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.     

Effect of Zn addition in Sn-rich alloys on interfacial reaction with Au foils

To restrain the formation of AuSnx intermetallic components （IMCs） in solder joints, Zn was added into Sn-rich solders. The solder joints were fabricated by a laser reflow soldering method, and then they were aged at 125 ℃. The results show that the total thickness of AuSnx IMCs at the interface of pure Sn solder and Au foils reaches about 54 μm under the condition of 600 h aging. In Sn-1.5Zn solder joints, however, formation of AuSn4 IMCs is restrained greatly. As the content of Zn in the solder is increased to 3.5%（mass fraction）, no AuSn4 IMC is observed at the interface. Au-Zn phases form beside AuSn2 and AuSn IMCs layers. As for Sn-9.0Zn solder joints, Au-Zn and Au-Zn-Sn phases and few AuSnx IMCs form at the interface. Moreover, total thickness of the phases and IMCs is far less than that ofAuSnx IMCs in the pure Sn solder joints.     

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。     

EFFECT OF LASER INPUT ENERGY ON AuSnx INTERMETALLIC COMPOUNDS FORMATION IN SOLDER JOINTS WITH DIFFERENT THICKNESS OF Au SURFACE FINISH ON PADS

Formation of AuSnx intermetallic compounds （IMCs） in laser reflowed solder joints was investigated. The results showed that few IMCs formed at the solder/0. 1μm Au interface. Needlelike AuSn4 IMCs were observed at the solder/0.5μm Au interface. In Sn-2.0Ag-O,75Cu-3,0Bi and Sn-3.5Ag-O.75Cu solder joints, when the laser input energy was increased, AuSn4 IMCs changed .from a layer to needlelike or dendritic distribution at the solder/0.9μm Au interface. As for the solder joints with 4.0 μm thickness of Au surface finish on pads, AuSn4 , AuSnx, AuSn IMCs, and Au2Sn phases formed at the interface. Moreover, the content of AuSnx IMCs, such as, AuSn4 and AuSn2, which contained high Sn concentration, would become larger as the laser input energy increased. In the Sn-37Pb solder joints with 0.9 μm or 4.0 μm thickness of the Au surface finish on pads, AuSn4 IMCs were in netlike distribution. The interspaces between them were filled with Pb-rich phases.     

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.     

底充胶叠层PBGA无铅焊点随机振动应力应变分析

建立了底充胶叠层塑料球栅阵列(plastic ball grid array, PBGA)无铅焊点三维有限元分析模型,研究了PBGA结构方式、焊点材料、底充胶弹性模量和密度对叠层无铅焊点随机振动应力应变的影响. 结果表明,底充胶可有效降低焊点内的随机振动应力应变;在其它条件相同下,对于Sn95.5Ag3.8Cu0.7,Sn96.5Ag3Cu0.5,Sn-3.5Ag和Sn63Pb37这四种焊料,采用Sn-3.5Ag的底充胶叠层焊点内的随机振动最大应力应变最小,采用Sn96.5Ag3Cu0.5的焊点内的最大应力应变最大;随着底充胶弹性模量的增大,叠层无铅内的随机振动应力应变值相应减小;随着底充胶密度的增大,叠层无铅内的随机振动应力应变值相应增大.     

老化对Sn-Ag-Cu焊料/Ni-P镀层界面结构和剪切强度的影响

对Sn-3．5Ag-0．7Cu／Ni—P界面上的焊点进行了150℃固相老化和250℃液相回流老化实验．两种条件下焊料体内和界面处金属间化合物的成分、长大速率及形貌均有较大差异．在液相回流条件下金属间化合物长大更快,对焊点的可靠性有较大的影响．延长固相老化时间,焊点内生成大尺寸的Ag3Sn相;高温液相回流有Ni3P层生成,降低焊点的焊接强度．     

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.     

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.     

升温速率对复合钎料显微组织和力学性能的影响

不同的钎焊工艺条件会对复合钎料中增强相颗粒（如Ni,Ag,Cu等金属颗粒）周围金属间化合物的形貌和尺寸产生影响,而增强相颗粒周围金属间化合物的尺寸又会对复合钎料的力学性能产生影响。在共晶Sn-3．5Ag钎料中外加微米级铜颗粒制成复合钎料,研究了不同的升温速率对复合钎料内部颗粒显微组织和力学性能的影响。结果表明,复合钎料中铜增强颗粒周围存在着厚度不均的金属间化合物层,不同的升温速率对这层金属间化合物的形貌基本没有影响,只会对其厚度尺寸有影响。此外,建立了不同升温速率与铜颗粒增强的Sn-Ag基复合钎料增强颗粒周围金属间化合物尺寸和力学性能的关系。     

工艺条件对颗粒增强复合钎料组织性能的影响

选用微米级Cu、Ni颗粒作为增强相外加到Sn-3.5Ag共晶基体钎料中制成颗粒增强Sn-Ag基复合钎料。主要利用电子显微镜研究不同工艺条件下,复合钎料钎焊接头内部增强颗粒周围金属间化合物(IMCs)形貌的演变情况,并分析了增强颗粒形态变化对复合钎料钎焊接头力学性能的影响。结果表明,随着升温速率的降低,Ni增强颗粒周围金属间化合物的形态由向日葵状转变为多边形状;Cu增强颗粒周围金属间化合物的形态始终保持大瓣向日葵状。此外,降温速率对Cu、Ni颗粒周围金属间化合物的形态没有影响。从而分析了不同工艺条件下增强颗粒周围金属间化合物形态的演变规律,以及对复合钎料钎焊接头剪切强度的影响。     

微量锌对Sn-3.5Ag无铅钎料/铜界面金属间化合物生长的抑制

在钎焊和时效条件下,研究了Sn-3.5Ag无铅钎料中添加0.2%的Zn元素后对钎料/铜界面组织形貌的影响.结果表明,钎焊条件下,将0.2%的Zn元素加入到Sn-3.5Ag钎料中对Cu-Sn间的金属间化合物及其扇贝形形状不产生影响.时效处理后,0.2%Zn元素的加入对界面IMC层的厚度、组成及形态都有影响.在Sn-3.5...     

