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.     

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.     

Interfacial Reaction Between Cu Substrates and Zn-Al Base High-Temperature Pb-Free Solders

Chemical reactions between Cu substrates and Zn-Al high-temperature solder alloys, Zn-4Al and Zn-4Al-1Cu (mass%), at temperatures ranging from 420°C to 530°C were experimentally investigated by a scanning electron microscope using backscattered electrons (SEM-BSE) and an electron probe microanalyzer (EPMA). Intermediate phases (IMPs), β(A2) or β′(B2), γ(D8₂), and ε(A3) phases formed and grew during the soldering and aging treatments. The consumption rate of the IMP for Cu substrates is described by the square root of t in both the alloys, while the additional Cu in the molten Zn-Al alloy slightly suppresses the consumption of Cu substrates. The growth of IMPs during soldering treatment is controlled by the volume diffusion of constituent elements, and its activation energy increases in the order of Q _ε < Q _γ < Q _β. In view of the aging process, the growth of IMPs is considered to be controlled by the volume diffusion. In particular, the layer thickness of γ rapidly grows over 200°C, although the thickness of the β layer grows very slowly.     

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.     

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.     

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     

Interfacial Reactions Between Pb-Free Solders and In/Ni/Cu Multilayer Substrates

This study investigates the interfacial reactions between Sn-3.0wt.% Ag-0.5wt.%Cu (SAC) and Sn-0.7wt.%Cu (SC) on In/Ni/Cu multilayer substrates using the solid–liquid interdiffusion bonding technique. Samples were reflowed first at 160°C, 180°C, and 200°C for various periods, and then aged at 100°C for 100 h to 500 h. The scalloped Cu₆Sn₅ phase was formed at the SAC/In/Ni/Cu and SC/In/Ni/Cu interfaces. When the reflowing temperatures were 160°C and 180°C, a ternary Ni-In-Sn intermetallic compound (IMC) was formed when the samples were further aged at 100°C. This ternary Ni-In-Sn IMC could be the binary Ni₃Sn₄ phase with extensive Cu and In solubilities, or the ternary Sn-In-Ni compound with Cu solubility, or even a quaternary compound. As the reflow temperature was increased to 200°C, only one Cu₆Sn₅ phase was formed at the solder/substrate interface with the heat treatment at 100°C for 500 h. Mechanical test results indicated that the formation of the Ni-In-Sn ternary IMC weakened the mechanical strength of the solder joints. Furthermore, the solid–liquid interdiffusion (SLID) technique in this work effectively reduced the reflow temperature.     

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.      

Transient Crack Growth Behavior Under Cycle/Time-Dependent Step Loading for Pb-Containing and Pb-Free Solders

In the present study, fatigue crack growth tests of Pb-containing [Sn-37Pb (wt.%)] and Pb-free [Sn-3.0Ag-0.5Cu (wt.%)] solders were performed under cycle/time-dependent step loading at a constant J-integral range (ΔJ). The C ^* parameter was also estimated for discussing time-dependent crack growth behavior. The experimental results indicated that acceleration of the crack growth rate at the beginning of the second loading step was induced when the C ^* value for the first loading step was high, regardless of time- or cycle-dependent crack growth and for both Sn-37Pb and Sn-3.0Ag-0.5Cu solders. The length of the acceleration region of the crack growth rate for both solders was in good agreement with the creep damage zone size estimated by the creep zone model proposed by Riedel and Rice.     

Modeling Fracture of Sn-Rich (Pb-Free) Solder Joints Under Mechanical Shock Conditions

With the increasing focus on developing environmentally benign electronic packages, lead-free solder alloys have received a great deal of attention. Mishandling of packages during manufacture, assembly, or by the user may cause solder joint failure. In this work, we conducted finite-element analysis to model solder joint fracture under dynamic loading conditions. The solder is modeled as a porous plastic material, and the intermetallic compound (IMC) material is characterized as an elastic material. The fracture of the solder is governed by void nucleation, and the IMC fracture is brittle in nature. The randomness of the void volume fraction in the solder and the defects in the IMC are considered and implemented in the finite-element package ABAQUS. The finite-element results show that the fracture mechanisms of the solder joints depend on the strain rate and IMC thickness. High strain rate and larger IMC thickness favor IMC-controlled fracture, which is brittle in nature. Low strain rate and smaller IMC thickness lead to solder-controlled fracture, which is governed by void growth and nucleation. Based on this finding, a mechanistic explanation for solder joint fracture is suggested.     

