Pb-free solders for flip-chip interconnects

A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag₃Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni₃Sn₄ formed and on copper, Cu₆Sn₅Cu₃Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu. Editor’s Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/Frear-0106.html For more information, contact D.R. Frear, Interconnect Systems Laboratories, Motorola, Tempe, AZ 85284; (480) 413-6655; fax (480) 413-4511; e-mail darrel.frear@motorola.com.     

Effects of rapid solidification on the microstructure and microhardness of a lead-free Sn-3.5Ag solder

A lead-free Sn-3.5Ag solder was prepared by rapid solidification technology. The high solidification rate, obtained by rapid cooling, promotes nucleation, and suppresses the growth of Ag3Sn intermetallic compounds （IMCs） in Ag-rich zone, yielding fine Ag3Sn nanoparticulates with spherical morphology in the matrix of the solder. The large amount of tough homogeneously-dispersed IMCs helps to improve the surface area per unit volume and obstructs the dislocation lines passing through the solder, which fits with the dispersion-strengthening theory. Hence, the rapidly-solidified Sn-3.5Ag solder exhibits a higher rnicrohardness when compared with a slowly-solidified Sn-3.5Ag solder.     

Creep deformation behavior of Sn-3.5Ag solder at small length scales

To adequately characterize the behavior of solder spheres in electronic packaging, their mechanical behavior needs to be studied at small-length scales. The creep behavior of single Sn-3.5Ag solder spheres on a copper substrate was studied between 25°C and 130°C using a microforce testing system. In the low-stress regime, the creep stress exponent changed from 6 at lower temperatures to 4 at higher temperatures, indicating creep by dislocation climb. The activation energy for creep was also found to be temperature dependent, and correlated with values for dislocation core diffusion and lattice diffusion in pure tin. A change in the stress exponent with increasing stress was also observed and explained in terms of a threshold stress for dislocation motion, due to the presence of obstacles in the form of Ag₃Sn particles. For more information, contact N. Chawla, Arizona State University, Department of Chemical and Materials Engineering, Ira A. Fulton School of Engineering, Tempe, AZ 85287-6006; e-mail nchawla@asu.edu.     

62Sn36Pb2Ag钎料中Ag元素对AgCu/SnPbAg/CuBe焊缝性能的影响

分别采用62Sn36Pb2Ag钎料和63Sn37Pb共晶钎料焊接AgCu合金块和CuBe合金片进行试验,对比分析两种钎料形成的焊缝性能和显微组织结构,阐述了62Sn36Pb2Ag钎料中Ag元素的存在对AgCu/SnPbAg/CuBe焊缝性能的影响机制.结果表明,62Sn36Pb2Ag钎料中的Ag元素对于润湿铺展状态的改...     

Observations of nucleation catalysis effects during solidification of SnAgCuX solder joints

While modification of a strong (high Cu) Sn-Ag-Cu (SAC) solder alloy with a substitutional alloy addition (X=Co, Fe, Zn, and Ni) for Cu has been demonstrated to enhance solder joint strength and ductility after aging at 150°C for 1,000 h, control of the as-solidified SAC+X solder joint microstructure is also needed to inhibit under cooling and nucleation of brittle pro-eutectic phases (e.g., Ag₃Sn). Bulk undercooling measurements of SAC+X alloys and microstructural analysis of SAC+X solder joints were used to rank the effectiveness and consistency of low-level (X < 0.15 wt.%) substitutional additions to a base SAC composition, Sn-3.5Ag-0.95Cu (wt.%). This SAC composition was selected to favor thermodynamically the nucleation of pro-eutectic Cu₆Sn₅ over that of Ag₃Sn and the formation of an enhanced ternary eutectic fraction in the joint microstructure, while retaining a pasty range that is only 3°C. Using differential scanning calorimetry with sample pans that serve as either inert (aluminum) or actively wetting (copper) substrates, reflow cycles were studied that simulated surface mount (1.5°C/s) and ball-grid array (0.17°C/s) cooling rates. Of the SAC+X solders tested with copper pans, X = Zn appeared to be most effective and consistent, providing catalytic enhancement of the nucleation temperature for even the minimum concentration (0.05 wt.%) and lowest cooling rate.     

