetallics due to the diffusion of Sn atoms into the Cu lattice during the electrodeposition process. From rotating disk electrode measurements, the diffusion coefficient of Sn(II) ions in both DES at different temperatures, and the diffusion activation energy, were determined.

Phase field modelling combined with data-driven approach to unravel the orientation influenced growth of interfacial Cu6Sn5 intermetallics under electric current stressing

Microstructure of interfacial intermetallics plays an important role in determining the service performance and reliability of interconnects especially due to the anisotropic properties of intermetallic grains, preferential growth of intermetallics induced by the electric current is observed in experiments, but the exact mechanisms for this have not been understood completely. For this endeavor, a phase field model considering the free energy arisen from the applied electric current is developed to tackle the intermetallic grain growth behavior in Sn/Cu interconnects, the focus falls on the influence of anisotropic electric conductivity. Simulation results show that electric current stressing preferentially accelerates the intermetallic growth, and the orientation effects are more pronounced with higher value of electric current density. Due to the competitive growth of multiple Cu6Sn5 grains in the presence of electric current, most region of the intermetallic layer is occupied by the grains whose c-axis is along the direction of the electric current. The intermetallic grain with higher electric conductivity along the electron flow holds smaller current field, while the phase boundaries own higher electric field. It is found that the higher local electric field concentrating at phase boundary drives faster phase boundary migration. The data generated from physics-based phase field simulations are utilized to train a neural network model that functionally maps the area of a particular grain with the applied current density, simulation time, grain identification, orientation of the grain and its neighboring grains. The prediction model reveals that that electric current stressing preferentially accelerates the intermetallic growth, and the orientation effects are more pronounced with higher value of electric current density. The results from phase field simulation and physically informed machine learning model further deepen understandings of the microstructure evolution and selective intermetallic growth in the context of electric current, and shed light on the in-silico studies and design route of interconnects under other types of loadings.

Superior Fast-Charging Lithium-Ion Batteries Enabled by the High-Speed Solid-State Lithium Transport of an Intermetallic Cu6 Sn5 Network.

Superior fast charging is a desirable capability of lithium-ion batteries, which can make electric vehicles a strong competition to traditional fuel vehicles. However, the slow transport of solvated lithium ions in liquid electrolytes is a limiting factor. Here, a Lix Cu6 Sn5 intermetallic network is reported to address this issue. Based on electrochemical analysis and X-ray photoelectron spectroscopy mapping, it is demonstrated that the reported intermetallic network can form a high-speed solid-state lithium transport matrix throughout the electrode, which largely reduces the lithium-ion-concentration polarization effect in the graphite anode. Employing this design, superior fast-charging graphite/lithium cobalt oxide full cells are fabricated and tested under strict electrode conditions. At the charging rate of 6 C, the fabricated full cells show a capacity of 145 mAh g-1 with an extraordinary capacity retention of 96.6%. In addition, the full cell also exhibits good electrochemical stability at a high charging rate of 2 C over 100 cycles (96.0% of capacity retention) in comparison to traditional graphite-anode-based cells (86.1% of capacity retention). This work presents a new strategy for fast-charging lithium-ion batteries on the basis of high-speed solid-state lithium transport in intermetallic alloy hosts.

Properties of Sn-3 wt%Ag-5 wt%Cu alloys with Cu6Sn5 intermetallics grain refined by Mg

This paper investigates the influence of Mg additions on the microstructure, thermal properties, electrical properties, and joint strength of bulk and ball grid array (BGA) reflowed Sn-3 wt%Ag-5 wt%Cu solder alloy and the joint intermetallics (IMCs). The cross-sectional microstructure analysis revealed that the addition of Mg effectively triggered the grain refinement of primary Cu6Sn5 IMCs in the bulk solder alloys. In addition, the thickness of the interfacial Cu6Sn5 IMCs layer was suppressed. The optimal addition for refinement is in the vicinity of 0.10 wt%Mg. Furthermore, synchrotron tomography three-dimensional reconstructed imaging reveals that the grain refinement of primary Cu6Sn5 IMCs is also effective even in BGA scale solder joint at normal reflow conditions. These primary Cu6Sn5 IMCs showed a non-faceted morphology. 0.10 wt%Mg addition reduced the number and size of the Cu6Sn5 IMCs. The grain refinement of primary Cu6Sn5 IMCs could be attributed to the presence of Mg, Mg2Sn, and MgO phases that potentially serve as heterogenous nucleation sites. The thermal analysis showed that the degree of undercooling values was significantly reduced to the minimum with 0.10 wt%Mg addition, which increased when the amount of Mg increased to 0.15 wt%. The mechanical properties showed that the ductility of the solder joint at high shear speed was improved.

