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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Impact of thermal cycling on the evolution of grain, precipitate and dislocation structure in Al, 0.5% Cu, 1% Si thin films

Thermal cycles have been performed both outside and inside a transmission electron microscope (TEM) in order to analyze the evolution of the microstructure of Al, 0.5% Cu, 1% Si thin films deposited onto oxidized Si substrates. It is shown that grain growth and dislocation activity start almost simultaneously and cooperate throughout the plastic regime of the stress–temperature curve to generate bamboo-type grains with low dislocation density. Si precipitates serve as anchoring points for dislocations and grain boundaries. Thermal cycling and diffusion cause the growth of these precipitates and a diminution of their number. Diffusion also proves to play an important role regarding plastic relaxation at the Al/SiO_x interface and at the grain boundaries where an intense hillock and whisker formation has been observed in scanning electron microscope (SEM). The stress–temperature evolution is discussed in light of these observations.     

Ni80Fe20/Cu基磁性多层膜和自旋阀的微结构

用高分辨电子显微学及平行电子能量损失谱方法研究了Ni80Fe20/Cu基磁性多层膜和自旋阀的显微结构.高分辨像显示,磁性多层膜及自旋阀均具有沿薄膜生长方向的柱晶结构.Ni,Fe,Cu和Mn元素的成分分布图显示,柱晶内仍保持完整的层状结构.沿薄膜生长方向的自旋阀元素分布曲线分析表明,NiFe层中的Ni元素沿柱晶晶界向相邻Cu层扩散.讨论了这些低维磁电子学材料的显微结构对磁输运性能的影响.     

A physical model and analysis for whisker growth caused by chemical intermetallic reaction

The formation of intermetallic compound Cu₆Sn₅ gives rise to the internal stress in the lead-free coating, which causes the growth of Sn whiskers. This phenomenon is characterized with the expansion of inclusion in a plate perfectly bonded between two infinite solids. Based on the grain boundary diffusion mechanism, a model is established to evaluate the growth rate of Sn whiskers. The results show that the growth rate of whisker varies with the relative site between whisker and inclusion. When the distance between the whisker and inclusion exceeds a critical value, negative growth rate will appear, and it approaches zero as the distance increases. They explain some phenomena observed in experiments.     

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.     

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.     

Theory of Tin Whisker Growth: “The End Game”

Previous theories of the tin whisker growth proposing various dislocation mechanisms have been largely disproved. This paper presents a new and different theory for the mechanism of tin whisker growth. The theory addresses the fundamental requirements for Sn to diffuse to the base of the whisker grain and proposes a mechanism for whisker initiation and growth. Part of this is a theoretical proposal as to what makes the whisker grain different. The role of oxidation in whisker growth is also briefly addressed. Using this theory, attempts are made to illustrate how different whisker shapes are created. Finally, a proposed potential solution to tin whisker growth is presented, assuming that this theory is correct     

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     

Application of a focused ion beam mill to the characterisation of a microstructure in tin plating on a Fe 42wt% Ni substrate

The application of a focused ion beam (FIB) mill equipped with a microsampling unit to a tin-plated specimen was reported briefly. Tin-plating has a serious problem: Whiskers are liable to grow on the surface of tinplates. In order to clarify the mechanism of the whisker growth, detail characterisation is conducted using transmission electron microscopy (TEM). However, it is difficult to prepare specimens for TEM observation without the influences of mechanical damages. It was demonstrated that FIB etching was successfully used to observe a three-dimensional microstructure by scanning ion microscopy (FIB-imaging) and to prepare thin films for TEM observation. The observation has revealed the formation of precipitates of Ni(3)Sn(4) that is considered to be strongly related to the whisker growth.     

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.     

Effect of Pulse-Plated Nickel Barriers on Tin Whisker Growth for Pure Tin Solder Joints

We investigate the influence of pulse-plated Ni barriers, compared to direct current (DC)-plated Ni barriers, on the growth of Sn whiskers in laminated Cu/Ni/Sn samples. The results indicate that the pulse-plated Ni barriers exhibit much better resistance to Sn whisker growth than the DC-plated Ni barriers, i.e., when exposed to ambient of 60°C and 93% relative humidity (RH) for 40 days only a few small hillocks were observed as opposed to the long whiskers and large nodules of Sn for the DC-plated Ni barriers. The underlying mechanisms are addressed based on the texture characteristics of the plated Ni and Sn layers and the formation of intermetallic compounds.     

The Influence of Sn Orientation on Intermetallic Compound Evolution in Idealized Sn-Ag-Cu 305 Interconnects: an Electron Backscatter Diffraction Study of Electromigration

Previous research showed the relationship between Sn grain orientation and the intermetallic growth rate in Sn-Ag-Cu (SAC)305 interconnects. Samples with the Sn c-axis aligned parallel to the current flow have an intermetallic compound growth rate significantly faster than samples with the c-axis perpendicular to the current flow. This study continues the previous research by investigating intermetallic growth in polygranular joints and in joints that have a thin Ni layer at the cathodic or anodic interface of the interconnect. Planar SAC305 interconnects were sandwiched between two Cu pads (sometimes incorporating a thin Ni layer at the interface) and subjected to uniaxial current. The crystallographic orientation of Sn in these samples was characterized with electron backscatter diffraction before and after electromigration testing. The results show that polycrystalline joints have relatively slow intermetallic growth rates, close to those found in single-crystal joints with the c-axis perpendicular to the current. When a Ni layer was present on the anode side, the intermetallic grew at a rate comparable to that in samples without a Ni layer. However, when the Ni layer was on the cathode side, the intermetallic growth was significantly retarded. The measured growth rates of the intermetallic, combined with literature values for the diffusion of Cu in Sn, were used to calculate values for the effective charge, z ^*, which is significantly smaller for samples with current parallel to the c-axis than for either polycrystalline samples or samples with the c-axis perpendicular to the electron flow.     

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.