微量Ni对Sn2.5Ag0.7Cu钎料组织和性能的影响

研究微量Ni元素对Sn2.5Ag0.7Cu钎料显微组织和力学性能的影响。结果表明,Sn2.5Ag0.7Cu合金主要由β-Sn相、Ag3Sn相和Cu6Sn5相组成;添加微量的Ni元素后,可以有效地细化合金的内部组织,且共晶组织内部产生以Cu6Sn5相为基的(Cu,Ni)6Sn5相,或Ag3Sn相为基的(Ag,Ni)3Sn相。焊点界面主要为Cu基体、IMC层和钎料3个区域;随着钎焊时间的延长或钎焊温度的增加,IMC层在Cu基体侧较为光滑平坦,而钎料侧呈现扇贝状分布;钎焊接头的剪切强度都是呈先增大后减小趋势,在钎焊时间240 s和钎焊温度300℃达到最大值48 MPa。     

Sn对Mg-5Li合金铸态和挤压态组织的影响

在氩气保护气氛下熔炼,得到Mg-5Li-xSn（x=0.15,0.25和0.65,质量分数）系列合金。通过光学显微镜、扫描电镜、X射线衍射仪和能谱仪分析合金的显微组织。结果表明,Mg-5Li合金中添加的Sn元素可以起到明显的晶粒细化作用,当Sn含量从0.15%增加到0.65%时,铸态合金的平均晶粒尺寸从556μm细化到345μm,相应的挤压态合金的晶粒从33μm减小到23μm。近似网状的第二相Mg2Sn分布在铸态合金的晶界上,挤压之后,颗粒状的Mg2Sn主要分布在晶粒内部。这些金属间化合物在挤压动态再结晶中可以作为有效的形核质点,从而起到细化晶粒的作用。     

快速凝固Sn2.5Ag0.7Cu钎料中金属间化合物的形态及对焊点性能的影响

利用SP009A型半自动非金属系制造器,通过铜制单辊快淬工艺制得快速凝固态Sn2.5Ag0.7Cu钎料合金薄带,采用JSM-5610LV扫描电镜及能谱仪,研究快速凝固态钎料合金的微观形貌及金属间化合物(IMC)特征;通过钎焊接头组织与剪切断口分析,研究IMC对钎焊接头韧性的影响机制。结果表明:快速凝固态钎料合金焊点界面处形成的排列紧密的小尺寸β-Sn能有效抑制界面处IMCCu6Sn5的长大;在钎焊过程中,钎料中过饱和固溶体析出大量尺寸细小、弥散分布的金属间化合物Cu6Sn5和Ag3Sn,凝固时可作为第二相粒子与初生相混杂在一起,形成细小共晶组织分布于钎缝中,改善了焊点韧性。     

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%.     

微量铈对Sn57Bi1Ag焊料合金组织性能的影响

研究了微量铈对Sn57Bi1Ag焊料合金性能(物理性能、润湿性能及力学性能等)与组织的影响。结果表明,与Sn57Bi1Ag焊料合金相比,添加铈的作用较明显,适量的铈可有效细化组织,抑制焊料/Cu界面的金属间化合物的生长;能略微降低焊料熔化温度;但是提高了焊料合金的电阻率;未能改善焊料合金的耐蚀性能;当铈含量(质量分数)为0.05%时,焊料有较好的润湿性。当铈含量为0.05%～0.25%时焊料合金具有较好的综合性能。     

Zn元素对Sn0.5Ag0.7Cu/Cu接头剪切性能和时效接头组织结构的影响

为了改善Sn0.5Ag0.7Cu/Cu接头组织结构和力学性能,通过在Sn0.5Ag0.7Cu钎料中添加Zn元素,以Sn0.5Ag0.7Cu-xZn (x=0, 0.1, 0.4, 0.7, 1)钎料合金对紫铜基板进行了熔钎焊试验,并对接头进行微观组织及力学性能分析. 结果表明,改变了接头结合界面处金属间化合物(intermetallic compound,IMC)组织结构,增强了接头剪切断裂的韧性断裂特征,提高了接头抗剪强度. 当Zn元素的加入量为0.4% (质量分数)时,接头抗剪强度达到最高的47.81 MPa. 添加Zn元素等温时效处理后,对接头中IMC层的生长有着抑制作用,并且随着时效温度的提高和时效时间的延长,脆性层Cu₅Zn₈会破碎直至消失,因此在改善接头结合界面处IMC组织性能的同时,不会改变其组成和结构.     