Nanoporous Intermetallic Cu3 Sn/Cu Hybrid Electrodes as Efficient Electrocatalysts for Carbon Dioxide Reduction.

Designing highly selective and cost-effective electrocatalysts toward electrochemical carbon dioxide (CO2 ) reduction is crucial for desirable transformation of greenhouse gas into fuels or high-value chemical products. Here, the authors report intermetallic Cu3 Sn that is in situ formed and seamlessly integrated on self-supported bimodal nanoporous Cu skeleton (Cu3 Sn/Cu) via a spontaneous alloying of Sn and Cu as robust electrocatalyst for selective electroreduction of CO2 to CO. By virtue of Sn atoms strengthening CO adsorption on Cu atoms, the intermetallic Cu3 Sn has an intrinsic activity of ≈10.58μAcm-2 , more than 80-fold higher than that of monometallic Cu. By virtue of hierarchical bicontinuous nanoporous Cu architecture facilitating electron transfer and CO2 and proton mass transport and offering high specific surface areas for full use of electroactive Cu3 Sn sites, the nanoporous Cu3 Sn/Cu hybrid electrodes produce CO at a low overpotential of 0.09V, and exhibit high partial current density of ≈15mAcm-2 geo at overpotential of 0.59V, along with excellent stability and selectivity of 91.5% Faradaic efficiency. The outstanding electrochemical performance make them attractive alternatives to precious Au- and Ag-based electrocatalysts for building low-cost CO2 electrolyzers to selectively produce CO.

Specific heat capacity of the intermetallics ε-Cu3Sn, η/η′-Cu6Sn5, Al3Ni and Al3Ni2

The ε-Cu3Sn, η/η′-Cu6Sn5, Al3Ni and Al3Ni2 intermetallics have been produced as pure phases by the mushy zone resolidification in a temperature gradient. Powder XRD and SEM/EDX analysis were used for sample characterization. Heat capacity measurements have been performed in temperature ranges starting from 210 K up to temperatures close to the stability limits of the investigated phases. Based on the experimental results, the specific heat capacities of the intermetallics have been described from 0 K using an extended Einstein model. The model was chosen as one of most promising models for describing heat capacities for the 3rd generation of CALPHAD type thermodynamic databases and as it allows the determination of the standard entropies of intermetallic compounds.

In-situ observation of high-temperature Pb-free electric interconnections by synchrotron microradiography

Despite a large amount of research on transient liquid phase (TLP) bonding methods for high operating temperature Pb-free solder electric interconnections using Cu6Sn5 intermetallics (IMCs), two fundamental difficulties remain, namely, slow TLP process kinetics and uncontrolled void formation. Here we observe the TLP processes for rapid Cu6Sn5 growth using a recently developed technique via real-time synchrotron X-ray imaging. The technique enables in-situ characterization of the growth kinetics and real-time observation of the IMC evolution at the molten solder/solid substrate interfaces and the formation of voids and cracking during TLP bonding, which will contribute to the development of products suitable for high reliability and high-temperature applications, e.g., electric vehicles.

Rapid fabrication of tin-copper anodes for lithium-ion battery applications

The intermetallic Cu6Sn5 is ubiquitous in electronic interconnects where research has focused on controlling the size and distribution of this phase for improved performance. Cu6Sn5 also finds application as an anode material for advanced lithium-ion batteries. Cu6Sn5 anodes can be fabricated via an in-situ growth method involving the reaction between molten Sn and the Cu current collector. This manufacturing route offers some advantages over traditional anode fabrication however the process is slow, limiting its practical application. In this work we show the addition of 6 wt% Ni to the Cu current collector greatly accelerates the growth of (Cu,Ni)6Sn5 in Cu-xNi/Sn solid-melt couples, leading to a growth rate of up to 50x faster, reducing the processing time above 200 °C to less than 10 min. This research studies the dynamics of the formation of (Cu,Ni)6Sn5 between Cu-xNi alloys and liquid Sn through real-time observation using synchrotron X-ray imaging. The (Cu,Ni)6Sn5 growth dynamics are characterised, and the growth kinetics are analysed. Subsequently, the mechanism of the accelerated growth is investigated with electron backscatter diffraction and transmission electron microscopy. The results show the accelerated growth is due to the formation of η-(Cu,Ni)6Sn5 grains with two distinct Ni concentration ranges, leading to finer grains and spalling, which in turn facilitates the diffusion of Sn, enhancing the η-(Cu,Ni)6Sn5 formation kinetics.

