Investigation of Sn Whisker Growth in Electroplated Sn and Sn-Ag as a Function of Plating Variables and Storage Conditions

Sn whiskers are becoming a serious reliability issue in Pb-free electronic packaging applications. Among the numerous Sn whisker mitigation strategies, minor alloying additions to Sn have been proven effective. In this study, several commercial Sn and Sn-Ag baths of low-whisker formulations are evaluated to develop optimum mitigation strategies for electroplated Sn and Sn-Ag. The effects of plating variables and storage conditions, including plating thickness and current density, on Sn whisker growth are investigated for matte Sn, matte Sn-Ag, and bright Sn-Ag electroplated on a Si substrate. Two different storage conditions are applied: an ambient condition (30°C, dry air) and a high-temperature/high-humidity condition (55°C, 85% relative humidity). Scanning electron microscopy is employed to record the Sn whisker growth history of each sample up to 4000 h. Transmission electron microscopy, x-ray diffraction, and focused ion beam techniques are used to understand the microstructure, the formation of intermetallic compounds (IMCs), oxidation, the Sn whisker growth mechanism, and other features. In this study, it is found that whiskers are observed only under ambient conditions for both thin and thick samples regardless of the current density variations for matte Sn. However, whiskers are not observed on Sn-Ag-plated surfaces due to the equiaxed grains and fine Ag₃Sn IMCs located at grain boundaries. In addition, Sn whiskers can be suppressed under the high-temperature/high-humidity conditions due to the random growth of IMCs and the formation of thick oxide layers.     

Effect of Cu additives on Sn whisker formation of Sn(Cu) finishes

Sn whisker formation on Sn(Cu) finishes has been studied. (1) With respect to the thickness effect, we found that Sn whisker density for pure Sn and Sn0.7Cu finishes has a linear relationship with the finish thickness. The safety thickness for Sn and Sn0.7Cu finishes is about 10 μm and 20 μm, respectively. (2) With respect to the alloying effect, we found that Sn whisker formation could be retarded by increasing Cu content in the Sn(Cu) finishes. We conclude that the Cu additives could reduce the two major driving forces of the Sn whisker formation, i.e., metal underlayer dissolution and thermal stress. The Cu additives self-formed a Cu-Sn compound barrier layer, which effectively prevents the reaction and dissolution with the metal underlayer. On the other hand, the Cu additives precipitated out as Cu-Sn compound in the Sn(Cu) finish layer, which is believed to be the reason for smaller values of the coefficient of thermal expansion (CTE) for Sn(Cu) alloys. The smaller CTE values results in a lower thermal stress level in the Sn(Cu) finishes.     

Mitigation of Sn Whisker Growth by Small Bi Additions

In this study, the morphological development of electroplated matte Sn and Sn-xBi (x = 0.5 wt.%, 1.0 wt.%, 2.0 wt.%) film surfaces was investigated under diverse testing conditions: 1-year room-temperature storage, high temperature and humidity (HTH), mechanical loading by indentation, and thermal cycling. These small Bi additions prevented Sn whisker formation; no whisker growth was observed on any Sn-xBi surface during either the room-temperature storage or HTH testing. In the indentation loading and thermal cycling tests, short (<5 μm) surface extrusions were occasionally observed, but only on x = 0.5 wt.% and 1.0 wt.% plated samples. In all test cases, Sn-2Bi plated samples exhibited excellent whisker mitigation, while pure Sn samples always generated many whiskers on the surface. We confirmed that the addition of Bi into Sn refined the grain size of the as-plated films and altered the columnar structure to form equiaxed grains. The storage conditions allowed the formation of intermetallic compounds between the plated layer and the substrate regardless of the Bi addition. However, the growth patterns became more uniform with increasing amounts of Bi. These microstructural improvements with Bi addition effectively released the internal stress from Sn plating, thus mitigating whisker formation on the surface under various environments.     

Whisker mitigation measures for Sn-plated Cu for different stress tests

The effectiveness of the widely-used whisker mitigation measures for Sn-plated Cu base material (annealing at 150 °C for 1 h or a Ni interlayer) were investigated after temperature cycling and after storage at room temperature. It was found that these measures prevent whisker growth during isothermal storage, but not during temperature cycling. These mitigation measures do apparently not reduce the compressive stress that builds up during temperature cycling due to different coefficients of thermal expansion of Sn and Cu. A change of the Sn microstructure to globular grains is proposed and investigated as potential whisker mitigation measure for temperature cycling.     

