Size and Substrate Effects upon Undercooling of Pb-Free Solders

The degrees of undercooling of various Pb-free solders are determined using differential scanning calorimetry. The effects of size, composition, and substrate upon undercooling are examined. Ni is the most effective element among Cu, Ni, and Ag in reducing the undercooling of Sn solders, both as an alloying addition and as a substrate. The degrees of undercooling and their variations are more significant for smaller-sized solders, but the relative orders of undercooling of various solders remain the same. It is concluded that the primary factors controlling undercooling are the primary solidification phase and the substrate. Different compositions of melts could have different primary solidifications, resulting in different degrees of undercooling. When the primary solidification phase and the substrates are the same, the degrees of undercooling could be different if the compositions of the melts are different. However, this compositional effect is not very significant.     

Oxidation Behavior of Rare-Earth-Containing Pb-Free Solders

We have previously shown that small additions of the rare-earth (RE) element La to Sn-Ag-Cu alloys significantly increases their ductility, without significant loss in the overall strength. However, due to the high reactivity of La with oxygen, oxidation of the La-containing phases can affect the mechanical performance of the solder. In this work, we have investigated the effect of the addition of 2 wt.% Ce, La and Y on the oxidation behavior of Sn-3.9Ag-0.7Cu. Oxidation kinetics were established by heating samples in ambient air to 60°C, 95°C or 130°C for up to 250 h. Microstructural characterization of the samples, before and after oxidation, was conducted in order to determine the influence of RE-containing phases on the oxidation kinetics. The oxidation mechanism, including the phenomenon of Sn whiskering during oxidation, is also discussed.     

The Effect of Sb Addition on Sn-Based Alloys for High-Temperature Lead-Free Solders: an Investigation of the Ag-Sb-Sn System

Today there is renewed interest in alloys belonging to the Sb-Sn-X (X = Cu, Ag, Bi) ternary systems and their phase equilibria, phase transformations, and thermodynamic properties because of their possible use as high-temperature lead-free solders in the electronics industry. The integral mixing enthalpy of Ag-Sb-Sn liquid alloys has been measured along five different sections (Ag_0.25Sn_0.75, Ag_0.50Sn_0.50, Sb_0.30Sn_0.70, Sb_0.50Sn_0.50, and Sb_0.70Sn_0.30) at 530°C, 600°C, and 630°C, using a high-temperature Calvet calorimeter by dropping pure elements (Ag or Sb) in the binary alloy liquid bath. The ternary extrapolation models of Muggianu and Toop were used to calculate the integral enthalpy of mixing and to compare measured and extrapolated values. Selected ternary alloys have been prepared for thermal investigation by using a differential scanning calorimeter at different heating/cooling rates in order to clarify the temperature of the invariant reactions and the crystallization path.     

Effects of Phase Change of Pb-Free Flip-Chip Solders During Board-Level Interconnect Reflow

The impact of phase change (from solid to liquid) on the reliability of Pb-free flip-chip solders during board-level interconnect reflow is investigated. Most of the current candidates for Pb-free solder are tin-based with similar melting temperatures near 230 degC. Thus, Pb-free flip-chip solders melt again during the subsequent board-level interconnect reflow cycle. Solder volume expands more than 4% during the phase change from solid to liquid. The volumetric expansion of solder in a volume constrained by chip, substrate, and underfill creates serious reliability issues. The issues include underfill fracture and delamination from chip or substrate. Besides decreasing flip-chip interconnect reliability in fatigue, bridging through underfill cracks or delamination between neighboring flip-chip interconnects by the interjected solder leads to failures. In this paper, the volume expansion ratio of tin is experimentally measured, and a Pb-free flip-chip chip-scale package (FC-CSP) is used to observe delamination and solder bridging after solder reflow. It is demonstrated that the presence of molten solder and the interfacial failure of underfill can occur during solder reflow. Accordingly, Pb-free flip-chip packages have an additional reliability issue that has not been a concern for Pb solder packages. To quantify the effect of phase change, a flip-chip chip-scale plastic ball grid array package is modeled for nonlinear finite-element analysis. A unit-cell model is used to quantify the elongation strain of underfill and stresses at the interfaces between underfill and chip or underfill and substrate generated by volume expansion of solder. In addition, the strain energy release rate of interfacial crack between chip and underfill is also calculated     

Brittle to Ductile Fracture Transition in Bulk Pb-Free Solders

The fracture toughness of bulk Sn, Sn-Cu, Sn-Ag, and Sn-Ag-Cu lead-free solders was measured as function of the temperature by means of a pendulum impact test (Charpy test). A ductile to brittle fracture transition was found, i.e., a sharp change in the fracture toughness. No transition was found for the eutectic Sn-Pb. The transition temperature of high purity Sn, Sn-0.5%Cu and Sn-0.5%Cu(Ni) alloys is around -125degC. The Ag-containing solders show a transition at higher temperatures: in the range of -78 to -45degC. The increase of the Ag content shifts the transition temperature towards higher values, which is related to the higher volume fraction of SnAg particles in the solder volume. At fixed volume fraction, smaller particle size shifts the transition temperature towards higher values. Therefore, a careful microstructure control is needed during the solder solidification after reflow in order to decrease the low temperature brittleness hazard.     