Wafer Level Solid Liquid Interdiffusion Bonding: Formation and Evolution of Microstructures

Wafer-level solid liquid interdiffusion (SLID) bonding, also known as transient liquid-phase bonding, is becoming an increasingly attractive method for industrial usage since it can provide simultaneous formation of electrical interconnections and hermetic encapsulation for microelectromechanical systems. Additionally, SLID is utilized in die-attach bonding for electronic power components. In order to ensure the functionality and reliability of the devices, a fundamental understanding of the formation and evolution of interconnection microstructures, as well as global and local stresses, is of utmost importance. In this work a low-temperature Cu-In-Sn based SLID bonding process is presented. It was discovered that by introducing In to the traditional Cu-Sn metallurgy as an additional alloying element, it is possible to significantly decrease the bonding temperature. Decreasing the bonding temperature results in lower CTE induced global residual stresses. However, there are still several open issues to be studied regarding the effects of dissolved In on the physical properties of the Cu-Sn intermetallics. Additionally, partially metastable microstructures were observed in bonded samples that did not significantly evolve during thermal annealing. This indicates the Cu-In-Sn SLID bond microstructure is extremely stable.

The formation of intermetallic layer structure of SAC405/Cu and SAC405/ENImAg solder joint interfaces

PurposeThe surface finish is an essential step in printed circuit boards design because it provides a solderable surface for electronic components. The purpose of this study to investigate the effects of different surface finishes during the soldering and ageing process.Design/methodology/approachThe solder joints of Sn-4.0Ag-0.5Cu/Cu and Sn-4.0Ag-0.5Cu/electroless nickel/immersion silver (ENImAg) were investigated in terms of intermetallic (IMC) thickness, morphology and shear strength. The microstructure and compositions of solder joints are observed, and analyzed by using scanning electron microscopy (SEM-EDX) and optical microscope (OM).FindingsCompounds of Cu6Sn5 and (Cu, Ni)6Sn5 IMC were formed in SAC405/Cu and SAC405/ENImAg, respectively, as-reflowed. When the sample was exposed to ageing, new layers of Cu3Sn and (Ni, Cu)3Sn5 were observed at the interface. Analogous growth in the thickness of the IMC layer and increased grains size commensurate with ageing time. The results equally revealed an increase in shear strength of SAC405/ENImAg because of the thin layer of IMC and surface finish used compared to SAC405/Cu. Hence, a ductile fracture was observed at the bulk solder. Overall, the ENImAg surface finish showed excellent performance of solder joints than that of bare Cu.Originality/valueThe novel surface finish (ENImAg) has been developed and optimized. This alternative lead-free surface finish solved the challenges in electroless nickel/immersion gold and reduced cost without affecting the performance.

Combining multi-phase field simulation with neural network analysis to unravel thermomigration accelerated growth behavior of Cu6Sn5 IMC at cold side Cu–Sn interface

In Pb-free solder alloys used in solder balls of diameter of 50 µm or smaller, larger proportion of Cu6Sn5 intermetallics formation is a major reliability concern, and this is aggravated in presence of external thermal gradient. A complete understanding of the mechanism for intermetallics compound (IMC) growth under thermomigration is essential for devising solder materials resistant to degradation under thermal gradient. This work integrates neural network analysis with multi-phase field method to quantify the mechanism of thermomigration at the cold side of a solder-substrate system. At hot side temperature of 523.15 K, 1D multi-phase field model is built for a combined driving force of bulk diffusion and thermomigration, and is solved using finite element method (FEM). The free energy density function for the thermomigration driving force is introduced, and coupled with the functions for bulk and interfacial free energy density of each phase. Data of heats of transport, temperature difference and growth rate constant of IMC are obtained from multiple FEM simulations, and the FEM-generated dataset is employed in the neural network. The machine learning predicted growth rate constant is tallied with experimental value, and heat of transport of Cu in IMC phase (QCuimc) is determined from the inverse method. The obtained value of optimized QCuimc is +35.10 kJ/mol. 2D IMC grain growth simulations are performed with hot-side at 523.15 K and the cold side lowered to 523.0817 K and 522.0 K respectively, thereby revealing that the accelerated grain growth for larger temperature difference is noticed within the first 20 s of the simulations.