Sn3.0Ag0.5Cu/Cu无铅焊点剪切断裂行为的体积效应

采用直径范围为200—600μm的Sn3.0Ag0.5Cu无铅钎料球在Cu焊盘上制作热风重熔焊点,将重熔焊点在150℃下进行老化,并对重熔和老化焊点进行剪切测试.结果表明:重熔和老化后焊点的剪切强度都随体积的增大而减小,表现出显著的体积效应.SEM断面观察显示:较小体积焊点剪切断裂发生在钎料块体内部,表现出较好韧性;较大体积焊点则发生在近焊盘的界面处,呈现脆性断裂特征.焊盘界面处和钎料内部微观组织SEM观察表明:小体积焊点内部Ag_3Sn化合物以小颗粒状弥散分布,起到强化作用;而大体积焊点内部Ag_3Sn化合物为树枝网状分布,表现出硬脆性.金属间化合物(如Ag_3Sn和Cu_6Sn_5)的形貌和分布对焊点的断裂行为有显著的影响,是焊点剪切断裂行为体积效应的内在原因.     

Sn3.0Ag0.5Cu0.05Cr/Cu焊点界面IMC层热时效形貌及生长行为研究

研究了Sn3.0Ag0.5Cu0.05Cr焊料(SACCr)制成的Cu/Solder/Cu焊点在150℃时效0、168、500及1000 h下界面金属间化合物(IMC)层的形貌及生长行为,并与Sn3.0Ag0.5Cu(SAC)焊料的焊点进行了比较。结果表明,相对于SAC的焊点,SACCr中弥散或固溶分布的微量Cr延缓了焊点界面IMC层的生长。时效时间越长,Cr的阻抑效果越明显。150℃时效1000 h的Cu/SACCr/Cu焊点界面IMC层的平均厚度是Cu/SAC/Cu的45%,仅为5.13μm。     

合金元素对中温Sn-Ag-Cu焊料互连组织及剪切强度的影响

针对SAC305和改良添加了Ni、Sb、Bi元素的2种焊料及其分别与NiSn、NiAu、NiPdAu 3种镀层器件钎焊形成的互连焊点,采用SEM、EDS、EPMA、TEM、DSC等方法研究了Ni、Au、Pd、Sb、Bi等添加元素对金属间化合物(IMC)种类及厚度、焊料第二相形貌及分布以及焊点剪切强度的影响。结果发现,受Ni元素界面耦合作用的影响,焊点器件侧和印刷电路板(PCB)侧生成的IMC均为(Cu, Ni)6Sn5化合物;焊料中Sb、Ni元素减缓IMC生长,因此同一镀层下改良焊料的界面IMC厚度小于SAC305的;镀层中Au元素降低IMC生长速率,而Pd元素促进IMC生长,因此同一焊料下NiPdAu镀层样品的界面IMC厚度最大,而NiAu镀层样品的界面IMC厚度最小;镀层中Au、Pd元素的加入,促进焊料中Ag3Sn相从弥散颗粒状分布转为网状分布,焊点强度得到提升;焊料中Ag、Cu元素的加入,增加弥散分布的(Cu, Ni)6Sn5和Ag3Sn体积分数,提高焊点剪切强度;焊料中添加Bi元素导致焊料熔点降低,但可析出Bi单质起到弥散强化作用;因此,添加了Ni、Sb、Bi元素的改良焊料的焊点剪切强度,均高于同等条件下SAC305焊点样品的剪切强度。     

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。     

Investigation of small Sn–3.5Ag–0.5Cu additions on the microstructure and properties of Sn–8Zn–3Bi solder on Au/Ni/Cu pads

