稀土Pr对低银Sn-0.3Ag-0.7Cu-0.5Ga钎料蠕变行为的影响（英文）

为进一步促进电子封装用低银无铅钎料的发展,本实验采用纳米压痕法研究了新型含Pr低银Sn-0.3Ag-0.7Cu-0.5Ga(SAC-Ga)钎料显微组织与蠕变性能之间的关系。结果表明,SAC-Ga、SAC-Ga-0.06Pr、SAC-Ga-0.5Pr 3种钎料的蠕变位移分别为1717,1144,1472nm;稀土Pr可通过细化Cu6Sn5金属间化合物并促使其均匀分布从而明显提高SAC-Ga钎料的蠕变强度;与SAC-Ga-0.06Pr钎料相比,SAC-Ga-0.5Pr由于过量稀土Pr的表面氧化而导致其蠕变强度有所下降。此外,本实验采用Dorn模型研究了含Pr的SAC-Ga钎料的室温蠕变行为并计算了对应的钎料蠕变应力指数n;阐明了Pr对SAC-Ga钎料蠕变强度的强化机理,即当位错遇到细小且均匀分布的Cu6Sn5金属间化合物时,位错移动只能采用绕过机制,从而提高了含Pr低银钎料的抗蠕变性能。     

微连接Cu/SAC305/Cu界面元素扩散与几何尺寸效应

通过对不同钎料层厚度(15~50μm)的Cu/SAC305/Cu三明治结构焊缝进行高温时效处理,研究在高温时效过程中钎料层厚度对IMC生长行为的影响.结果表明,钎料层厚度对高温时效过程中的界面元素固态扩散的影响显著.钎料层厚度越小,在时效过程中界面处越有利于Cu₃Sn的生长,160℃时效相同时间后Cu₆Sn₅层与Cu₃Sn层的厚度比越小;时效过程中IMC层(Cu₆Sn₅层+Cu₃Sn层)的生长速率随着钎料层厚度的减小也呈现减小的趋势;扩散系数受钎料层尺寸的影响,扩散系数与钎料层厚度之间近似满足抛物线关系.     

热浸镀锡铜磷钎料的性能

以Cu93P钎料为基体,在其表面热浸镀锡,制备CuPSn钎料,采用扫描电镜、万能力学试验机、显微硬度计、差热分析仪、箱式电阻炉和体视显微镜分析锡镀层的界面形貌,钎料的抗拉强度、显微硬度、熔化温度和润湿性。结果表明：在Cu93P钎料表面热浸镀锡过程中,液态锡与钎料发生了界面反应,生成Cu₆Sn₅金属间化合物,即钎料基体与锡镀层形成良好的冶金结合;随着热浸镀温度的升高和时间的延长,CuPSn钎料的抗拉强度和显微硬度均呈降低趋势,抗拉强度的降低源于界面处产生的Cu₆Sn₅脆性化合物和孔洞,显微硬度的降低源于热浸镀的去应力退火作用;Cu93P钎料表面热浸镀锡可降低钎料的熔化温度,提高钎料的润湿性,Cu93P钎料表面热浸镀5.20%（质量分数）锡之后,Cu88.16P6.64Sn5.20在纯铜板上的润湿铺展面积比基体Cu93P钎料增加43.15%。     

热循环对Sn58Bi(纳米Ti)/Cu焊点界面与性能影响

为了改善Sn-58Bi低温钎料的性能,通过在Sn-58Bi低温钎料中添加质量分数为0.1%的纳米Ti颗粒制备了Sn-58Bi-0.1Ti纳米增强复合钎料。在本文中,研究了纳米Ti颗粒的添加对-55～125 _^oC热循环过程中Sn-58Bi/Cu焊点的界面金属间化合物(IMC)生长行为的影响。研究结果表明：回流焊后,在Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的界面处都形成一层扇贝状的Cu₆Sn₅ IMC层。在热循环300次后,在Cu₆Sn₅/Cu界面处形成了一层Cu₃Sn IMC。Sn-58Bi/Cu焊点和Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度均和热循环时间的平方根呈线性关系。但是,Sn-58Bi-0.1Ti/Cu焊点的IMC层厚度明显低于Sn-58B/Cu焊点,这表明纳米Ti颗粒的添加能有效抑制热循环过程中界面IMC的过度生长。另外计算了这两种焊点的IMC层扩散系数,结果发现Sn-58Bi-0.1Ti/Cu焊点的IMC层扩散系数(整体IMC、Cu₆Sn₅和Cu₃Sn IMC)明显比Sn-58Bi/Cu焊点小,这在一定程度上解释了Ti纳米颗粒对界面IMC层的抑制作用。     

