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.     

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 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.     

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.     

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     

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.     

Microstructure Development of Mechanical-Deformation-Induced Sn Whiskers

The development of the microstructure of mechanical-deformation-induced Sn whiskers on electroplated films has been examined using a focused ion beam system (FIB). The 6-μm-thick matte Sn films were compressed by using a ZrO₂ ball indenter under ambient conditions. After compression, tin whiskers and small nodules were found adjacent to, and several grains further away from, the indents. The cross-sectional microstructures of the indents and whiskers indicate that the lateral boundaries of the newly created grains caused by recrystallization are the main routes for stress relaxation.     

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     

The Effect of Annealing on Tin Whisker Growth

This paper presents a design-of-experiments study on the effect of annealing and simulated reflow on tin whisker growth. Copper, brass, and alloy 42 coupons plated with either bright or matte tin were subjected to one of three elevated temperature exposures. After the elevated temperature exposures, specimens along with a set of control specimens were then kept in room ambient conditions and monitored periodically using an environmentally scanning electron microscope. Surface observations up to 16 months of room ambient exposure revealed that tin whiskers formed on the surfaces of each specimen. However, various differences in whisker growth between the matte- and bright tin-plated specimens were observed. Columnar-type whiskers grown on the matte tin plated specimens were initiated from one grain at the surface, as opposed to the growth on bright tin which were independent from the surface morphology. Maximum length and length distribution data for matte and bright tin plating for the various exposures are presented. The result of this study shows annealing to be effective in reducing the maximum length of whiskers, particularly on bright finished coupons     

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.     

Effects of POSS-Silanol Addition on Whisker Formation in Sn-Based Pb-Free Electronic Solders

Previous studies have indicated that silanol in the form of polyhedral oligomeric silsesquioxane (POSS) trisilanol could form strong bonds with solder matrix without agglomeration, and inhibit diffusion of metal atoms when subjected to high ambient temperature and/or high current density. Addition of POSS-trisilanol has also been shown to improve the comprehensive performance of Sn-based Pb-free solders, such as shear strength, resistance to electromigration, as well as thermal fatigue. The current study investigated the whisker formation/growth behaviors of Sn-based Pb-free solders (eutectic Sn-Bi) modified with 3 wt.% POSS-trisilanol. Solder films on Cu substrates were aged at ambient temperature of 125°C to accelerate whisker growth. The microstructural evolution of the solder films’ central and edge areas was examined periodically using scanning electron microscopy. Bi whiskers were observed to extrude from the surface due to stress/strain relief during growth of Sn-Cu intermetallic compounds (IMCs). Addition of POSS-trisilanol was shown to retard the growth of Bi whiskers. The IMCs formed between POSS-modified solders and the Cu substrate showed smoother surface morphology and slower thickness growth rate during reflow and aging. It was indicated that POSS particles located at the phase boundaries inhibited diffusion of Sn atoms at elevated temperatures, and thus limited the formation and growth of IMCs, which resulted in the observed inhibition of Bi whisker growth in POSS-modified solders.     

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     

The Effect of Micro-Alloying of Sn Plating on Mitigation of Sn Whisker Growth

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.     

Sn whisker evaluations in 3D microbumped structures

Sn whiskering remains a reliability concern in electronic applications. Despite extensive research on growth rates and mitigation strategies, no predictive theory is in place. Literature data are available for Cu/Sn-based films and coatings as well as for board-level and flip-chip solder bumps but data are scarce for scaled-down solder volumes and for higher intermetallic-to-solder ratios. The current work investigates whiskers in “isolated geometries” for 3D solder-capped Cu microbumps with >2 orders of magnitude smaller solder volumes compared to state-of-the-art. To the best of the authors’ knowledge, this is the first time Sn whisker growth is reported in isolated solder volumes (e.g. <8 μm-side cube). Whiskers propensity was evaluated using JEDEC industrial specifications. The tested structures were: 5/3.5 μm-thick Cu/Sn films and 15 μm-diameter electroplated solder capping (Sn, SnAg, SnCu) on Cu microbumps (as-plated vs. reflowed). Selected Sn whiskers and “whisker-like” features were analysed and identified experimentally with SEM, EDX and FIB. In the absence of a predictive model, first-order and “what if” calculations based on IMC molar volume and oxide cracking hypotheses were carried out. This approach quantifies “figures of merit” for Sn whisker propensity with (1) different bump-limiting metallization (BLM) cases e.g. Cu, Ni, Co and (2) further microbump scaling. Future research recommendations are outlined to mitigate manufacturing risks by controlling “sit time” between bumping and stacking.     

