Morphology and growth kinetics of Ag3Sn during soldering reaction between liquid Sn and an Ag substrate

For the soldering of recycled Ag sputtering targets, the interfacial reaction between liquid Sn and an Ag substrate at temperatures ranging from 250 –425°C has been investigated. Experimental results show that a scallop-shaped layer of Ag₃Sn intermetallic compounds formed during the soldering reaction. Kinetics analysis indicated that the growth of such interfacial Ag₃Sn intermetallic compounds is diffusion-controlled with activation energy of 70.3kJ/mol. During the reaction, the Ag substrate dissolves into the molten Sn solder and causes the appearance of needle-shaped Ag₃Sn precipitates in the Sn matrix.     

Intermetallic Compounds Formed in Sn-20In-2.8Ag Solder BGA Packages with Ag/Cu Pads

The interfacial reactions in a Sn-20In-2.8Ag solder ball grid array (BGA) package with immersion Ag surface finish are investigated. After reflow, the Ag thin film dissolves quickly into the solder matrix, and scallop-shaped intermetallic layers, with compositions of (Cu_0.98Ag_0.02)₆(In_0.59Sn_0.41)₅, appear at the interfaces between Sn-20In-2.8Ag solder ball and Cu pad. No evident growth of the (Cu_0.98Ag_0.02)₆(Sn_0.59In_0.41)₅ intermetallic compounds was observed after prolonged aging at 100 °C. However, the growth accelerated at 150 °C, with more intermetallic scallops floating into the solder matrix. The intermetallic thickness versus the square root of reaction time (t ^1/2) shows a linear relation, indicating that the growth of intermetallic compounds is diffusion-controlled. Ball shear tests show that the strength of Sn-20In-2.8Ag solder joints after reflow is 4.4 N, which increases to 5.18 N and 5.14 N after aging at 100 and 150 °C, respectively.     

电迁移对Ni/Sn3.0Ag0.5Cu/Cu焊点界面反应的影响

研究了温度为150℃,电流密度为5.0×10³A/cm²的条件下电迁移对Ni/Sn3.0Ag0.5Cu/Cu焊点界面反应的影响.回流焊后在Sn3.0Ag0.5Cu/Ni和Sn3.0Ag0.5Cu/Cu的界面上均形成了（Cu,Ni）₆Sn₅型化合物.时效过程中界面化合物随时效时间增加而增厚,时效800 h后两端的化合物并没有发生转变,仍为（Cu,Ni）₆Sn₅型.电流方向对Cu基板的消耗起着决定作用.当电子从基板端流向芯片端时,电流导致基板端Cu焊盘发生局部快速溶解,并导致裂纹在Sn3.0Ag0.5Cu/（Cu,Ni）₆Sn₅界面产生,溶解到钎料中的Cu原子在钎料中沿着电子运动的方向向阳极扩散,并与钎料中的Sn原子发生反应生成大量的Cu₆Sn₅化合物颗粒.当电子从芯片端流向基板端时,芯片端Ni UBM层没有发生明显的溶解,在靠近阳极界面处的钎料中有少量的Cu₆Sn₅化合物颗粒生成,电迁移800 h后焊点仍保持完好.电迁移过程中无论电子的运动方向如何,均促进了阳极界面处（Cu,Ni）₆Sn₅的生长,阳极界面IMC厚度明显大于阴极界面IMC的厚度.与Ni相比,当Cu作为阴极时焊点更容易在电迁移作用下失效.     

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.     

RE对Sn2.5Ag0.7Cu/Cu焊点性能的影响

利用X射线衍射分析仪(XRD)和JSM-5610LV扫描电镜(SEM)研究RE含量对Sn2.5Ag0.7Cu/Cu焊点界面区显微组织、剪切强度和蠕变断裂寿命的影响。结果表明:Sn2.5Ag0.7CuxRE焊点界面区金属间化合物由靠近钎料侧Cu6Sn5和靠近Cu基板侧Cu3Sn构成;添加微量RE可细化Sn2.5Ag0.7Cu焊点内钎料合金的显微组织和改善钎焊接头界面区金属间化合物的几何尺寸及形态;当RE添加量为0.1%时,焊点的剪切强度最高,蠕变断裂寿命最长。     

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.     

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.     