无铅焊料在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为

研究了Sn-3.5Ag-0.75Cu和Sn-0.75Cu焊料合金在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为,并与Sn-37Pb焊料合金的腐蚀浸出行为对比分析。研究表明,这3种焊料合金中Sn的浸出量随时间的延长趋于平缓,且Sn-0.75Cu焊料合金中Sn的浸出量最高,添加Ag元素后明显抑制了Sn-3·5Ag-0·75Cu焊料合金中Sn的浸出;Ag,Cu,Pb的浸出量随时间的延长呈线性增加,且Ag,Cu的浸出量较少。3种焊料合金浸出后表面产物层较厚,主要由Sn_4(OH)_6Cl_2和SnO组成,其中Sn-0.75Cu焊料合金的表面产物层有裂纹和孔洞,Sn-3.5Ag-0.75Cu焊料合金的表面产物相对致密,而Sn-37Pb焊料合金的表面产物局部出现剥落现象。这3种焊料合金浸出动力学行为存在差异,主要与表面产物的相组成和形貌有关。     

Interfacial reactions of liquid Sn and Sn-3.5Ag solders with Ag thick films

The interfacial reactions of liquid Sn and Sn-3.5Ag solders with Ag thick films are investigated in the temperature range from 250–325 °C, and the morphology of intermetallic compounds formed after such soldering reactions is observed. In kinetics analysis of the growths of intermetallic compounds, it was found that both Sn/Ag and Sn-3.5Ag/Ag reactions were interfacial-controlled, and the growth rates for both cases were similar. The rate of Ag dissolution into liquid solder attendant on the formation of interfacial intermetallic compounds after Sn/Ag reaction was about four times higher than that after Sn-3.5Ag/Ag reaction, as evidenced by experimental results.     

The effect of reflow process variables on the wettability of lead-free solders

A quantitative dynamic solder wettability measurement was utilized to evaluate the effects of reflow processing on the wettability parameters associated with the lead-free solders 96.5Sn-3.5Ag and 58Bi-42Sn. Solder wettability was determined with respect to the final degree of spread and the extent of solder wetting onto the terminal areas of surface-mount components. The solder alloy composition of 96.5Sn-3.5Ag exhibited better wetting characteristics than the 58Bi-42Sn alloy. This wetting behavior was enhanced under the reflow conditions of a nitrogen atmosphere and the use of a gold metallization. The wetting of the conventional 63Sn-37Pb solder alloy was improved over the comparatively processed 58Bi-42Sn alloy. However, the 63Sn-37Pb solder alloy displayed a greater sensitivity to reflow atmosphere than the 96.5Sn-3.5Ag alloy, which generally exhibited better wetting characteristics than the Sn-Pb alloy.     

Growth Behavior of Intermetallic Compounds at SnAgCu/Ni and Cu Interfaces

The growth behavior of reaction-formed intermetallic compounds (IMCs) at Sn3.5Ag0.5Cu/Ni and Cu interfaces under thermal-shear cycling conditions was investigated. The results show that the morphology of (Cu _x Ni_1–x )₆Sn₅ and Cu₆Sn₅ IMCs formed both at Sn3.5Ag0.5Cu/Ni and Cu interfaces gradually changed from scallop-like to chunk-like, and different IMC thicknesses developed with increasing thermal-shear cycling time. Furthermore, Cu₆Sn₅ IMC growth rate at the Sn3.5Ag0.5Cu/Cu interface was higher than that of (Cu _x Ni_1–x )₆Sn₅ IMC under thermal-shear cycling. Compared to isothermal aging, thermal-shear cycling led to only one Cu₆Sn₅ layer at the interface between SnAgCu solder and Cu substrate after 720 cycles. Moreover, Ag₃Sn IMC was dispersed uniformly in the solder after reflow. The planar Ag₃Sn formed near the interface changed remarkably and merged together to large platelets with increasing cycles. The mechanism of formation of Cu₆Sn₅, (Cu _x Ni_1–x )₆Sn₅ and Ag₃Sn IMCs during thermal-shear cycling process was investigated.     

