Mitigation of Sn Whisker Growth by Composite Ni/Sn Plating

Tin (Sn) is a key industrial material in coatings on various components in the electronics industry. However, Sn is prone to the development of filament-like whiskers, which is the leading cause of many types of damage to electronics reported in the last several decades. Due to its properties, a tin-lead (Sn-Pb) alloy coating can mitigate Sn whisker growth. However, the demand for Pb-free surface finishes has rekindled interest in the Sn whisker phenomenon. In order to achieve properties similar to those naturally developed in a Sn-Pb alloy coating, we carried out a study on deposited films with other Sn alloys, such as tin-bismuth (Sn-Bi), tin-zinc (Sn-Zn), and tin-copper (Sn-Cu), electrodeposited onto a brass substrate by utilizing a pulse plating technique. The results indicated that the Sn alloy films modified the columnar grain structure of pure Sn into an equiaxed grain structure and increased the incubation period of Sn whisker growth. The primary conclusions were based on analysis of the topography and microstructural characteristics in each case, as well as the stress distribution in the plated films computed by x-ray diffraction, and the␣amount of Sn whisker growth in each case, over 6 months under various environmental influences.     

Whisker Growth Behavior of Sn and Sn Alloy Lead-Free Finishes

Sn whisker growth behavior, over periods of time up to 10,080 h at room temperature, was examined for Sn and Sn-Cu, Sn-Ag, Sn-Bi, and Sn-Pb coatings electroplated on copper in 2 μm and 5 μm thicknesses to understand the effects of the alloying elements on whisker formation. Sn-Ag and Sn-Bi coatings were found to significantly suppress Sn whisker formation compared with the pure Sn coatings, whereas whisker growth was enhanced by Sn-Cu coatings. In addition, annealed Sn and Sn-Pb coatings were found to suppress Sn whisker formation, as is well known. Compared with the 2-μm-thick coatings, the 5-μm-thick coatings had high whisker resistance, except for the Sn-Cu coating. Whisker growth was correlated with coating crystal texture and its stability during storage, crystal grain microstructure, and the formation of intermetallic compounds at Sn grain boundaries and substrate–coating interfaces.     

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.     

Equi-Axed Grain Formation in Electrodeposited Sn-Bi

Sn is widely used as a coating in the electronics industry because it provides excellent solderability, ductility, electrical conductivity, and corrosion resistance. However, Sn whiskers have been observed to grow spontaneously from Sn electrodeposits and are known to cause short circuits in fine-pitched pre-tinned electrical components. We report here a deposition strategy that produces an equi-axed and size-tunable grain structure in Sn-Bi alloys electrodeposited from a commercial bright Sn electrolyte. An equi-axed grain structure should allow a more uniform creep to relieve compressive stress with no localized surface disturbance. The standard potential for Bi is about 0.45 V more positive than Sn. Pulsed deposition can selectively turn on and off the Sn deposition reaction. During the off cycle, a displacement reaction between metallic Sn on the electrode surface and Bi³⁺ in solution selectively dissolves Sn and deposits Bi, effectively terminating the growth from the previous cycle and forcing the Sn to nucleate a new grain on the Bi-enriched surface. The grain size is tunable by varying the pulsing conditions, and an equi-axed structure can be obtained with as little as 3 at.% Bi. This surface enrichment of Bi by potential modulation is similar to that which occurs naturally in Sn-Pb, and provides an avenue for breaking up the columnar grain structure inherent to pure Sn, thus providing an additional diffusion path for Sn that may prevent whisker growth.     

Mitigation and Verification Methods for Sn Whisker Growth in Pb-Free Automotive Electronics

This work describes mitigation methods against Sn whisker growth in Pb-free automotive electronics using a conformal coating technique, with an additional focus on determining an effective whisker assessment method. We suggest effective whisker growth conditions that involve temperature cycling and two types of storage conditions (high-temperature/humidity storage and ambient storage), and analyze whisker growth mechanisms. In determining an efficient mitigation method against whisker growth, surface finish and conformal coating have been validated as effective means. In our experiments, the surface finish of components comprised Ni/Sn, Ni/SnBi, and Ni/Pd. The effects of acrylic silicone, and rubber coating of components were compared with uncoated performance under high-temperature/humidity storage conditions. An effective whisker assessment method during temperature cycling and under various storage conditions (high temperature/humidity and ambient) is indicated for evaluating whisker growth. Although components were finished with Ni/Pd, we found that whiskers were generated at solder joints and that conformal coating is a useful mitigation method in this regard. Although whiskers penetrated most conformal coating materials (acrylic, silicone, and rubber) after 3500 h of high-temperature/humidity storage, the whisker length was markedly reduced due to the conformal coatings, with silicone providing superior mitigation over acrylic and rubber.     