Selective etching and hardness properties of quenched SAC305 solder joints

PurposeThe purpose of this paper is to investigate the morphology of intermetallic (IMC) compounds and the mechanical properties of SAC305 solder alloy under different cooling conditions.Design/methodology/approachSAC305 solder joints were prepared under different cooling conditions/rates. The performance of three different etching methods was investigated: simple chemical etching, deep etching based on the Jackson method and selective removal of β-Sn by a standard three-electrode cell method. Phase and structural analyses were conducted by X-ray diffraction (XRD). The morphology of etched solder was examined by a field emission scanning electron microscope. The hardness evaluations of the solder joints were conducted by a Vickers microhardness tester.FindingsThe Ag3Sn network was significantly refined by the ice-quenching process. Further, the thickness of the Cu6Sn5 layer decreased with an increase in the cooling rate. The finer Ag3Sn network and the thinner Cu6Sn5 IMC layer were the results of the reduced solidification time. The ice-quenched solder joints showed the highest hardness values because of the refinement of the Ag3Sn and Cu6Sn5 phases.Originality/valueThe reduction in the XRD peak intensities showed the influence of the cooling condition on the formation of the different phases. The micrographs prepared by electrochemical etching revealed better observations regarding the shape and texture of the IMC phases than those prepared by the conventional etching method. The lower grain orientation sensitivity of the electrochemical etching method (unlike chemical etching) significantly improved the micrographs and enabled accurate observation of IMC phases.

Influence of cooling conditions on the interfacial Cu6Sn5 intermetallic compound in Sn-37Pb/Cu solder joints during reflow

Despite a shift to Pb-free solders in the majority of electronic assemblies, Pb-containing solders are still used in a variety of applications. Recent research has revealed the complexities of the intermetallic Cu6Sn5 in terms of its crystal structure and stability when present as the reaction product between Pb-free solders and common substrates. In light of these findings, the effect of multiple reflow cycles with different cooling conditions on the microstructure of the interfacial Cu6Sn5 intermetallic compound (IMC) between Sn-Pb solders and Cu substrates was re- examined. For this purpose, the Sn-37Pb (in wt.%) solder was reflowed on a Cu substrate at a temperature of around 240 °C and cooled at a rate of around 30 °C/min under each of two conditions; (i) direct-cooling to room temperature, and (ii) interrupted-cooling with extended isothermal holding periods of 30 and 180 seconds at 140 °C. This second condition was chosen to encourage the polymorphic transformation that occurs in the Cu6Sn5 (at an equilibrium temperature of 186 °C) at a temperature which minimises the stresses involved. Smaller cracks and a thinner interfacial IMC layer were observed in the solder joints that were reflowed repeatedly with the interrupted-cooling conditions. However, despite the higher number of cracks in the samples undergoing conventional reflow, the shear strength was not significantly affected.

Morphologies of Primary Cu6Sn5and Ag3Sn Intermetallics in Sn–Ag–Cu Solder Balls

This article focuses on the morphologies of primary Cu6Sn5 and Ag3Sn intermetallics in small Sn–Ag–Cu (O $270~\mu \text{m}$ ) solder balls. The Cu6Sn5 phase showed a large variety of different shapes and sizes, ranging from facetted hexagonal rods, to partly facetted splitting crystals and parallel growing branches, to dendritic crystals without facets. The results of electron backscatter diffraction (EBSD) measurements confirm [0001] as the major growth direction and the { $10\bar {1}0$ } planes as facets of the hexagonal rods. The formation of crystals splitting parallel to the { $10\bar {1}0$ } planes may be caused by a slight deviation of the major growth direction toward $\langle 2\bar {1}\bar {1} 0\rangle $ . Primary Ag3Sn intermetallics showed less morphology variations and solidified as typical plate structures with a planar and an irregular side. Sixfold star-shaped formations of multiple plates arranged around a common center have been investigated by EBSD. All plates appear to have the same hexagonal orientation and possible growth directions are parallel to the { $10\bar {1}0$ } planes. However, these pseudohexagonal structures showed color differences between plates of different growth directions, if investigated with polarized light microscopy. Those orientation differences were not detectable by EBSD. Possible interpretations are discussed on the basis of the orthorhombic distorted lattice and by possible twinning mechanisms.