Structural and elastic properties of eutectic Sn-Cu lead-free solder alloy containing small amount of Ag and In

Sn-Cu alloys have been considered as a candidate for high temperature lead-free microelectronic solders. In the present study, the change in microstructure, attenuation and elastic behavior associated with alloying of Ag and/or In into the eutectic Sn-Cu solder alloy system have been evaluated. The study involved measurements of longitudinal and shear wave velocities, attenuation, hardness, bulk and shear moduli, Young's and Poisson's ratio. The results of attenuation show that a clear attenuating effect in the ternary Sn-Cu-Ag and Sn-Cu-In alloys is realized, whereas the quaternary Sn-Cu-Ag-In solder displays an obscure attenuating effect. The obscure effect is mainly attributed to the competition for In between Sn and Ag, which results in weak interface formed between intermetallic compounds (IMCs) and β-Sn matrix. Likewise, Poisson's ratio results indicate that its value decreases with increasing the elastic moduli and ultrasonic velocities of Ag and In-containing alloys. The analyzed enhanced ductility of Sn-0.7Cu and Sn-0.7Cu-2In alloys and brittleness of Sn-0.7Cu-2Ag and Sn-0.7Cu-2Ag-2In alloys were rationalized on the basis of Poisson's ratio and the quotient of shear modulus to bulk modulus (Pugh's ratio). Microstructural analysis revealed that the origin of change in the elastic properties of the ternary and quaternary alloys is ascribed to smaller β-Sn dendrite grain dimensions and formation of new IMCs in the ternary and quaternary alloys.     

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.     

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.     

SnAgCu-xPr钎料组织及性能

研究了不同含量Pr元素（质量分数分别为0,0.05%,0.5%）对Sn-3.8Ag-0.7Cu无铅钎料凝固特性、润湿铺展性能以及微观组织的影响.结果表明,SAC,SAC-0.05Pr以及SAC-0.5Pr的凝固所需过冷度分别为20.6,5.0,5.1℃,说明适量Pr元素的加入能够显著降低SnAgCu钎料凝固所需的过冷度;同时,Pr元素的加入细化了钎料组织,降低钎料组织中初晶β-Sn的尺寸,抑制了SnAgCu/Cu焊点内部不同形貌大块化合物Ag3Sn初晶的形成;当Pr元素的添加量为0.05%时,钎料润湿性能最优、组织最佳;0.5%Pr元素的添加会在钎料以及焊点内部形成PrSn3相,对焊点的性能造成不利的影响.     

Microstructural evolution and tensile properties of Sn-5Sb solder alloy containing small amount of Ag and Cu

The near peritectic Sn-5Sb Pb-free solder alloy has received considerable attention for high temperature electronic applications, especially on step soldering technology, flip-chip connection. In the present study, a separate addition of the same amount of Ag and Cu are added with the near-peritectic Sn-5Sb solder alloy to investigate the effect of a third element addition on the microstructural, thermal and mechanical properties of the newly developed ternary solder alloys. The results indicate that the melting point of Sn-5Sb solder is enhanced by Ag and Cu additions. Besides, the Ag and Cu content refine the microstructure and form new intermetallic compounds (IMCs) with the near-peritectic Sn-5Sb solder alloy. The tensile tests revealed that all alloys exhibit higher mechanical strength with increasing strain rate and/or decreasing testing temperature, suggesting that the tensile behavior of the three alloys is strain rate and temperature dependence. The yield and ultimate tensile strength are higher for Sn-5Sb-0.7Cu alloy compared with Sn-5Sb and Sn-5Sb-0.7Ag alloys. Good mechanical performance of Sn-5Sb-0.7Cu solder is often correlated to a fine β-Sn grain size and more dispersed Cu-Sn IMC particles, which makes the solder exhibit high strength and yield stress.     

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。     

Microstructural evolution of intermetallic compounds in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn and 1.5In)/Cu solder joints during liquid aging

In this paper, the microstructural evolution of IMCs in Sn–3.5Ag–X (X = 0, 0.75Ni, 1.0Zn, 1.5In)/Cu solder joints and their growth mechanisms during liquid aging were investigated by microstructural observations and phase analysis. The results show that two-phase (Ni₃Sn₄ and Cu₆Sn) IMC layers formed in Sn–3.5Ag–0.75Ni/Cu solder joints during their initial liquid aging stage (in the first 8 min). While after a long period of liquid aging, due to the phase transformation of the IMC layer (from Ni₃Sn₄ and Cu₆Sn phases to a (Cu, Ni)₆Sn₅ phase), the rate of growth of the IMC layer in Sn–3.5Ag–0.75Ni/Cu solder joints decreased. The two Cu₆Sn₅ and Cu₅Zn₈ phases formed in Sn–3.5Ag–1.0Zn/Cu solder joints during the initial liquid aging stage and the rate of growth of the IMC layers is close to that of the IMC layer in Sn–3.5Ag/Cu solder joints. However, the phase transformation of the two phases into a Cu–Zn–Sn phase speeded up the growth of the IMC layer. The addition of In to Sn–3.5Ag solder alloy resulted in Cu₆(Sn_x,In_1?x)₅ phase which speeded up the growth of the IMC layer in Sn–3.5Ag–1.5In/Cu solder joint.     

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.