Reaction diffusions of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn intermetallic compound in the couple of Sn-3.5Ag eutectic solder and copper substrate

The growth kinetics of intermetallic compound layers formed between Sn-3.5Ag solder and Cu substrate were investigated as a consequence of solid-state isothermal aging. Isothermal aging was carried out in a temperature range between 70°C and 200°C for 0 to 60 days. A quantitative analysis of the intermetallic compound layer thickness as a function of time and temperature was performed. The diffusion couples showed a composite intermetallic layer comprised of Cu₆Sn₅ and Cu₃Sn. The growth of intermetallic compounds followed diffusion-controlled kinetics and the layer thickness reached only 9 μm after 60 day of aging at 150°C. The apparent activation energies were calculated for the growth of the total intermetallic compound (Cu₆Sn₅+Cu₃Sn); Cu₆Sn₅ and Cu₃Sn intermetallic are 65.4, 55.4 and 75.7 kJ/mol, respectively.     

Sn5Sb1Cu0.1Ni0.1Ag/Cu(Ni)焊点的抗时效性能

采用扫描电镜(SEM)研究在150 ℃等温时效下Cu/Sn5Sb1Cu0.1Ni0.1Ag/Cu与Ni/Sn5Sb1Cu0.1Ni0.1Ag/Ni焊点的界面扩散行为. 结果表明,在时效过程中,随着时效时间的增加,Cu/Sn5Sb1Cu0.1Ni0.1Ag/Cu焊点界面金属间化合物(intermetallic compound,IMC)形貌由开始的细针状生长为棒状,IMC层厚度增加,界面IMC主要成分为(Cu,Ni)₆Sn₅. Ni/Sn5Sb1Cu0.1Ni0.1Ag/Ni焊点的界面IMC形貌由细小突起状转变为较为密集颗粒状,且IMC层厚度增加,界面IMC主要成分为(Cu,Ni)₃Sn₄. 经过线性拟合,两种焊点的界面IMC层生长厚度与时效时间t1/2呈线性关系,Sn5Sb1Cu0.1Ni0.1Ag/Cu界面间IMC的生长速率为7.39 × 10?2 μm2/h,Sn5Sb1Cu0.1Ni0.1Ag/Ni界面间IMC的生长速率为2.06 × 10?2 μm2/h. 镀镍层的加入可以显著改变界面IMC的形貌,也可降低界面IMC的生长速率,抑制界面IMC的生长,显著提高抗时效性能.     

Effect of bismuth on the growth kinetics of intermetallic compounds in Sn-3.5Ag solder joints: A growth kinetic model

The effect on the growth kinetics of the intermetallic compounds (IMCs) in solder/Cu joints, caused by adding Bi to eutectic Sn-3.5Ag solder alloy, was examined at the aging temperatures of 150°C and 180°C. The Cu₆Sn₅ layer growth was significantly enhanced, but the Cu₃Sn layer growth was slightly retarded by the addition of Bi, resulting in significant growth enhancement of the total (Cu₆Sn₅+Cu₃Sn) IMC layer with increasing Bi addition. The IMC layer growth in the Bi-containing solder joints was accompanied by the accumulation of Bi ahead of the Cu₆Sn₅ layer that resulted in the formation of a liquid layer at the Cu₆Sn₅/solder interface. A kinetic model was developed for the planar growth of the Cu₆Sn₅ and Cu₃Sn layers in the solder joints, accounting for the existence of interfacial reaction barriers. Predictions from the kinetic model showed that the experimental results could be well explained by the hypothesis that the formation of a Bi-rich liquid layer at the Cu₆Sn₅/solder interface reduces the interfacial reaction barrier at the interface.     

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.     

Sn whisker growth in Sn-9Zn-0.5Ga-0.7Pr lead-free solder

The spontaneous growth of Sn whisker in Sn-Zn series solder is newly reported in this work. It is found that during the exposure of Sn-9Zn-0.5Ga-0.7Pr bulk solder to ambient conditions for a few hours, many different lengths of needle-like Sn whiskers originate spontaneously from the Sn-Pr intermetallic compounds of the solder and grow rapidly at a rate of about 3.5 Å/s. It is proposed that the driving force for whisker formation is the compressive stress resulting from the oxidation of Sn-Pr compounds, and that the free Sn atoms released from oxidation reaction feed the whisker growth during exposure.     

Active soldering of ZnS–SiO2 sputtering targets to copper backing plates using an Sn3.5Ag4Ti(Ce, Ga) filler metal

An Sn3.5Ag4Ti(Ce, Ga) active solder is used for joining ZnS–SiO₂ ceramic sputtering targets with copper backing plates at 250 °C in air. Direct soldering using the Sn3.5Ag4Ti(Ce, Ga) metal filler has been found to be a reliable and simple technique for ZnS–SiO₂ ceramic bonding with ZnS–SiO₂ and copper. The shear strengths for ZnS–SiO₂/ZnS–SiO₂ and ZnS–SiO₂/Cu joints are 6.5 and 5.2 MPa, respectively. The bonding mechanism is described, with emphasis placed on the action of a rare earth element (Ce) and the active metal reaction. The interfacial reaction between Sn3.5Ag4Ti(Ce, Ga) filler metal and copper at temperatures ranging from 120 to 200 °C is conducted and discussed.     