Stress Relaxation Mechanisms of Sn and SnPb Coatings Electrodeposited on Cu: Avoidance of Whiskering

The interrelations of microstructural evolution, phase formation, residual stress development, and whiskering behavior were investigated for the systems of Sn coating on Cu and SnPb coating on Cu during aging at room temperature. It was shown that the whisker-preventing effect of Pb addition to pure Sn can be attributed to a Pb-induced change of the stress relaxation mechanism in the coating: Pure Sn coatings, with a columnar grain morphology, relax mechanical stress via localized, unidirectional grain growth from the surface of the coating (i.e., whisker formation occurs), whereas SnPb coatings, with an equiaxed grain morphology, relax mechanical stress via uniform grain coarsening without whisker formation. It can thus be suggested that tuning of the Sn grain morphology (i.e., establishing an equiaxed grain morphology) is a straightforward method of microstructural control to suppress whisker formation at room temperature. Experimental results obtained in this project validate this conclusion.     

Optimum Thickness of Sn Film for Whisker Growth

By depositing different thicknesses of Sn films over a silicon wafer precoated with Cr and Ni adhesion layers and then by bending the tinned wafer using a dead load applied at the center to introduce the same compressive stresses in the Sn films, the growth rate of whiskers appeared to have a maximum for a certain thickness. This is explained by assuming the Sn atoms to flow along the vertical grain boundaries (perpendicular to the interface) into the interface between Sn and Ni and then along the interface to the root of the whisker through some more vertical grain boundaries. The resistance along the vertical grain boundaries appeared to control the rate of whisker growth for thick films.     

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.     

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.     

Sn-Cu Intermetallic Grain Morphology Related to Sn Layer Thickness

Tin is widely used as a coating material for copper metal in the electronics industry where tin whisker growth is a concern because it affects the reliability of electronic devices. Because whisker growth reduces joint reliability, it is important to monitor the growth of Cu₃Sn and Cu₆Sn₅, which is usually done by using an X-ray diffraction method to estimate the thickness of the tin layer. In this study, we use the sequential electrochemical reduction analysis (SERA) technique to measure the thickness of layers of pure tin, Cu₆Sn₅, and Cu₃Sn. We also discuss the depletion rate of tin layers at high-temperature aging and the growth of these intermetallics.     

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.     

Hillock and Whisker Growth on Sn and SnCu Electrodeposits on a Substrate Not Forming Interfacial Intermetallic Compounds

Intermetallic compound (IMC) formation at the interface between the tin (Sn) plating and the copper (Cu) substrate of electronic components has been thought to produce compressive stress in Sn electrodeposits and cause the growth of Sn whiskers. To determine if interfacial IMC is a requirement for whisker growth, bright Sn and a Sn-Cu alloy were electroplated on a tungsten (W) substrate that does not form interfacial IMC with the Sn or Cu. At room temperature, conical Sn hillocks grew on the pure Sn deposits and Sn whiskers grew from the Sn-Cu alloy electrodeposits. These results demonstrate that interfacial IMC is not required for initial whisker growth.     

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     

Sn Corrosion and Its Influence on Whisker Growth

The microstructure and crystal structure of condensation-induced corrosion products, vapor phase induced oxidation products, Cu-Sn intermetallics, and Sn whiskers that formed on electroplated matte Sn on Cu-alloy after exposure 2500 h in a 60 degC/93%RH ambient were characterized with scanning electron microscopy, (SEM), focused ion beam (FIB) microscopy, energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and selected area electron diffraction (SAD). The corrosion product was identified as crystalline SnO₂. The oxidation of Sn in condensed water was at least four orders of magnitude larger than that in moist vapor at 60 degC. All Sn whiskers were found to be within 125 mum of the corrosion product. Based on these observations, a theory was developed. The theory assumes that oxidation leads to the displacement of Sn atoms within the film. Because the grain boundaries and free surfaces of the film are pinned, the oxidation-induced excess Sn atoms are constrained within the original volume of the Sn-film. The trapped excess Sn atoms create localized stress, excess strain energy, in the Sn-film. If and when the pinning constraint is relaxed, as for example would occur when the surface oxide on the film cracks, then the Sn atoms can diffuse to lower energy configurations. When this occurs, whisker nucleation and growth begins. The theory was tested by detailed measurements and comparison of the corrosion volume and the whisker volume in two different samples. The volume comparisons were consistent with the theory     

