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.     

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...     

Effects of cooling rates on microstructure and microhardness of lead-flee Sn-3.5%Ag solders

The microstructure and microhardness of Sn-3.5%Ag solders were explored in the cooling rate ranging from 0.08 to 10^4 K/s. Under rapid cooling condition, the strong kinetic undercooling effect leads to the actual solidification process starting at the temperature lower than the equilibrium eutectic point, and the actual metastable eutectic point shifts to the higher Ag concentration. Hence, the higher the applied cooling rate is, the more the volume fraction of primary β-Sn crystal forms. At the same time, the separation of primary β-Sn crystal favors restraining the formation of bulk Ag3Sn intermetallic compounds （IMCs） in solder due to the mismatch crystalline orientation relationship, those Ag3Sn phase separating through the eutectic reaction could hardly cling to the primary β-Sn crystal and grow up. Additionally, the Vickers hardness test shows that free β-Sn and spherical Ag3Sn phase in the rapidly solidified alloy strongly improves the microhardness of the Sn-3.5%Ag solder.     

Interfacial reactions between liquid Sn-8Zn-3Bi solders and Cu substrates

The morphology and growth kinetics of intermetallic compounds formed during the soldering reactions between Sn-8Zn-3Bi and Cu substrates at various temperatures ranging from 225 to 350 °C were investigated. The results indicated that a planar layer of Cu_32.1Zn_66.7Sn_0.7Bi_0.5 (γ phase) along with a great number of scallop-shaped intermetallic compounds Cu_19.3Zn_77.8Sn_2.9 (ɛ phase) appeared at the interfaces at temperatures lower than 325 °C. At temperatures higher than 325 °C, the interfacial intermetallics of a composition similar to the planar intermetallics appeared in cluster shape. Kinetics analysis indicated that the intermetallic growth was diffusion-controlled with activation energy of 24.6 KJ/mol.     

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.     

冷却速率对Sn-3.5Ag合金微观组织及力学性能的影响

研究了不同冷却速率对Sn-3.5Ag合金的微观组织、维氏硬度和力学性能的影响。通过采用空冷、水冷和急冷的方式获得了冷却速率分别为101、103和106 K/s的Sn-3.5Ag合金样品,对样品进行显微分析和力学性能测试后得出冷却速率对β-Sn二次枝晶臂间距和Ag3Sn相的分布有显著影响。随冷却速率的加快,β-Sn晶粒尺寸和二次枝晶臂间距逐渐减小,Ag3Sn晶粒尺寸也逐渐变小、分布更加均匀,样品硬度、力学性能也随冷却速率的增加而提高。研究结果表明,合金微观组织结构和Ag3Sn相的分布规律对合金力学性能有显著的影响,Ag3Sn相在合金中起了弥散强化的作用。     

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。     

稀土镧对Sn3．5Ag0．5Cu钎料组织性能的影响

运用莱卡显微镜、显微硬度计、拉伸试验机等仪器设备,研究添加不同含量稀土元素La对Sn3．5Ag0．5Cu钎料及其与Cu基体焊合后微观组织及性能影响。结果表明：添加不同含量的稀土La均能使Sn3．5Ag0．5Cu钎料及其与Cu基体焊合后组织与性能得到改善,其中以La含量达到0．05％时为最优,显微硬度及剪切强度分别提高14％和10．7％;基于热力学理论计算结果表明稀土元素La具有“亲Sn”倾向,可减小钎料中锡基化合物界面锡的活度,降低IMC的长大驱动力。     

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.     

Sn-9Zn-0.1S/Cu焊点液固界面金属间化合物的生长动力学

采用扫描电镜和光学显微镜观察研究了230~260℃焊接温度范围内Sn-9Zn-0.1S/Cu焊点界面金属间化合物的结构及生长动力学.结果表明,在该焊点界面形成的化合物可分为两层:靠铜侧的是厚且平直的γ-Cu₅Zn₈化合物层;靠焊料侧的则为另一薄且呈扇贝、粒状的CuZn化合物层.提高钎焊温度及延长反应时间基本不改变Sn-9Zn-0.1S/Cu焊点界面金属间化合物的结构和成分,但会使形成的界面金属间化合物层厚度增加.γ-Cu₅Zn₈金属间化合物层的厚度与反应时间的平方根呈线性关系,表明其生长由扩散机制控制.根据阿伦尼乌斯公式,Sn-9Zn-0.1S/Cu焊点界面γ-Cu₅Zn₈金属间化合物层反应活化能为22.09 kJ/mol.     

SnAgCu/Cu和SnPb/Cu界面热-剪切循环条件下化合物的生长行为

对热剪切循环条件下Sn-3.5Ag-0.5Cu/Cu和Sn-Pb/Cu界面上原子扩散和化合物的生长行为进行了研究。结果表明:再流焊后,在两界面上均形成一种Cu6Sn5化合物;随着热剪切循环周数的增加,两界面上化合物的形态均从扇贝状向层状生长,其厚度随循环周数的增加而增加,且生长基本遵循抛物线规律,说明Cu原子的扩散控制了Cu6Sn5化合物的生长。界面近域的钎料内,颗粒状的Ag3Sn聚集长大成块状。     

Active soldering of indium tin oxide (ITO) with Cu in air using an Sn3.5Ag4Ti(Ce,Ga) filler

Indium tin oxide (ITO) ceramics are bonded with ITO and Cu at 250 °C in air using an active solder Sn3.5Ag4Ti(Ce, Ga). The mechanism for such low temperature soldering of ITO ceramics in air has been investigated. Electron probe microanalyzer (EPMA) analyses reveal that the element oxygen distributes uniformly within the solder matrix after soldering, while Ti segregates effectively at the ITO/solder and Cu/solder interfaces at such a low temperature, giving satisfactory joining results of Cu/Cu, ITO/ITO, and ITO/Cu in air.     