In Situ Measurement of Stress and Whisker/Hillock Density During Thermal Cycling of Sn Layers

Compressive stress is believed to be the primary driving force that makes Sn whiskers/hillocks grow, but the mechanisms that create the stress (e.g., intermetallic compound growth) are difficult to control. As an alternative, the thermal expansion mismatch between the Sn layer and the substrate can be used to induce stress in a controlled way via heating and cooling. In this work, we describe real-time experiments which quantify the whiskering behavior and stress evolution during cyclic heating. The density of whiskers/hillocks is measured with an optical microscope, while the stress is measured simultaneously with a wafer-curvature-based multi-beam optical stress sensor. Results from three thermal cycles are described in which the samples are heated from room temperature to 65 °C at rates of 10, 30, and 240 °C/h. In each case, we find that the whisker/hillock formation is the primary source of stress relaxation. At fast heating rates, the relaxation is proportional to the number of hillocks, indicating that the stress is relaxed by the nucleation of many small surface features. At slower heating rates, the whisker/hillock density is lower, and continual growth of the features is suggested after nucleation. Long whiskers are found to be more likely to form in the slow heating cycle.     

Investigation of relation between intermetallic and tin whisker growths under ambient condition

The relation between the whisker growth and intermetallic on various lead-free finish materials that have been stored at ambient condition for 2 yrs (6.3 × 10⁷ s) is investigated. The matte Sn plated leadframe (LF) had the needle-shaped whisker and the nodule-shaped whisker was observed on the semi-bright Sn plated LF. Both the Sn plated LFs had a same columnar grain structure and both whiskers were grown in connection with the scalloped intermetallic compound (IMC) layer. The morphology of the IMC layer is similar, regardless of the area which has whisker or not. On the Sn–Bi finish and bright Sn plated LF, hillock-shaped and sparsely grown branch-shaped whiskers were observed, respectively. The IMC grew irregularly under both the areas with or without whisker. The IMC growth along the Sn grain boundaries generated inner compressive stress at the plating layer. Atomic force microscopy (AFM) profiling analysis is useful for characterization the IMC growth on the Sn and Cu interface. The measured root mean square (RMS) values IMC roughness on semi-bright Sn, matte Sn, and bright Sn plated LF were 1.82 μm, 1.46 μm, and 0.63 μm, respectively. However, there is no direct relation between whisker growth and the RMS value. Two layers of η′-Cu₆Sn₅ were observed using field emission transmission electron microscopy (FE-TEM): fine grains and coarse grains existed over the fine grains.     

Significance of Nucleation Kinetics in Sn Whisker Formation

Sn whiskers are believed to form in response to stress in layers used as protective coatings. However, what makes them form at specific sites on the surface is not known. We have used thermal expansion mismatch to induce stress and observe the resulting whisker formation. Cross-sectional measurements of the region around whiskers show that there are oblique grain boundaries under the whiskers that are not seen in the as-deposited columnar structure. The kinetics also suggest that the whiskering sites may be formed by a nucleation process. Based on these results, we propose a nucleation mechanism in which the boundaries of the surrounding grains migrate due to strain energy differences and create oblique boundaries at which whiskers can form. A simple model is developed to predict the stress-dependence of the nucleation rate.     

Whisker growth on surface treatment in the pure tin plating

Whisker behavior at various surface treatment conditions of pure Sn plating are presented. The temperature cycling test for 600 cycles and the ambient storage for 1 year was performed, respectively. From the temperature cycling test, bent-shaped whiskers were observed on matte and semibright Sn plating, and flower-shaped whisker on bright Sn plating. The bright Sn plating has smaller whiskers than the other types of Sn plating, and the whisker growth density per unit area is also lower than the others. After 1 year under ambient storage, nodule growth of FeNi42 lead frame (LF) was observed in some parts. The Cu LF showed about a 9.0 μm hillock-shaped whisker. This result demonstrated that the main determinant of whisker growth was the number of temperature cycling (TC) in the FeNi42 LF, whereas it was the time and temperature in the Cu LF. Also, whisker growth and shape varied with the type of surface treatment and grain size of plating.     

