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.     

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.     

An Investigation into Zinc Diffusion and Tin Whisker Growth for Electroplated Tin Deposits on Brass

It is widely documented that whisker growth is more rapid for tin deposits on brass compared with deposits produced on other substrate materials, such as copper. As a result, studies investigating the effect of process variables on tin whisker formation are often conducted on brass substrates to take advantage of the increased whisker growth rates. Although it has been understood since the 1960s that the increased whisker growth results from zinc diffusion, to date there has not been any detailed analysis of the zinc/zinc oxide distribution at the surface of the tin deposit. Using a commercial bright tin electroplating bath, the formation of zinc oxide at the surface of tin deposits on brass has been investigated. Analyses show that zinc oxide is present on the surface of the deposit within 1 day of electroplating. During storage at room temperature, a network of zinc oxide is formed at the surface grain boundaries, the extent of which increases with time. The critical role that zinc surface diffusion plays in whisker growth for tin deposits on brass has been demonstrated by electrochemical oxidation of the tin shortly after electroplating. This develops a tin oxide film that is thicker than the native air-formed oxide and subsequently serves as a diffusion barrier to zinc surface diffusion, thereby mitigating whisker growth.     

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     

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.     

无铅Sn-Cu电镀层锡须的形成与长大

通过扫描电镜观察,研究不同处理工艺中电子元件引线框架表面Sn-Cu电镀层上锡须的形成与长大,结果显示,高温高湿处理易于促使锡须的形成与长大,经过一定的时间后,锡须生长速度减缓;循环热处理或室温处理对锡须的形成影响较小;当施加恒定外应力后进行室温处理,锡须的形成完全受到抑制.锡须的形成与长大是由于电镀层中存在压应力,压应力促使镀层中锡发生再结晶并长大成锡须.     

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.     

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     

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.     

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.     

元器件纯锡镀层表面晶须风险评估与对策

讨论了各种锡晶须的形态以及其长度的具体测量方法,并在试验研究的基础上进一步分析抑制非光滑(哑光)纯锡镀层上锡晶须生长的对策.研究结果表明,增加锡镀层厚度(＞7 μm),或通过使用添加剂来产生更加粗糙的表面以适当增大晶粒尺寸,电镀完成后及时进行退火程序是进一步减轻雾锡镀层上锡晶须困扰的有效手段.如果引入Ni作为中间镀层,则需要达到一定的厚度(估计＞0.7 μm),方可达到预期的效果.     

热湿存储环境下须状晶体的生长机理与影响因素

纯哑锡表面的晶须特性已经成为IC封装中无铅焊接工艺实施的主要影响因素之一。由于其它替代方法,例如预先在引脚上镀Ni/Pd/Au层,会导致成本无法预估以及可靠性下降等问题,因此,目前的关注点是进一步减少纯锡表面须状晶体的生长。     

An Investigation of Microstructure and Microhardness of Sn-Cu and Sn-Ag Solders as Functions of Alloy Composition and Cooling Rate

The microstructure and microhardness of Sn-xAg and Sn-xCu solders were investigated as functions of alloy composition and cooling rate. The Ag compositions examined varied from 0.5 wt.% to 3.5 wt.%, while Cu varied from 0.5 wt.% to 2.0 wt.%. Three cooling rates were employed during solidification: 0.02°C/s (furnace cooling), about 10°C/s (air cooling), and 100°C/s or higher (rapid solidification). Sn grain size and orientation were observed by cross-polarization light microscopy and electron-backscattering diffraction (EBSD) techniques. The microhardness was measured to correlate the mechanical properties with alloy compositions and cooling rates. From this study, it was found that both alloy composition and cooling rate can significantly affect the Sn grain size and hardness in Sn-rich solders. The critical factors that affect the microstructure–property relationships of Sn-rich solders are discussed, including grain size, crystal orientation, dendrite cells, twin boundaries, and intermetallic compounds (IMC).     

Characterization of Interface Strength as Function of Temperature and Moisture Conditions

Since Moisture Sensitivity Level (MSL) tests are part of the international reliability qualification standards, all the microelectronics components/products have to pass these specifications. Therefore, it is important to be able to efficiently and accurately characterize and predict the moisture related material and interface behavior in the real manufacturing, processing, testing and application conditions. The success of interfacial fracture mechanics approach to analyze moisture-induced failures in IC packaging strongly depend on accurate characterization of the critical adhesion strength, Gc. However, its measurement is complicated by the fact that adhesion depends not only on moisture concentration, C, but also temperature, T, and mode mixity, ψ. This paper described our research to develop a reliable methodology for interface toughness evaluation as function of temperature, humidity and mode mixity. Our methodology includes using the four-point bending test and shaft-loaded-blister method. Dedicated specimens consisting of various types of moulding compounds bonded onto leadframe are manufactured. Besides temperature, moisture content and mode mixity effects, also the influences of surface treatment (leadframe oxidation and contamination) and production process on the interface fracture toughness are evaluated. Multi-physics-based numerical methods are used to transfer the experimental critical loads to an interface strength parameter. These analysis covers mechanical, moisture diffusion, vapor pressure, hygro-swelling and CTE-mismatch modeling. To test and improve the methodology, various effects are evaluated, such as crack-length dependency, material properties, specimen- width, displacement-rate of the upper support/shaft, etc. The results of the proposed methodology indicate, as expected, a change in interface toughness by mode mixity, moisture content and temperature. It is found that Gc decreases with increasing moisture content and temperature. The presence of moisture at the given interface is observed as the important factor in the reduction of interfacial strength (>>20 %～45%). Furthermore, Gc increases by a factor 3～4 when the mode mixity shifts towards mode II.