Si元素对Ti-Cu-Zr-Ni基非晶钎料微观组织和性能的影响

采用电弧熔炼和快冷甩带工艺制备了(Ti_0.46Cu_0.14Zr_0.27Ni_0.13)_1-xSi_x非晶钎料,研究了添加一定量的Si对钎料非晶形成能力的影响。结果表明,当Si的含量达到0.5%时钎料的非晶形成能力最强,钎料的润湿面积为3.06 cm₂,过冷液相区宽度(?T_x)?T_x=56 ℃,约化玻璃转变温度(T_rg)T_rg=0.5387,液相线温度为949 ℃。以此非晶合金作为钎料对SiC和TC4进行真空钎焊,所得钎焊接头剪切强度为80 MPa。Si元素的加入显著提高了钎料的非晶形成能力。     

Cu/Sn-58Bi/Cu焊点在电迁移过程中晶须和小丘的生长

利用SEM和EDS研究了Cu/Sn--58Bi/Cu焊点在电流密度为5×10³ A/cm², 80℃条件下晶须和小丘的生长. 通电540 h后, 在焊点阴极界面区出现了钎料损耗, 同时形成了晶须, 而在阳极Cu基板的钎料薄膜上形成了大量弯曲状晶须和块状小丘. EDS检测表明, 这些 晶须和小丘为Sn和Bi的混合物. 通电630 h后, 阳极上的晶须和小丘数量明显增多, 原来形成晶须的尺寸和形状没有变化, 阴极界面处 形成Cu₆Sn₅金属间化合物. 上述现象表明: 电迁移引发了金属原子的扩散迁移, 从而在阳极Cu基板上形成了一层钎料薄膜. 钎料薄膜中金属间化合物的形成导致压应力的产生, 促使晶须和小丘生长, 而阴极钎料损耗区域内晶须的形成与Joule热聚集有关.     

稀土镧钕对Ti15Cu15Ni钎料硬度及TC4接头抗剪强度的影响

在Ti15Cu15Ni钎料合金基础上添加微量稀土镧钕,以应用普遍的TC4为母材,研究稀土镧钕添加量对钎料合金及钎焊接头性能的影响.结果表明,稀土相分布于α-Ti及金属间化合物的相界,阻碍位错运动,使钎料硬度增加,在稀土含量为1%时达到最大40HRC.稀土镧钕对Ti15Cu15Ni抗剪强度具有较大影响,稀土含量小于0.5%时,抗剪强度随稀土含量增加而增加;稀土含量大于0.5%时,随着稀土含量增加,钎料合金抗剪强度呈下降趋势.当稀土含量等于0.5%时,抗剪强度达到最大为244.55 MPa.     

电场对浮法玻璃与可伐合金4J29钎焊接头组织与性能的影响

本文采用ALTSAB技术,选用SnAg3.5Ti2钎料,实现了可伐合金4J29与浮法玻璃的有效连接。研究了电压、温度对界面微观结构和剪切强度的影响,并探究了连接形成的机制。研究结果表明：随着电压和温度的升高,玻璃与钎料界面平直无显著变化,界面形成新的化学键≡Si-O-Ti和≡Si-O-Sn,发生氧化反应生成TiO、SnO; 钎料与合金侧有反应溶解现象,可伐合金侧生成了FeSn₂相,钎料中分布着一些细长棒状和针状的Ni₃Sn₄相,分析认为：钠离子耗尽层的产生以及Ti^₂₊、Sn^₂₊向玻璃基体中的扩散是形成有效连接的关键。接头剪切强度随电压和温度的升高而增大,当电压为1000V、温度400℃时,最大剪切强度为12.5Mpa。     

纳米锑掺杂对回流焊Sn-3.0Ag-0.5Cu-xSb焊点界面IMC生长的影响机理

研究了纳米锑掺杂对回流焊过程中Sn-3.0Ag-0.5Cu-xSb(x=0,0.2%,1.0%和2.0%)焊点界面金属间化合物(IMC)生长动力学的影响.借助扫描电镜(SEM)观察了焊点的微观结构,利用X射线能谱分析(EDX)及X射线衍射谱仪(XRD)确定了IMC的相和成分.结果表明,部分纳米锑颗粒溶解在富锡相中形成SnSb二元相,部分纳米锑颗粒溶解在Ag₃Sn相中形成Ag₃Sb相,剩余部分沉降在界面Cu₆Sn₅金属间化合物层表面.随着纳米锑含量的增加,IMC厚度减小.当纳米锑的含量为1.0%时,IMC厚度最小.通过曲线拟合,确定出界面IMC层生长指数和扩散系数.结果表明,IMC层生长指数和扩散系数均随着纳米锑含量的增加而减小.当纳米锑的含量为1.0%,IMC层生长指数和扩散系数均有最小值,分别为0.326和10.31×10^-10 cm²/s.由热力学相图和吸附理论可知,Sn,Sb元素之间易形成SnSb化合物,引起Sn元素的活性、Cu-Sn金属间化合物形成的驱动力和界面自由能下降,从而导致Cu₆Sn₅金属间化合物生长速率下降,抑制IMC生长.     