Tin Whisker Growth Induced by High Electron Current Density

The effect of electric current on the tin whisker growth on Sn stripes was studied. The Sn stripes, 1 μm in thickness, were patterned on silicon wafers. The design of the Sn stripes allowed the simultaneous study of the effect of current crowding and current density. Current stressing was performed in ovens set at 30, 50, or 70°C, and the current density used ranged from 4.5 × 10⁴ A/cm² to 3.6 × 10⁵ A/cm². It was found that the stress induced by the electric current caused the formation of many Sn whiskers. A higher current density caused more Sn whiskers to form. Of the three temperatures studied, 50°C was the most favorable one for the formation of the Sn whiskers. In addition, the current-crowding effect also influenced whisker growth.     

Correlation between Experimental Results and FE Simulations to Evaluate Lead-Free BGA Assembly Reliability

Lead-free solder is taken into use in the electronics industry and there is a lack of data about the reliability of the lead-free assemblies. In this paper, a methodology on the acceleration factor (AF) assessment is described. The lead-free BGA assemblies are submitted to various accelerated ageing test (thermal cycles). An event detector from AnaTech is used in order to determine the cycles-to-failure. The three-dimensional nonlinear finite element model of BGA assembly is designed and built using ANSYS software. The thermo-mechanical simulations are carried out on this model in order to compute the strain energy density (SED) dissipated in the solder joints during the thermal cycles. Then the correlation between the experiments and the simulations allows to assess a SED critical value in order to predict the cycles-to-failure for another test.     

Board level solder joint reliability modeling and testing of TFBGA packages for telecommunication applications

For thin-profile fine-pitch BGA (TFBGA) packages, board level solder joint reliability during the thermal cycling test is a critical issue. In this paper, both global and local parametric 3D FEA fatigue models are established for TFBGA on board with considerations of detailed pad design, realistic shape of solder joint, and nonlinear material properties. They have the capability to predict the fatigue life of solder joint during the thermal cycling test within ±13% error. The fatigue model applied is based on a modified Darveaux’s approach with nonlinear viscoplastic analysis of solder joints. A solder joint damage model is used to establish a connection between the strain energy density (SED) per cycle obtained from the FEA model and the actual characteristic life during the thermal cycling test. For the test vehicles studied, the maximum SED is observed at the top corner of outermost diagonal solder ball. The modeling predicted fatigue life is first correlated to the thermal cycling test results using modified correlation constants, curve-fitted from in-house BGA thermal cycling test data. Subsequently, design analysis is performed to study the effects of 14 key package dimensions, material properties, and thermal cycling test condition. In general, smaller die size, higher solder ball standoff, smaller maximum solder ball diameter, bigger solder mask opening, thinner board, higher mold compound CTE, smaller thermal cycling temperature range, and depopulated array type of ball layout pattern contribute to longer fatigue life.     

Comprehensive board-level solder joint reliability modeling and testing of QFN and PowerQFN packages

For quad flat non-lead (QFN) packages, board-level solder joint reliability during thermal cycling test is a critical issue. In this paper, a parametric 3D FEA sliced model is established for QFN on board with considerations of detailed pad design, realistic shape of solder joint and solder fillet, and non-linear material properties. It has the capability to predict the fatigue life of solder joint during thermal cycling test within ±34% error. The fatigue model applied is based on a modified Darveaux’s approach with non-linear viscoplastic analysis of solder joints. A solder joint damage model is used to establish a connection between the strain energy density (SED) per cycle obtained from the FEA model and the actual characteristic life during thermal cycling test. For the test vehicles studied, the maximum SED is observed mostly at the top corner of peripheral solder joint. The modeling predicted fatigue life is first correlated to thermal cycling test results using modified correlation constants, curve-fitted from in-house QFN thermal cycling test data. Subsequently, design analysis is performed to study the effects of 17 key package dimensions, material properties, and thermal cycling test condition. Generally, smaller package size, smaller die size, bigger pad size, thinner PCB, higher mold compound CTE, higher solder standoff, and extra soldering at the center pad help to enhance the fatigue life. Comparisons are made with thermal cycling test results to confirm the relative trends of certain effects. Another enhanced QFN design with better solder joint reliability, PowerQFN, is also studied and compared with QFN of the same package size.     