热冲击下Sn2.5Ag0.7Cu0.1RE0.05Ni/Cu钎焊接头组织与性能

借助于SEM、EDS、XRD等检测手段对Sn2.5Ag0.7Cu0.1RE0.05Ni/Cu钎焊接头进行观察分析,研究了钎焊工艺参数及热冲击条件对Sn2.5Ag0.7Cu0.1RE0.05Ni/Cu钎焊接头界面金属间化合物和力学性能的影响。结果表明:添加0.05%(质量分数)Ni能细化Sn2.5Ag0.7Cu0.1RE钎料合金的初生β-Sn相和共晶组织;钎焊温度270℃和钎焊时间240 s时,钎焊接头抗剪切强度最大达26.9 MPa,较未添加Ni的钎焊接头提高8.9%;随着热冲击周期的增加,钎焊接头界面金属间化合物层平均厚度增加,界面粗糙度先增大后减小,钎焊接头强度降低;添加0.05%Ni能够抑制接头界面金属间化合物的成长、钎焊接头强度的降低,有利于改善接头可靠性。     

Scaling effect on Ag3Sn growth behaviours in micro-joints for flip chip assemblies

The scaling effect on Ag₃Sn growth behaviours in Sn–3.0Ag–0.5Cu (SAC305) micro-joints of flip chip assemblies was investigated using thermal shock (TS) tests. After assembly reflow, the large plate-like Ag₃Sn compounds only emerged from the Cu interface of small joints, which was strongly related with a higher local Ag concentration in the remaining solder. During TS cycling, the growth of Ag₃Sn grains exhibited comparatively more pronounced growth in the solder matrix of small joints, due to the stronger strain-enhanced coarsening induced by more cycle stress and strain. Coarsening kinetic models based on TS experiments were employed to predict Ag₃Sn growth, the kinetic constants N were determined to clarify the correlation of the joints scaling and Ag₃Sn coarsening in depth.     

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.     

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.     

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.     

Interfacial reactions and mechanical properties between Sn-4.0Ag-0.5Cu and Sn-4.0Ag-0.5Cu-0.05Ni-0.01Ge lead-free solders with the Au/Ni/Cu substrate

Sn-4.0Ag-0.5Cu (SAC) and Sn-4.0Ag-0.5Cu-0.05Ni-0.01Ge (SACNG) lead-free solders reacting with the Au/Ni/Cu multi-layer substrate were investigated in this study. All reaction couples were reflowed at 240 and 255 °C for a few minutes and then aged at 150 °C for 100-500 h. The (Cu, Ni, Au)₆Sn₅ phase was formed by reflowing for 3 min at the interface. If the reflowing time was increased to 10 min, both (Cu, Ni, Au)₆Sn₅ and (Ni, Cu, Au)₃Sn₄ phases formed at the interface. The AuSn₄ phase was found in the solder for all reaction couples. An addition of Ni and Ge to the solder does not significantly affect the IMC formation. After a long period of heat-treatment, the thickness of the (Cu, Ni, Au)₆Sn₅ and (Ni, Cu, Au)₃Sn₄ phases increased and the intermetallic compounds (IMCs) growth mechanism obeyed the parabolic law and the IMC growth mechanism was diffusion-controlled. The mechanical strengths for both the soldered joints decreased with increasing thermal aging time. The SACNG/Au/Ni/Cu couple had better mechanical strength than that in the SAC/Au/Ni/Cu couple.     

Sn-37PbNi界面反应行为的相图计算分析

采用Thermo-Calc软件及相关数据库,将相图计算应用到Sn-Pb共晶焊料与Ni基体的界面反应行为的分析当中.依据局部平衡理论,通过亚稳平衡状态的计算和中间相形成驱动力大小的比较,预测出了500 K焊接温度下Sn-37Pb与Ni基体界面处金属间化合物的形成序列为Ni3Sn4→Ni3Sn2→Ni3Sn.通过Sn-Pb-Ni三元系500 K和423 K下等温截面的计算,预测出了润湿反应和固态时效反应过程中系统的相转变的情况.计算与试验结果吻合较好.     

Ni元素对Sn2.5Ag0.7Cu0.1RE/Cu无铅微焊点界面IMC和力学性能的影响

以Sn2.5Ag0.7Cu0.1RE无铅钎料为研究对象,借助扫描电镜和X衍射等检测方法研究了Ni元素对Sn2.5Ag0.7Cu0.1RE/Cu无铅微焊点界面IMC和力学性能的影响.结果表明,添加适量Ni元素能显著细化Sn2.5Ag0.7Cu0.1RE钎料合金初生β-Sn相和共晶组织,抑制焊点界面区(Cu,Ni)6Sn5金属间化合物的生长和表面粗糙度的增加,提高无铅焊点抗剪强度.当Ni元素添加量为0.1%时,钎料合金组织细小均匀,共晶组织所占比例较多;焊点界面IMC薄而平整,(Cu,Ni)6Sn5颗粒尺寸小,对应焊点抗剪强度最高为45.6 MPa,较未添加Ni元素焊点提高15.2%.