SnZn系无铅钎料性能对比分析

对比研究了4种SnZn系无铅钎料的润湿性、抗蠕变性能以及力学性能.结果表明,SnZnAg/SnZnGa/SnZnAl的润湿性均高于SnZn钎料,合金元素的添加可以显著提高SnZn钎料的润湿性;SnZnAg钎料的抗蠕变性能最高,这主要是因为Ag-Zn金属间化合物颗粒钉扎位错引起的;合金元素的添加可以显著提高SnZn焊点的...     

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.     

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.     

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.     

Intermetallic compound growth suppression at high temperature in SAC solders with Zn addition on Cu and Ni-P substrates

The effect of adding 0.5-1.5 wt.% Zn to Sn-3.8Ag-0.7Cu (SAC) solder alloy during reflow and solid state ageing has been investigated. In particular, the role of the Zn addition in suppressing interfacial Intermetallic Compound (IMC) growth on Cu and Ni-P substrates has been determined. Solder-substrate couples were aged at 150 °C and 185 °C for 1000 h. In the case of 0.5-1.0 wt.% Zn on Cu substrate, Cu₃Sn IMC was significantly suppressed and the morphology of Cu₆Sn₅ grains was changed, leading to suppressed Cu₆Sn₅ growth. In the SAC-1.5Zn/Cu substrate system a Cu₅Zn₈ IMC layer nucleated at the interface followed by massive spalling of the layer into the solder, forming a barrier layer limiting Cu₆Sn₅ growth. On Ni-P substrates the (Cu,Ni)₆Sn₅ IMC growth rate was suppressed, the lowest growth rate being found in the SAC-1.5Zn/Ni-P system. In all cases the added Zn segregated to the interfacial IMCs so that Cu₆Sn₅ became (Cu,Zn)₆Sn₅ and (Cu,Ni)₆Sn₅ became (Ni,Cu,Zn)₆Sn₅. The effect of Zn concentration on undercooling, wetting angles and IMC composition changes during ageing are also tabulated, and a method of incorporating Zn into the solder during reflow without compromising solder paste reflow described.     

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.     

Creep properties of Sn-Ag solder joints containing intermetallic particles

The creep behavior of the eutectic tin-silver joints and tin-silver composite solder joints containing 20 vol.% of Cu₆Sn₅, Ni₃Sn₄, and FeSn₂ intermetallic reinforcements introduced by in-situ methods was investigated. These creep tests were carried out using single shear lap solder joints at room temperature, 85°C, and 125°C. The creep resistance was similar in magnitude for all alloys, and with increasing temperature, the stressexponents decreased in a manner consistent with power-law breakdown behavior. The FeSn₂ intermetallic reinforced composite solder was found to be the most creep-resistant alloy at room temperature. Creep failure was observed to occur within the solder matrix in all these solder joints. Although a detailed analysis of the processes involved was difficult because of smearing of the features in the fracture surface, there were indications of grain-boundary separation, ductile fracture, and interfacial separation. For more information, contact K.N. Subramanian, Michigan State University, Department of Materials Science and Mechanics, 3536 Engineering Building, East Lansing, Michigan 48824-1226; (517) 353-5397; fax (517) 353-9842; e-mail subraman@egr.msu.edu.     

Microstructure evolution in Cu pillar/eutectic SnPb solder system during isothermal annealing

The reaction between Cu pillar and eutectic SnPb solder during isothermal annealing was studied systematically. Intermetallic compounds (IMCs), such as Cu₆Sn₅ and Cu₃Sn, were formed in between Cu and SnThe parabolic rate law was observed on IMC formation, which indicated that the growth of IMCs was controlled by atomic diffusion (a diffusion-limited process). Annealing at 165 °C for 160 h decreased the growth rate of Cu₆Sn₅, and at the same time increased the growth rate of Cu₃Sn. This was when Sn in solder was exhausted completely. The activation energies for the growth of Cu₃Sn and Cu₆Sn₅ were measured to be 1.77 eV and 0.72 eV, respectively. The Kirkendall void that formed at the interface between Cu pillar and solder obeyed the parabolic rate law. The growth rate of the Kirkendall void increased when the Sn in solder was consumed in its entirety.     

Evolution of CuSn intermetallics between molten SnAgCu solder and Cu substrate

The evolution of SnCu intermetallic compounds (IMCs) between a molten SnAgCu alloy and the Cu under-bump metallization (UBM) throughout reflow is presented based on interruption of soldering reactions in experiments by removing the liquid solder from the substrate. This allows to capture and visualize interfacial reactants at arbitrary moments of the soldering process, and to gain an insight into their formation characteristics. The results show that the interfacial Cu₆Sn₅/Cu₃Sn structure is formed at an early stage of reflow and is maintained throughout the process. Based on the experiments, formation mechanisms of interfacial CuSn IMCs are discussed.     

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.     

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.