Internal Microstructure Investigation of Tin Whisker Growth Using FIB Technology

The problem of tin (Sn) whiskers has been a significant reliability issue in electronics for the past several decades. Despite the large amount of research conducted on this issue, a solution for mitigating the growth of whiskers remains a challenge for the research community. Whiskers have unpredictable growth and morphology, and a study of a whisker??s internal structure may provide further insights into the reason behind their complex growth. This study reports on the internal microstructure and morphology of complex-shaped Sn whiskers grown from an electroplated bright Sn layer on brass substrates exposed to ambient and 95% humid environment. The variables analyzed include surface and microstructure conditions of the film, and morphology and internal microstructure of the Sn whiskers using scanning electron microscopy with focused ion beam technology. Experimental results demonstrated that the whiskers with more complex morphology grow primarily from surfaces exposed to a controlled environment, and some of them have traits of polycrystalline growth rather than only single crystalline, as usually known.     

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.     

Comparative studies on microelectronic reliability issue of Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments

In this study, comparative studies on Sn whisker growth in Sn-0.3Ag-0.7Cu-1Pr solder under different environments were conducted to investigate factors like ambient temperature, oxygen level, and 3.5 wt% NaCl solution on whisker growth. The experimental results revealed that ambient temperature and oxygen level are two important factors that could determine the oxidation rate of PrSn₃ phase, thus indirectly affecting the growth rate of Sn whiskers. In addition, mechanisms of whisker growth under these three environments were established from the perspective of atom diffusion based on the “compressive stress-induced” theory. Although whiskers under different environments were all squeezed out from Pr oxides (hydroxides), the forms of their driving forces were different. For whiskers squeezed out in air whether at room temperature or 150 °C, the driving force is the compressive stress produced by lattice expansion due to the oxidation of PrSn₃ phase. The representative example was whiskers' growth at 150 °C, which could be simplified as three stages: (1) squeezing out, (2) cracking and (3) bursting out. For whisker growth in 3.5 wt% NaCl solution, the driving force for much fewer whiskers' growth was proposed to come from lateral stress provided by interfacial IMC layer growth. Moreover, Sn nanoparticles and their agglomerations were also found to form under the driving force of the potential difference between Sn atoms and Sn crystals. Their morphologies could also be affected by factors of ambient temperature, oxygen level and Cl⁻ ions in corrosive liquid.     

Tin whisker formation of lead-free plated leadframes

This paper presents the evaluation results of whiskers on two kinds of lead-free finish materials at the plating temperature and under the reliability test. The rising plating temperature caused increasing the size of plating grain and shorting the growth of whisker. The whisker was grown under the temperature cycling the bent shaped in matte pure Sn finish and hillock shape in matte Sn–Bi. The whisker growth in Sn–Bi finish was shorter than that in Sn finish. In FeNi42 leadframe, the 8.0–10.0 μm diameter and the 25.0–45.0 μm long whisker was grown under 300 cycles. In the 300 cycles of Cu leadframe, only the nodule-shaped grew on the surface, and in the 600 cycles, a 3.0–4.0 μm short whisker grew. After 600 cycles, the 0.25 μm thin Ni₃Sn₄ formed on the Sn-plated FeNi42. However, we observed the amount of 0.76–1.14 μm thick Cu₆Sn₅ and 0.27 μm thin Cu₃Sn intermetallics were observed between the Sn and Cu interfaces. Therefore, the main growth factor of a whisker is the intermetallic compound in the Cu leadframe, and the coefficient of thermal expansion mismatch in FeNi42.     

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.     

Eutectic Sn-Ag solder bump process for ULSI flip chip technology

A novel eutectic Pb-free solder bump process, which provides several advantages over conventional solder bump process schemes, has been developed. A thick plating mask can be fabricated for steep wall bumps using a nega-type resist with a thickness of more than 50 μm by single-step spin coating. This improves productivity for mass production. The two-step electroplating is performed using two separate plating reactors for Ag and Sn. The Sn layer is electroplated on the Ag layer. Eutectic Sn-Ag alloy bumps can be easily obtained by annealing the Ag/Sn metal stack. This electroplating process does not need strict control of the Ag to Sn content ratio in alloy plating solutions. The uniformity of the reflowed bump height within a 6-in wafer was less than 10%. The Ag composition range within a 6-in wafer was less than ±0.3 wt.% Ag at the eutectic Sn-Ag alloy, analyzed by ICP spectrometry. SEM observations of the Cu/barrier layer/Sn-Ag solder interface and shear strength measurements of the solder bumps were performed after 5 times reflow at 260°C in N₂ ambient. For the Ti(100 nm)/Ni(300 nm)/Pd(50 nm) barrier layer, the shear strength decreased to 70% due to the formation of Sn-Cu intermetallic compounds. Thicker Ti in the barrier metal stack improved the shear strength. The thermal stability of the Cu/barrier layer/Sn-Ag solder metal stack was examined using Auger electron spectrometry analysis. After annealing at 150°C for 1000 h in N₂ ambient, Sn did not diffuse into the Cu layer for Ti(500 nm)/Ni(300 nm)/Pd(50 nm) and Nb(360 nm)/Ti(100 nm)/Ni(300 nm)/Pd(50 nm) barrier metal stacks. These results suggest that the Ti/Ni/Pd barrier metal stack available to Sn-Pb solder bumps and Au bumps on Al pads is viable for Sn-Ag solder bumps on Cu pads in upcoming ULSIs