Sn-3.5Ag-0.5Cu/Cu界面的显微结构

研究了热-剪切循环条件下Sn-3．5Ag-0．5Cu钎料／Cu界面的显微结构，分析了界面金属间化合物的生长行为，并与恒温时效后的Sn-3．5Ag-0．5Cu／Cu界面进行了对比。结果表明：恒温时效至100h，Sn-3．5Ag-0．5Cu／Cu界面上已形成Cu6Sn5和Cu3Sn两层金属间化合物；而热-剪切循环至720周Sn-3．5Ag-0．5Cu／Cu界面上只存在Cu6Sn5金属间化合物层，无Cu3Sn层生成，在界面近域的钎料内，颗粒状的Ag3Sn聚集长大成块状；在热-剪切循环和恒温时效过程中，界面金属间化合物的形态初始都为扇贝状，随着时效时间的延长逐渐趋于平缓，最终以层状形式生长。     

The 260 °C phase equilibria of the Sn–Sb–Ag ternary system and interfacial reactions at the Sn–Sb/Ag joints

The isothermal section of the Sn–Sb–Ag ternary system at 260 °C has been determined in this study by experimental examination. Experimental results show no existence of ternary compounds in the Sn–Sb–Ag system. Two extensive regions of mutual solubility have been determined. The one located between the two binary isomorphous phases, Ag₃Sn and Ag₃Sb, is labeled as and the other one located between the two binary isomorphous phases, Ag₄Sn and Ag₄Sb, is labeled as ξ. The phase is a very stable phase and is in equilibrium with ξ, Sb, SbSn, Sb₂Sn₃, and liquid Sn phases. Each of the Sb and SbSn phases has a limited solubility of Ag. Only one stoichiometric compound, Sb₂Sn₃, exists. Besides phase equilibria determination, the interfacial reactions between the Sn–Sb alloys and the Ag substrate were investigated at 260 °C. It was found that the phase formations in the Sn–Sb/Ag couples are very similar to those in the Sn/Ag couples.     

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.     

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...     

Ag的添加量对Sn-9Zn无铅钎料性能的影响

研究Ag的添加量对Sn-9Zn无铅钎料性能的影响规律。结果表明,Ag不仅对Sn-9Zn无铅钎料的润湿性能和显微组织有明显作用,而且对钎料接头的力学性能也有较大的影响。添加0.3%Ag (质量分数, 下同)后,钎料的抗氧化性能得到提高,因此钎料的润湿性能得到改善。Sn-9Zn-0.3Ag具有比Sn-9Zn钎料更均匀的组织。研究结果还表明,添加0.3%Ag后,钎料接头的力学性能最佳,接头断口显示有大量的细小均匀的韧窝组织。当Ag的添加量添加到1%时,在韧窝底部出现Cu-Zn、Ag-Zn金属间化合物,此时,接头力学性能下降     

相图计算在电子材料焊接中的应用

焊料与基体的界面反应对高性能电子材料焊接接头的力学性能和可靠性都有着很重要的影响。把焊接过程分为界面反应和剩余焊料凝固两个过程进行讨论，在相图热力学的基础上，通过计算亚稳相图、比较界面处局部平衡时各相形成驱动力大小，预测了Sn-3．5％Ag／Cu、Sn-25％Ag／Cu和Sn-3．5％Ag／Ni扩散偶界面反应过程中的中间相形成序列；同时利用Scheil—Gulliver凝固模型模拟了Sn-25％Ag／Cu体系中过剩焊料的非平衡凝固过程，预测了焊料在随后冷却过程中的相演变信息。计算预测的结果与前人的实验结果吻合很好。     

锌对Sn3.5Ag0.5Cu钎料组织性能的影响

运用莱卡显微镜、X射线衍射仪等仪器设备,研究添加元素Zn对Sn3.5Ag0.5Cu钎料组织性能的影响.结果表明:Zn与Ag、Cu形成AgZn和CuZn3化合物,能显著细化Sn3.5Ag0.5Cu钎料组织,降低Sn3.5Ag0.5Cu钎料合金的润湿性,同时可提高Sn3.5Ag0.5Cu钎料合金抗拉强度.