The formation of intermetallic compounds and the shear strength of Sn–Zn–Bi solder alloys with various (0, 1, 3, 5 and 7 wt%) weight percentages of Sn–Ag–Cu were investigated on Au/Ni metallized Cu pads depending on the number of reflow cycles. In Sn–Zn–Bi solder joints, scallop-shaped AuZn₃ intermetallic compound (IMC) particles were found at the interfaces and in the solder ball regions, fine Bi- and needle-shaped Zn-rich phase were observed in the Sn matrix. After Sn–Ag–Cu additions, an additional Ag–Zn intermetallic compound layer was adhered to the top surface of the AuZn₃ layer at the interface and fine spherical-shaped AgZn₃ intermetallic compound particles were detected in the solder ball regions together with Bi- and Zn-rich phase volumes. After the addition of Sn–Ag–Cu, the shear strength of Sn–Zn–Bi solder joints increased due to the formation of the fine AgZn₃ intermetallic compound particles. The shear strengths of Sn–Zn–Bi and Sn–Zn–Bi/7 wt% Sn–Ag–Cu solder joints after one reflow cycle were about 44.5 and 53.1 MPa, respectively and their shear strengths after eight reflow cycles were about 43.4 and 51.6 MPa, respectively.     

ECAP对连铸Cu-Ag合金断口形态及力学性能的影响

采用连续铸造和等径角挤压变形(ECAP)加工集成技术制备Cu-Ag合金,研究其力学性能和相应的拉伸断口形态。研究发现,Cu-Ag合金的强度随着ECAP加工道次和Ag含量的增加而增加,而延伸率却下降。连续铸造和ECAP加工的合金与传统浇铸和ECAP加工的合金相比,缩颈前静态韧性有所提高。同时发现,只有连铸的Cu-Ag合金在断裂前表现出缩颈现象,而经ECAP挤压后试样的断裂变为剪切模式,随着ECAP道次的增加出现不同的剪切断裂角。基于实验结果,讨论了经ECAP挤压后连铸Cu-Ag合金的拉伸断裂机制。     

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.     

真空压铸Mg-7Al(-2Sn)合金组织性能研究及第一性原理计算

利用光学显微镜、扫描电子显微镜、能谱分析、X射线衍射、差热分析及拉伸试验比较分析了2%Sn(质量分数)对真空压铸和固溶态Mg-7Al合金的组织与力学性能的影响。结果表明,向Mg-7Al合金中添加2%Sn元素后,能够细化晶粒,抑制Mg17Al12相的生长,在组织中形成新相Mg2Sn,其以颗粒状弥散分布于基体中;固溶处理后Mg-7Al合金中第二相数目明显减少,AT72合金基体中仍存在细小颗粒状Mg2Sn。由于合金组织细化、第二相数量的增加,Mg17Al12相形貌改善以及具有良好热力学性质的Mg2Sn相的析出的综合作用,使得AT72合金表现出比Mg-7Al合金更好的室温及高温拉伸力学性能;固溶处理后的AT72合金表现出更为优异的力学性能,主要强化机制包括:固溶强化和弥散强化。此外,利用第一性原理计算从微观理论角度探讨了Sn合金化Mg-7Al合金力学性能改善的原因。     

AgCuZn-X(Ga, Sn, In, Ni)钎料显微组织及钎焊接头研究

研究了不同合金元素Ga,Sn,In和Ni添加对Cd银基钎料及其钎焊接头的显微组织影响,同时对AgCuZn-X(Ga,Sn,In,Ni)钎料的对接和搭接实验做了对比实验分析。结果表明,添加Ga,Sn,In和Ni4种元素的银钎料具有"特有的镓结构",具有较低的固相线和液相线,其钎缝力学性能优异,由SEM观察钎缝显微组织可知,低银含镓钎料具有与高银高镓钎料相近的织网状致密组织,添加适当的元素可以显著提高低银钎料的性能。     

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.     

等通道转角挤压Al-10Mg-4Si合金的组织与性能研究

在250℃下以Bc路径对Al-10Mg-4Si合金进行4道次和8道次的等通道转角挤压,以求达到改善合金组织和提高合金力学性能的目的.扫描电子显微镜(SEM)和透射电子显微镜(TEM)对挤压前后的微观组织分析表明:铸态合金基体晶粒比较粗大,第二相Mg_2Si以粗大的汉字状或骨骼状分布于基体晶界处;经ECAP挤压后,基体晶粒得到细化,原粗大的汉字状Mg_2Si被碎化为短棒状或多边形状颗粒,并呈一定的弥散分布.室温拉伸测试结果表明:ECAP4道次挤压后,合金的抗拉强度和伸长率由铸态的166MPa、1.64%提高为322MPa、21.7%;ECAP8道次挤压后,合金的伸长率继续提高为24.7%.但抗拉强度下降到293MPa.     