Suppressing effect of 0.5 wt.% nano-TiO2 addition into Sn-3.5Ag-0.5Cu solder alloy on the intermetallic growth with Cu substrate during isothermal aging

This study investigated the effects of adding 0.5 wt.% nano-TiO₂ particles into Sn3.5Ag0.5Cu (SAC) lead-free solder alloys on the growth of intermetallic compounds (IMC) with Cu substrates during solid-state isothermal aging at temperatures of 100, 125, 150, and 175 °C for up to 7 days. The results indicate that the morphology of the Cu₆Sn₅ phase transformed from scallop-type to layer-type in both SAC solder/Cu joints and Sn3.5Ag0.5Cu-0.5 wt.% TiO₂ (SAC) composite solder/Cu joints. In the SAC solder/Cu joints, a few coarse Ag₃Sn particles were embedded in the Cu₆Sn₅ surface and grew with prolonged aging time. However, in the SAC composite solder/Cu aging, a great number of nano-Ag₃Sn particles were absorbed in the Cu₆Sn₅ surface. The morphology of adsorption of nano-Ag₃Sn particles changed dramatically from adsorption-type to moss-type, and the size of the particles increased.The apparent activation energies for the growth of overall IMC layers were calculated as 42.48 kJ/mol for SAC solder and 60.31 kJ/mol for SAC composite solder. The reduced diffusion coefficient was confirmed for the SAC composite solder/Cu joints.     

The Mechanical and Microstructural Changes of Sn-Ag-Bi Solders with Cooling Rate and Bi Content Variations

The purpose of this study is to investigate the influence of cooling rate and Bi addition on the microstructure evolution and mechanical properties of Sn-3.5Ag alloy. A series of Sn-3.5Ag-xBi solders has been fabricated with Bi content in the range of 0.5-3.5 wt.%. After solution heat treatment at 170 °C for 24 h and subsequent aging heat treatment at 100 °C for 2 h, samples were divided into two groups. One group was rapidly quenched into iced water (water quenching) for the fast cooling rate (20 °C/s), while the second group was slowly cooled (furnace cooling) in the furnace for the slow cooling rate (0.2 °C/s) after the furnace reflow. The microstructural evolutions of the present solders have been investigated using x-ray diffraction and scanning electron microscopy. The microhardness was measured to correlate the mechanical properties to alloy compositions and cooling rate. It was found that the microhardness of Sn-3.5Ag-xBi solders increased with increasing cooling rate. The indentation creep curves have been evaluated from the obtained microhardness values. Results revealed the steady-state creep rate decreased with increasing Bi content exhibiting an anomalous behavior at 2.5Bi. The reason for improved creep resistance of Sn-3.5Ag-xBi solders is the result of the combination of the solid solution strengthening and precipitation strengthening of Bi. The mean values of stress exponent indicated that the operative creep mechanism is dislocation climb.     

Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu₆Sn₅ and Cu₃Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu₆Sn₅ and Cu₃Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.     

Environmentally friendly solders 3-4 beyond Pb-based systems

Based on environmental considerations, global economic pressures, enacted by legislations in several countries, have warranted the elimination of lead from solders used in electronic applications.Sn3.5Ag, SnAgCu, and Sn0.7Cu have emerged among various lead-free candidates as the most promising solder alloys to be utilized in microelectronic industries.However, with the vast development and miniaturization of modern electronic packaging, new requirements such as superior service capabilities have been posed on lead-free solders.In order to improve the comprehensive property of the solder alloys, two possible approaches were adopted in the current research and new materials developed were patented.One approach was involved with the addition of alloying elements to make new ternary or quaternary solder alloys.Proper addition of rare earth element such as La and Ce have rendered solder alloys with improved mechanical properties, especially creep rupture lives of their joints.Another approach, the composite approach, was developed mainly to improve the service temperature capability of the solder alloys.Composite solders fabricated by mechanically incorporating various reinforcement particles to the solder paste have again exhibited enhanced properties without altering the existing processing characteristics.The recent progress and research efforts carried out on lead-free solder materials in Beijing University of Technology were reported.The effects of rare earth addition on the microstructure, processing properties, and mechanical properties were presented.The behaviors of various Sn-3.5Ag based composite solders were also explicated in terms of the roles of reinforcement particles on intermetallic growth, steady-state creep rate, the onset of tertiary creep, as well as the overall creep deformation in the solder joints.Thermomechanical fatigue (TMF) behavior of the solder alloys and composite solders were investigated with different parameters such as ramp rate, dwell time, etc.The damage accumulation features and residual mechanical properties of the thermomechanically-fatigued composite solder joints were compared with non-composite solder joints.To match the lead-free alloys, various types of water soluble no-clean soldering flux have also been developed and their properties were presented.     