The Role of Silver in Mitigation of Whisker Formation on Thin Tin Films

The mitigating effect of alloying Sn thin films with Ag on the formation of Sn whiskers was investigated by time-resolved investigations employing x-ray diffraction for phase and stress analyses and focused ion beam microscopy for morphological characterization of the surfaces and cross-sections of the specimens. The investigated Sn-6 wt.%Ag thin films were prepared by galvanic co-deposition. The results are compared with those obtained from investigation of pure Sn films and discussed with regard to current whisker-growth models. The simultaneous deposition of Sn and Ag leads to a fine-grained microstructure consisting of columnar and equiaxed grains, i.e. an imperfect columnar Sn film microstructure. Isolated Ag3Sn grains are present at the Sn grain boundaries in the as-deposited films. Pronounced grain growth was observed during aging at room temperature, which provides a global stress relaxation mechanism that prevents Sn whisker growth.     

Crystal size and direction dependence of the elastic properties of Cu3Sn through molecular dynamics simulation and nanoindentation testing

The study aims at exploring the elastic properties of orthorhombic Cu₃Sn crystals through a proposed molecular dynamics (MD) simulation model based on the modified embedded atom method (MEAM) and nanoindentation testing. The focuses of the study are placed on their dependence on the crystal size and direction. The electronic nature of single crystal Cu₃Sn is also examined by using first-principles calculations based on density function theory (DFT). According to continuum mechanics, the elastic stiffness coefficients of the single crystal Cu₃Sn are derived from the calculated energy, and used in the generalized Hook’s law in compliance form to compute the associated elastic constants. The simulated elastic properties are compared with the results of the published first-principles calculations. For comparison with the present nanoindentation finding and the other published experimental data, the effective elastic properties of the polycrystalline Cu₃Sn together with their size dependence are also derived using the Voigt–Reuss bounds and Voigt–Reuss–Hill average based on the calculated single crystal data.The simulation results show that the orthorhombic Cu₃Sn crystals exhibit a high elastic anisotropy, which has been also confirmed by the electronic structure analysis, and also a strong size and direction dependence of elasticity. In addition, the calculated effective elastic properties of the polycrystalline Cu₃Sn agree well with the present nanoindentation results and the published theoretical/experimental data.     

Can Whiskers Grow on Bulk Lead-Free Solder?

Many possible mechanisms for whisker growth exist, each possible in various scenarios investigated in the literature. This contribution addresses the importance of residual mechanical stress in a solder alloy for providing some of the energy necessary to drive possible whisker growth. We investigate the indentations made on bulk lead-free solder (Sn3.5Ag) to introduce various levels of residual energy associated with localized residual stresses. We confirm that localized residual stresses, in the absence of a thin-film geometry, significant oxide thickness, and interdiffusional stresses from intermetallic Cu-Sn compounds, do not result in the formation of whiskers in bulk Sn3.5Ag. Thus, the combination of stresses associated with thin films (either thermal misfit, plating, or chemical) and the oxidation of Sn at the surface is likely required for continuous whisker growth.     

Altering the Mechanical Properties of Sn Films by Alloying with Bi: Mimicking the Effect of Pb to Suppress Whiskers

Stress is believed to be the main driving force for whisker formation in Sn coatings on Cu. This suggests that whiskering can be suppressed by enhancing stress relaxation in the Sn layer, which is believed to be the reason why Sn-Pb alloys do not form whiskers. However, Pb is no longer acceptable for use in electronics manufacturing. As an alternative, we used pulsed plating to create Sn-Bi coatings with an equiaxed microstructure similar to that of Sn-Pb alloys. An optical wafer curvature technique was used to measure stress relaxation kinetics in Sn, Sn-Pb and Sn-Bi alloy thin films during thermal cycles. The results show that Sn-Bi films have significantly enhanced stress relaxation relative to pure Sn films. Comparison between Sn-Bi samples with equiaxed and columnar microstructures shows that both microstructure and alloy composition play a role in enhancing the stress relaxation.     