Finite Element Modeling of Stress Evolution in Sn Films due to Growth of the Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> Intermetallic Compound

We use finite element simulations to quantitatively evaluate different mechanisms for the generation of stress in Sn films due to growth of the Cu₆Sn₅ intermetallic phase at the Cu-Sn interface. We find that elastic and plastic behavior alone are not sufficient to reproduce the experimentally measured stress evolution. However, when grain boundary diffusion is included, the model results agree well with experimental observations. Examination of conditions necessary to produce the observed stresses provides insight into potential strategies for minimizing stress generation and thus mitigating Sn whisker growth.     

Observed correlation of Sn oxide film to Sn whisker growth in Sn-Cu electrodeposit for Pb-free solders

Localized cracking of surface oxide has been proposed as a necessary step in the nucleation of Sn whiskers in Sn electrodeposited films. To evaluate the effects of the oxide film on Sn whisker growth, a bright Sn-Cu electrodeposited film was inserted into an ultrahigh vacuum Auger system, cleaned using an Ar⁻ ion beam to remove the oxide film, and aged in the 2×10⁻⁹ Pa Auger system chamber. Whiskers and other features present during Ar⁺ ion cleaning left visible “shadows” on the surface. During aging in the ultrahigh vacuum system, new whiskers, identified by the absence of the telltale shadows, nucleated and grew. Based on these observations, the presence or absence of an oxide film has a minimal effect on Sn whisker nucleation and growth.     

Humidity Effects on Sn Whisker Formation

Due to legislative issues, Pb-containing metallizations on semiconductor components are rapidly converted to Pb-free alternatives. One of the most popular alternatives is Sn electroplating. The major problem of these platings is the formation of Sn whiskers. In earlier publications, two mechanisms were uncovered that are responsible for whisker growth. However, these mechanisms do not explain whisker growth in high humidity. Therefore, Freescale, Infineon, Philips, and STMicrolectronics (E4) joined forces and started a design of experiment (DoE) in order to resolve this mechanism. It is shown that in high humidities, whiskers grow due to oxidation and corrosion of the Sn plating, irrespective of the base material. It is also shown that board assembly mitigates the whisker growth by this mechanism but does not completely prevent it     

Stress Relaxation in Sn-Based Films: Effects of Pb Alloying, Grain Size, and Microstructure

Stress is believed to provide the driving force for growth of Sn whiskers, so stress relaxation in the Sn layer plays a key role in their formation. To understand and enhance stress relaxation in Sn-based films, the effects of Pb alloying and microstructure on their mechanical properties have been studied by observing the relaxation of thermal expansion-induced strain. The relaxation rate is found to increase with film thickness and grain size in pure Sn films, and it depends on the microstructure in Pb-alloyed Sn films. Measurements of multilayered structures (Sn on Pb-Sn and Pb-Sn on Sn) show that changing the surface layer alone is not sufficient to enhance the relaxation, indicating that the Pb enhances relaxation in the bulk of the film and not by surface modification. Implications of our results for whisker mitigation strategies are discussed.     

Tin Whisker Nucleation and Growth on Sn-Pb Eutectic Coating Layer Inside Plated Through Holes With Press-Fit Pins

It has been long believed that residual stress is the root cause for tin whisker formation on pure tin-plated component leads. However, tin whisker formation could be observed on the surface of other tin-based alloys under certain conditions. In this study, the whisker formation was reported on a coating layer of Sn-Pb eutectic hot air solder leveling (HASL), which was under compression stress conditions due to the inserted compliant pins. In-Situ scanning electron microscopy was used to monitor the nucleation and growth of whiskers. In addition, a mechanical experiment and non-linear contact finite element analysis were used to estimate the magnitude of the stress in the HASL coating layer. It was found that the tin whisker formation with whisker size of more than 10 mum could occur on the surface of 60Sn-60Pb plating within less than 30 min at an ambient temperature under compressing stress conditions. The tin whisker initiation and growth were further studied at an elevated temperature of 70 degC to check if a higher temperature effects Tin whisker formation. It is believed that establishment of a quantitative relationship of whisker formation/growth under compressive stress and elevated temperature conditions could lead to better scientific methods for risk and reliability assessment and smooth transitions to lead-free assemblies.     

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.