Evolution of Ag3Sn at Sn-3.0Ag-0.3Cu-0.05Cr/Cu joint interfaces during thermal aging

The intermetallic compounds (IMC) in the solder and at the interface of Sn-3.0Ag-0.5Cu (SAC)/Cu and Sn-3.0Ag-0.3Cu-0.05Cr (SACC)/Cu joints were investigated after isothermal aging at 150 °C for 0, 168 and 500 h. Different shaped Ag₃Sn phases were found near the IMC layer of the latter joint. Interestingly, fine rod-shaped and branch-like Ag₃Sn were detected near the interface after soldering and long Ag₃Sn changed into shorter rods and small particles during aging. It is investigated that the Cr addition and thermal aging have effect on the evolution of Ag₃Sn morphologies and it is controlled by interfacial diffusion. Energy minimization theory and the redistribution of elements are used to explain the morphological evolution of Ag₃Sn. Small Ag₃Sn particles were also found on the IMC layer after aging, unlike the large Ag₃Sn at that of SAC/Cu joints. In conclusion, a favorable morphology of the joint interface leads to better bonding properties for SACC/Cu joints against thermal aging than that for SAC/Cu.     

Solderability and intermetallic compounds formation of Sn-9Zn-xAg lead-free solders wetted on Cu substrate

The eutectic Sn-9Zn alloy was doped with Ag (0 wt.%-1 wt.%) to form Sn-9Zn-xAg lead-free solder alloys. The effect of the addition of Ag on the microstructure and solderability of this alloy was investigated and intermetallic compounds (IMCs) formed at the solder/Cu interface were also examined in this study. The results show that, due to the addition of Ag, the microstructure of the solder changes. When the quantity of Ag is lower than 0.3 wt.%, the needle-like Zn-rich phase decreases gradually. However, when the quantity of Ag is 0.5 wt.%-1 wt.%, Ag-Zn intermetallic compounds appear in the solder. In particular, adding 0.3 wt.% Ag improves the wetting behavior due to the better oxidation resistance of the Sn-9Zn solder. The addition of an excessive amount of Ag will deteriorate the wetting property because the glutinosity and fluidity of Sn-9Zn-(0.5, 1)Ag solder decrease. The results also indicate that the addition of Ag to the Sn-Zn solder leads to the precipitation of ε-AgZn₃ from the liquid solder on preformed interfacial intermetallics (Cu₅Zn₈). The peripheral AgZn₃, nodular on the Cu₅Zn₈ IMCs layer, is likely to be generated by a peritectic reaction L + γ-Ag₅Zn₈ → ɛ-AgZn₃ and the following crystallization of AgZn₃.     

Effect of Purging Gas on Wetting Behavior of Sn-3.5Ag Lead-Free Solder on Nickel-Coated Aluminum Substrate

The wetting characteristics of Sn-3.5Ag lead-free solder alloy on nickel-coated aluminum substrates in air (ambient), nitrogen, and argon atmospheres were investigated. The contact angles for the solder alloy obtained under air and argon atmospheres were in the range of 36°-38°. With nitrogen atmosphere the contact angle was found to be significantly lower at about 26°. Solder solidifying in air exhibited needle-shaped tin-rich dendrites surrounded by a eutectic matrix. The amount of tin dendrites decreased in argon atmosphere. However, the morphology of tin dendrites transformed from needle-shaped to nearly non-dendritic shape as the soldering atmosphere was changed from air to nitrogen. The interfacial microstructures revealed the presence of Ni₃Sn and Ni₃Sn₄ IMCs at the interface. The enhanced wettability observed under nitrogen atmosphere is attributed to the higher thermal conductivity of nitrogen gas and the formation of higher amount of Ni₃Sn IMCs at the interface compared to air and argon atmospheres.     