电迁移致无铅钎料微互连焊点的 脆性蠕变断裂行为

研究了电迁移条件下不同电流密度(0.8~1.27×10⁴A/cm²)和通电时间(0~96 h)对无铅钎料模拟微互连焊点的蠕变断裂行为的影响.研究结果发现,电迁移作用加速了焊点的蠕变断裂过程,随着电迁移通电时间的延长及电流密度的增加,其蠕变应变速率显著增大,而蠕变寿命逐渐缩短;电迁移还导致焊点蠕变断裂机制发生明显变化,在高电流密度或长时间通电的电迁移后,微互连焊点在服役条件下会发生由延性断裂向脆性断裂的转变.     

Comparison of Impact Toughness and Fracture Morphologies Between Pb-Containing and Pb-Free Solder Joints Subject to the Charpy Impact Test

Charpy impact tests on three kinds of as-soldered U-notch specimens were performed with reference to the American Society of Testing Materials (ASTM) standard E23-07 by using a pendulum-type impact tester at room temperature. Three kinds of solders, conventional Sn-37Pb, Sn-3.8Ag-0.7Cu, and Sn-3.8Ag-0.7Cu doped with rare-earth (RE) elements, were selected to fabricate the joint specimens for the impact test. The three joints demonstrate similar impact toughness values, with averages of 11.4 kJ/m², 10.4 kJ/m², and 11.0 kJ/m², respectively. Under observation by scanning electron microscopy (SEM), the Sn-37Pb joint exhibited mainly ductile fracture morphology. Fractographic observations of lead-free joints exhibited a mixture of ductile and brittle morphologies. The addition of RE elements resulted in an impact toughness that was slightly higher than that of the Sn-3.8Ag-0.7Cu alloy. The impact toughness and the fracture mode were notably dependent on the type of solder. Additionally, the thickness of the intermetallic compound (IMC) layer had a remarkable influence on the fracture path and impact toughness of the solder joints. An erratum to this article can be found at     

无铅焊料的新发展

传统焊接技术使用锡铅焊料,对环境造成严重伤害。该文从环保角度出发,阐述了应用无铅焊料的必然性,并介绍了无铅焊料近几年的发展,指出现阶段无铅焊料离市场要求还有一定差距。     

无铅焊料的新发展

传统焊接技术使用锡铅焊料,对环境造成严重伤害。文章从环保角度出发,阐述了应用无铅焊料的必然性,并介绍了无铅焊料近几年的发展,指出现阶段无铅焊料离市场要求还有一定差距, 需进一步加强研究与开发。     

Current-Induced Phase Partitioning in Eutectic Indium-Tin Pb-Free Solder Interconnect

Structural changes from high-density electric currents were examined in a eutectic In-Sn/Cu interconnect. Under electrical loading, Sn and In migrated in opposite directions, creating a partition of the Sn- and In-rich phases between the anode and the cathode. At the anode, a net gain of Sn atoms resulted in the formation of massive, columnar hillocks on the surface, but a net loss of In led to dissolution and disappearance of the In-rich intermetallic layer. At the cathode, the exodus of Sn left valleys adjacent to the In-rich regions on the surface, while the amount of the In-rich phase grew, due to the net influx of In at the expense of the In-rich intermetallic layer.     

Brittle‐to‐Ductile Transition in Uniaxial Compression of Silicon Pillars at Room Temperature

Robust nanostructures for future devices will depend increasingly on their reliability. While great strides have been achieved for precisely evaluating electronic, magnetic, photonic, elasticity and strength properties, the same levels for fracture resistance have been lacking. Additionally, one of the self‐limiting features of materials by computational design is the knowledge that the atomistic potential is an appropriate one. A key property in establishing both of these goals is an experimentally‐determined effective surface energy or the work per unit fracture area. The difficulty with this property, which depends on extended defects such as dislocations, is measuring it accurately at the sub‐micrometer scale. In this Full Paper the discovery of an interesting size effect in compression tests on silicon pillars with sub‐micrometer diameters is presented: in uniaxial compression tests, pillars having a diameter exceeding a critical value develop cracks, whereas smaller pillars show ductility comparable to that of metals. The critical diameter is between 310 and 400 nm. To explain this transition a model based on dislocation shielding is proposed. For the first time, a quantitative method for evaluating the fracture toughness of such nanostructures is developed. This leads to the ability to propose plausible mechanisms for dislocation‐mediated fracture behavior in such small volumes.