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     

Effect of Ag and Cu Concentrations on the Creep Behavior of Sn-Based Solders

The creep behavior of Sn-1Ag-0.5Cu, Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu ball grid array (BGA) solder balls and 99.99% pure polycrystalline bulk Sn was studied using impression creep and related to the microstructure. Sn-Ag-Cu solders generally consist of primary dendrites/grains of β-Sn, and a eutectic microconstituent comprising fine Ag₃Sn and Cu₆Sn₅ particles in β phase. With increasing concentrations of Ag and Cu in the alloy, the proportion of the eutectic microconstituent in relation to the primary β phase increases. In pure Sn and Sn-1Ag-0.5Cu, the β grains form the continuous matrix, whereas in Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu, the eutectic microconstituent forms a continuous network around the β grains, which form isolated islands within the eutectic. The steady-state creep behavior of the alloys was dominated by the response of the continuous microstructural constituent (β-Sn or solid solution β for pure Sn and Sn-1Ag-0.5Cu, and the eutectic microconstituent for Sn-2.5Ag-0.5Cu and Sn-4Ag-0.5Cu). In general, the steady-state creep rate decreased with increasing alloy content, and in particular, the volume fraction of Ag₃Sn and Cu₆Sn₅ precipitates. The rate-limiting creep mechanism in all the materials investigated here was core diffusion controlled dislocation climb. However, subtle changes in the stress exponent n and activation energy Q were observed. Pure Sn shows n = 5, Q = 42 kJ/mol, Sn-1Ag-0.5Cu shows n = 5, Q = 61 kJ/mol, whereas both Sn-2.5Ag-1Cu and Sn-4Ag-0.5Cu show n = 6 and Q = 61 kJ/mol. Rationalizations for the observed changes of n and Q are provided, based on the influence of the microstructure and the solute concentrations.     

Electromigration Behaviors and Effects of Addition Elements on the Formation of a Bi-rich Layer in Sn58Bi-Based Solders

This study investigates the electromigration (EM) behaviors and effects of the addition elements on the formation of a Bi-rich layer in Sn58Bi-based solders including Sn58Bi (SB), Sn58Bi0.5Ag (SBA) and Sn58Bi0.5Ag0.1Cu0.07Ni0.01Ge (SBACNG) solders. The EM tests were conducted at a relatively high temperature of 373 K and at a current density of 30 kA/cm². Although the dominant diffusing atom was Bi, hillocks were formed from Sn more easily than from Bi. The electrical resistance increased in the solder during the current stressing, and the dominant factor was attributed to the formation of a Bi-rich layer. SBACNG solder showed the highest resistance to the formation of a Bi-rich layer, followed by SBA, and then SB solder. The possible addition elements enhancing the resistance of SBACNG solder are Ag, Ni and Ge. The effects of the addition elements are summarized as follows: (1) Ag distributes in the Sn phase as Ag₃Sn intermetallic compounds (IMCs) that enhance the mechanical strength of Sn; (2) Ni distribution in Bi as Ni-Bi IMCs stabilizes Bi and suppresses its migration; and (3) Ge may distribute in Bi, stabilizing Bi, or Ge exists at the phase boundaries as a precipitate that inhibits Bi migration.     

连接器锡晶须形成机理及研究

针对锡晶须的形成原因,把机械地从外部到镀层表面形成的应力所产生的锡晶须定义为外部应力型,并主要叙述以连接器为主的外部应力型晶须;另一方面,把从基底材料的扩散和表面氧化等自然现象所产生的锡晶须定义为内部应力型晶须.推荐了锡晶须的测试方法,阐述了锡晶须的形成机理,并简要介绍了对锡晶须研究的现状及今后的研究课题.     