Two-Phase η′ + η Region in Cu6Sn5 Intermetallic: Insight into the Order–Disorder Transition from Diffusion Couples

The ongoing electrification and miniaturization increase the quality demands on solder joints. A bottleneck for solder joint reliability can be the intermetallic Cu6Sn5 phase, which undergoes a phase transition, implying a volume change in a relevant temperature range. There are contradicting reports on the sign and magnitude of this volume change, which possibly implements stresses and cracks in solder joints. To clarify the characteristics of the phase transition, different samples were manufactured by applying industrial-like standards and isothermal heat treatments around the predicted phase transition temperature. Using x-ray diffraction, a coexistence of ordered η′ and disordered η was detected in samples treated at 438–445 K. The lattice parameters show that the volume of the disordered η phase is approximately 0.64–0.65% smaller than the one of the ordered η′ phase. A comparison with order–disorder transitions in structurally related phases shows that the volume change based on order–disorder transitions is normally of opposite sign and around 0.1–0.2%. Therefore, an effect of different compositions is considered responsible for the volume change. Adopting the exact composition Cu6Sn5 (Cu1.20Sn) for the η′ phase, it was estimated, based on density functional theory calculations from the literature, that the coexisting η phase assumes lower Cu content of Cu1.171Sn at 438 K and Cu1.174Sn at 445 K. In contrast, the lattice parameters of η′, generated at different temperatures, imply a largely temperature-independent composition of Cu1.20Sn. This leads to adjustments of the Cu-Sn phase diagram.

Interplay of Wettability, Interfacial Reaction and Interfacial Thermal Conductance in Sn-0.7Cu Solder Alloy/Substrate Couples

Directional solidification experiments coupled with mathematical modelling, drop shape analyses and evaluation of the reaction layers were performed for three different types of joints produced with the Sn-0.7 wt.%Cu solder alloy. The association of such findings allowed understanding the mechanisms affecting the heat transfer efficiency between this alloy and substrates of interest. Nickel (Ni) and copper (Cu) were tested since they are considered work piece materials of importance in electronic soldering. Moreover, low carbon steel was tested as a matter of comparison. For each tested case, wetting angles, integrity and nature of the interfaces and transient heat transfer coefficients, ‘h’, were determined. Even though the copper has a thermal conductivity greater than nickel, it is demonstrated that the occurrence of voids at the copper interface during alloy soldering may decrease the heat transfer efficiency, i.e., ‘h’. Oppositely, a more stable and less defective reaction layer was formed for the alloy/nickel couple. This is due to the suppression of the undesirable thermal contraction since the hexagonal Cu6Sn5 intermetallics is stable at temperatures below 186°C in the presence of nickel.

Substructure of Intermetallic Thin-Film Cu3Sn

The crystalline structure of intermetallic Cu3Sn synthesized by successively condensing thin layers of copper and tin on a substrate at 150°C has been studied. Cu3Sn compound exists in a very narrow homogeneity range and has a long-period close-packed ordered D019 superstructure. It has been found that the crystal lattice exhibits many slip traces associated with dislocation motion. The dislocation motion is due to the stressed state of the crystal, which can be characterized as uniform extension. Electron micrographs show that slip traces in the Cu3Sn crystal are parallel to the ( $$\bar {1}\bar {1}21$$ ) and ( $$11\bar {2}1$$ ) planes belonging to pyramidal slip system II, which is a main slip system along with pyramidal and basal ones. Slip traces result from the motion of partial dislocations, as indicated by the amount of slip, which is equal to half the interplanar distance. Since the crystal is ordered, slip is accomplished by a pair of superpartial dislocations and a slip trace may be a superstructural or complex stacking fault.