Reaction properties and interfacial intermetallics for Sn−xAg−0.5Cu solders as a function of Ag content

Wetting and interfacial reactions were investigated for Sn−xAg−0.5Cu alloys, in which the Ag content had a variation from x=1.0 to x=4.0. Differential scanning calorimetry (DSC) was used to investigate the range of the melting temperature and the solidification temperature by measuring the endothermic and the exothermic heat flow, respectively. Low Ag contents increased the melting temperature ranges and deteriorated the wetting properties such as zero cross time and wetting force measured at two seconds. The extent of undercooling increased and the thickness of intermetallic compounds (IMC) decreased as the Ag content decreased. As the Ag content decreased, the initial IMC thickness decreased due to the large undercooling and, during the solid aging at 170°C, the IMC growth slightly decelerated because of the small diffusion coefficient. For the application of good drop shock reliability, Sn−Ag−Cu solder of low Ag content should be beneficial due to the restraint of the IMC growth (Cu₆Sn₅ and Cu₃Sn) and of the coarse plate-like IMC (Ag₃Sn).     

等通道转角挤压Mg-3.52Sn-3.32Al合金的组织与力学性能

采用等通道转角挤压（ECAP）Bc路径对固溶态Mg-3.52Sn-3.32Al合金分别挤压1、4和8道次。利用光学显微镜、扫描电子显微镜、透射电子显微镜和X射线衍射仪分析合金的组织和相组成,并测试了其室温拉伸力学性能。结果表明,经ECAP挤压后,固溶态合金组织中析出大量细小的Mg2Sn相和极少量的Mg17Al12相。随挤压道次增加,合金的综合力学性能先提高后降低。经4道次挤压后,合金的综合拉伸力学性能相对较佳,抗拉强度、伸长率和硬度分别达到250 MPa、20.5%和61.3 HV9.8,较未ECAP时分别提高43.7%、105%和26.9%。经ECAP挤压的合金室温拉伸断口均呈韧性断裂。等通道转角挤压Mg-3.52Sn-3.32Al合金的力学性能受晶粒尺寸、析出相以及组织织构的共同影响。     

Dissolution and interfacial reactions of thin-film Ti/Ni/Ag metallizations in solder joints

The dissolution and interfacial reactions involving thin-film Ti/Ni/Ag metallizations on two semiconductor devices, diode and metal-oxide-semiconductor field-effect transistor (MOSFET), a Sn–3.0Ag–0.7Cu solder, and a Au-layer on the substrates are studied. To simulate the dissolution kinetics of the Ag-layer in liquid solder during the reflow process, the computational thermodynamics (Thermo-Calc) and kinetics (DICTRA: DIffusion Controlled TRAnsformations) tools are employed in conjunction with the assessed thermochemical and mobility data. The simulated results are found to be consistent with the observed as-reflowed microstructures and the measured Ag contents in the solder. In the as-reflowed joints two different intermetallic compounds (IMC) are found near the diode/solder interface. Both are in the form of particles of different morphologies, not a continuous layer, and are referred to as IMC-I and IMC-II. The former corresponds to Ni₃Sn₄ with Cu atoms residing in the Ni sublattice. It is uncertain whether IMC-II is Cu₆Sn₅ phase with Ni atoms residing in the Cu sublattice or a Cu–Ni–Sn ternary phase. Near the as-reflowed MOSFET/solder interface, both particles and a skeleton-like layer of Ni₃Sn₄ are observed. The primary microstructural dynamics during solid state aging are the coarsening of IMC particles and the reactions involving the unconsumed (after reflow) Ni- and the Ti-layer with Sn and Au. While the reaction with the Ni-layer yields only Ni₃Sn₄ intermetallic, the reaction involving the Ti-layer suggests the formation of Ti–Sn and Au–Sn–Ti intermetallics. The latter is due to the diffusion of Au from the substrate side to the die side. It is postulated that the kinetics of Au–Sn–Ti layer is primarily governed by the diffusion of Au through the Ni₃Sn₄ layer by a grain boundary mechanism.