Correlations Between the Microstructure and Fatigue Life of Near-Eutectic Sn-Ag-Cu Pb-Free Solders

Relationships between the microstructure of near-eutectic Sn-Ag-Cu Pb-free solder joints and room-temperature fatigue lifetimes were studied. Correlations between the lifetimes of single Sn grained, SAC205 solder joints with the orientation of the Sn grain, and with differences in Ag₃Sn and Cu₆Sn₅ precipitate microstructures were sought. Correlations between the number of Sn grains and fatigue life were observed. Surprisingly, it was found that Ag₃Sn precipitates were highly segregated from Cu₆Sn₅ precipitates on a length scale of approximately 20 μm. Furthermore, large (factor of two) variations of the Sn dendrite arm size were observed within given samples. Such variations in values of dendrite arm size within a single sample were much larger than observed variations of this parameter between individual samples. Few significant differences were observed in the average size of precipitates in different samples. Although effects of average precipitate microstructure on lifetimes were not clearly delineated, one sample showed an anomalously high number of the smallest size (30 nm to 50 nm) Ag₃Sn precipitates, and this sample also exhibited a much longer lifetime than all the other samples. Thus, some evidence was presented that samples of particular orientations and precipitate microstructures can exhibit anomalous fatigue lifetimes.     

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.     

添加微量高熔点金属对无铅焊料性能的影响

研究了在SnAgCu、SnAgBi、SnZn三个系列无铅焊料中添加质量分数为0.1%的高熔点金属(Ni、Co、Fe)对其熔融特性、力学基本性能和浸润性的影响。结果表明,添加微量高熔点金属对焊料的熔融特性影响小于2%。添加微量Ni能明显改善SnAgCu系和SnZn系焊料的力学性能,并能使SnAgBi系焊料在铜表面的接触角降低约10%~14%。添加微量Co或Fe后的新焊料仅少部分性能指标有所提高,而部分性能参数则严重下降。     

Sn-Ag系电子无铅软钎料的超电势研究

随着微电子表面组装技术（SMT）的迅速发展和公众环境意识的增强，无铅软钎料成为近年来研究的焦点。主要研究了Sn-Ag系合金钎料的超电势电化学性能，并且与传统的Sn-Pb近共晶合金进行了对比。试验证明在酸、碱两种不同的溶液环境中，无铅软钎料在Sn-Pb合金的超电势有明显的差异。并指出含铋的钎料的超电势随着铋的含量的增加而降低，从而提出了在无铅软钎料研究中应当考虑因超电势变化而引起的问题。     

电子组装钎料研究的新进展

随着微电子技术的发展,印制电路板的组装密度不断提高,人们越恶霸虎重视焊点工作的可靠性。在分析焊点失效和原因的基础上,论述了改善焊点可靠性的途径,同时,随着人们对环保要求的提高,积极开发和推广使用无铅钎料及免清洗钎剂也是当务之急,结合我们的研究成果,详细介绍了无铅钎料开发的现状及前景。     

Numerical Investigation of Underfill Failure Due to Phase Change of Pb-Free Flip Chip Solders During Board-Level Reflow

In this paper, the effects of phase change of Pb-free flip chip solders during board-level interconnect reflow are investigated using numerical technique. Most of the current Pb-free solder candidates are based on Sn and their melting temperatures are in the range of 220 $^{circ}$ C–240 $^{circ}$ C. Thus, Pb-free flip chip solders melt again during subsequent board-level interconnect (BGA) reflow cycle. Since solder volume expands as much as 4% during the phase change from solid to liquid, the volumetric expansion of solder in a predefined volume by chip, substrate, and underfill creates serious reliability issues. One issue is the shorting between neighboring flip chip interconnects by the interjected solder through underfill crack or delaminated interfaces. The authors have observed the interjection of molten solder and the interfacial failure of underfill during solder reflow process. In this paper, a flip chip package is modeled to quantify the effect of the volumetric expansion of Pb-free solder. Three possible cases are investigated. One is without existence of micro crack and the other two are with the interfacial crack between chip and underfill and the crack through the underfill. The strain energy release rate around the crack tip calculated by the modified crack closure integral method is compared with interfacial fracture toughness. Parametric studies are carried out by changing material properties of underfill and interconnect pitch. Also, the effects of solder interconnect geometry and crack length are explored. For the case with interfacial crack, the configuration of a large bulge with small pitch is preferred for the board-level interconnect, whereas a large pitch is preferred for cracks in the mid plane of the underfill.      

电子焊料的工艺性能及影响因素

通过分析焊料在钎焊过程中的行为,提出了电子焊料的工艺性能主要包括熔化/固化温度、抗氧化性、润湿性和漫流性。给出了各工艺性能的定义。分析表明:相关的影响因素主要包括合金的组成、纯度和化学均匀性;母材的成分、性质和表面的洁净度;液态焊料的表面张力;钎焊温度、气氛、助焊剂的活性;液态焊料表面膜的组成、结构和性能等。     

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.     

电子工业用无铅钎料的研究及其可靠性

基于环保和可持续发展,本文概述了SnAg、SnZn、SnBi、SnCu、SnSb等系列Sn基无铅软钎料研究成果,分析了电子工业用无铅钎料的可靠性问题。