添加Ag对Sn-9Zn无铅钎料合金性能的影响

通过试验研究了添加Ag对Sn-9Zn无铅钎料合金在Cu表面的润湿性、焊点剪切强度、抗蠕变性能与组织的影响。结果表明，当添加量较低时，Ag能够改善Sn-9Zn合金熔体对Cu的润湿性和焊点剪切强度，而添加量较高时Ag则会使它们降低；就焊点润湿性和剪切强度而言，最佳Ag含量（质量分数）为0．30％～0．60％。Ag的添加能显著提高Sn-9Zn合金体材的抗蠕变性能。显微分析表明，在含Ag合金中形成了弥散分布、尺度为微米级的Ag—Zn化合物颗粒，这可能是合金得到强化的原因。     

N2对Sn-Ag-Cu钎料与元器件引线无铅镀层润湿性的影响

以Sn-3．5Ag-0．5Cu钎料主要研究对象，配合免清洗助焊剂，基于润湿平衡原理测量了钎料对Sn、Sn—Cu、Sn—Bi三种镀层的润湿特性，研究了五种温度、三种镀层、两种气氛条件对润湿行为的影响。结果表明，空气气氛下，温度较低时Sn-Bi镀层的润湿性能相对较好，温度较高时三种镀层的润湿性相当；采用氮气保护后可明显改善钎料润湿性，润湿时间缩短22％-40％，同一温度下的三种镀层的润湿性能相当。     

Interfacial Reactions and Bonding Strength of Sn-xAg-0.5Cu/Ni BGA Solder Joints

The present study details the microstructure evolution of the interfacial intermetallic compounds (IMCs) layer formed between the Sn-xAg-0.5Cu (x = 1, 3, and 4 wt.%) solder balls and electroless Ni-P layer, and their bond strength variation during aging. The interfacial IMCs layer in the as-reflowed specimens was only (Cu,Ni)₆Sn₅ for Sn-xAg-0.5Cu solders. The (Ni,Cu)₃Sn₄ IMCs layer formed when Sn-4Ag-0.5Cu and Sn-3Ag-0.5Cu solders were used as aging time increased. However, only (Cu,Ni)₆Sn₅ IMCs formed in Sn-1Ag-0.5Cu solders, when the aging time was extended beyond 1500 h. Two factors are expected to influence bond strength and fracture modes. One of the factors is that the interfacial (Ni,Cu)₃Sn₄ IMCs formed at the interface and the fact that fracture occurs along the interface. The other factor is Ag₃Sn IMCs coarsening in the solder matrix, and fracture reveals the ductility of the solder balls. The above analysis indicates that during aging, the formation of interfacial (Ni,Cu)₃Sn₄ IMCs layers strongly influences the pull strength and the fracture behavior of a solder joint. This fact demonstrates that interfacial layers are key to understanding the changes in bonding strength. Additionally, comparison of the bond strength with various Sn-Ag-Cu lead-free solders for various Ag contents show that the Sn-1Ag-0.5Cu solder joint is not sensitive to extended aging time.     

Sn-0.75Cu钎料接头在NaCl溶液中的电化学腐蚀行为(英文)

采用动电位极化及浸出方法研究Sn-0.75Cu钎料及Sn-0.75Cu/Cu接头在3.5%NaCl溶液中的电化学腐蚀行为。极化曲线测试结果表明Sn-0.75Cu钎料的腐蚀速率比Sn-0.75Cu/Cu接头的低。在特殊电位时的形貌观察及相分析表明,在Sn-0.75Cu钎料表面活化溶解区形成腐蚀产物Sn3O(OH)2Cl2。从活化/钝化区开始,Sn-0.75Cu钎料的表面完全被腐蚀产物Sn3O(OH)2Cl2覆盖,并且在极化测试后出现蚀坑。与Sn-0.75Cu钎料合金相比,Sn-0.75Cu/Cu接头的钎料表面在活化区形成较多的Sn3O(OH)2Cl2,在极化测试结束时腐蚀坑的尺寸较大。浸出实验结果证实了Sn-0.75Cu/Cu接头较快的电化学腐蚀速率引起较多的Sn从中接头中释放出来。