Finite element analysis of thermal and mechanical stresses due to the grain anisotropy of polycrystalline β-Sn

In order to investigate the stress and strain distributions caused by the grain anisotropy of polycrystalline β-Sn, a finite-element (FE) analysis was conducted using a polycrystalline model that considers the effect of grain anisotropy on the elastic and plastic properties. Even in the case of thermal free expansion with a temperature change of 75 °C, plastic strains can be generated locally in polycrystalline β-Sn. This might be due to the high anisotropy of the thermal expansion coefficient and the low yield strength of β-Sn. It was found that both in-phase and out-of-phase thermal stresses can be present in the polycrystalline β-Sn simultaneously. The highest stress and strain appeared in the grains whose orientation is relatively different from those of neighboring grains, near the grain boundaries. This might cause the formation of a grain boundary void in the Pb-free solder. Comparing the strain distribution due to the thermal expansion coefficient anisotropy and the Young's modulus anisotropy, it was determined that the maximum value of the plastic strain due to the thermal expansion coefficient anisotropy is approximately 10% higher than that due to the anisotropy of Young's modulus, and the high strain areas are also different in the two cases. The thermo-mechanical fatigue life of β-Sn might be shorter than that estimated using the isothermal low cycle fatigue life at the same level as the macroscopic strain and could not be estimated by the previous method.     

Mechanism of Reaction Between Nd and Ga in Sn-Zn-0.5Ga-xNd Solder

The mechanism of reaction between Nd and Ga in Sn-Zn-0.5Ga-xNd solder was investigated in order to enhance the reliability of soldered joints. It was found that, after aging treatment at ambient temperature and 125°C for over 3000 h, no Sn whisker growth was observed in Sn-9Zn-0.5Ga-0.08Nd soldered joints. X-ray diffraction (XRD) analysis and thermodynamic calculations indicated that Ga reacted with Nd instead of Sn-Nd intermetallic compound (IMC), eliminating Sn whisker growth. Shear force testing was carried out, and the results indicated that Sn-9Zn-0.5Ga-0.08Nd solder still had excellent mechanical properties after aging treatment. This new discovery can provide a novel approach to develop high-reliability solder without risk of Sn whiskers.     

A Statistical Study of Sn Whisker Population and Growth During Elevated Temperature and Humidity Tests

Storage tests at elevated temperature and humidity conditions have been widely adopted as one of the major acceleration tests for Sn whisker growth. However, the driving force associated and the nucleation and growth process of whiskers are yet to be fully understood. In this paper, Sn whisker growth on Cu leadframe material at two different test conditions is compared. Both loose and board-mounted components were used. At each read point, the length and location of every whisker observed was recorded. Statistical characteristics and growth rate of the whisker population will be presented for each of the tests conditions. On loose components, corrosion of the Sn finish was observed near the tip and the dam bar cut area of the leads with backscatter scanning electron microscopy (SEM) and optical microscopy. The entire population of whiskers was located in these corroded areas, and there were zero whiskers located in the noncorroded areas on the same leads. On board-mounted components, the corrosion level of the Sn finish, as well as the whisker population and length was greatly reduced compared to those on the loose components. These results suggest that the corrosion of Sn finish in high-temperature and high-humidity conditions is the major driving force for whisker growth. The cause for the difference between the loose and board-mounted components is also analyzed     

The influence of thermal aging on joint strength and fracture surface of Pb/Sn and Au/Sn solders in laser diode packages

The joint strength and fracture surface of Pb/Sn and Au/Sn solders in laserdiode packages after thermal-aging testing were studied experimentally. Specimens were aged at 150°C for up to 49 days. The joint strength decreased as aging time increased. The microstructure and fracture surface of the Pb/Sn and Au/Sn solder joints showed that the joint strength decrease was caused by both the enlargement of the initial voids and an increase in the number of voids as aging time increased. The formation of Kirkendall voids with intermetallic-compound (IMC) growth of the Pn/Sn solder as aging time increased was also a possible mechanism for the joint-strength reduction. Finite-element method (FEM) simulations were performed on the joint-strength estimation of Pb/Sn and Au/Sn solders in thermal-aging tests. The coupled thermal-elasticity-plasticity model was used to simulate distributions of the thermal and residual stresses, creep deformation, and joint-strength variations in the solder joints under various thermal-aging tests. Simulation results were in good agreement with the experimental measurements that the solder-joint strength decreased as aging time increased. The result suggests that the FEM is an effective method for analyzing and predicting the solder-joint strength in laserdiode packages.