无铅焊料的研究（3）——物理性质与界面反应

针对具有潜在应用价值的数种无铅焊料合金系统(包括Sn-Cu、Sn-Ag、Sn-In和Sn-Ag-Cu合金,尤其是具有应用潜力的共晶合金),整理分析了有关其界面反应与物理性质方面的研究结果,可作为无铅焊料相关研究的参考.     

电子封装与组装焊点界面反应及微观组织研究进展

软钎焊焊点界面反应是连接金属的最古老的冶金工艺过程。随着倒装芯片(FC)、球栅阵列(BGA)和芯片级封装(CSP)等面封装技术的兴起,近年来Sn基钎料被广泛应用于微电子制造,包括芯片和基板之间的封装互连以及基板与印制电路板之间的组装互连。这就需要系统地研究Sn基钎料焊点界面反应及微观组织。从形态学、热力学和动力学的角度回顾总结了SnPb共晶钎料、高Pb钎料和无Pb钎料与Cu、Ni、Au/Ni/Cu、PdAg焊盘之间的界面反应。     

无铅BGA封装可靠性的力学试验与分析

着重研究了机械冲击和应力对无铅BGA封装焊点可靠性的影响,介绍了BGA封装的可靠性力学试验(跌落、弯曲试验)及其分析方法.通过对力学试验中失效焊点的分析以及借助ANSYS模拟工具,找出引起失效的根本原因,为开发性能更好、高可靠性的无铅材料、改进无铅工艺提供依据.     

SnBiEr/Cu界面反应及时效过程中IMC的研究

采用SEM观察等手段研究了Sn58BixEr(x=0,0.1,0.5;表示添加质量分数0.01%,0.5%的Er)/Cu钎焊接头界面反应以及在120℃时效过程中金属间化合物(IMC)的生长行为。实验结果表明:Sn58BixEr/Cu钎焊接头IMC层厚度随着钎焊温度的升高而增厚,添加微量的Er能够有效抑制界面IMC的生长。在时效过程中,界面IMC层的厚度随着时效时间的增加而逐渐增厚。通过对实验数据进行拟合,得出120℃时效温度下Sn58Bi0.1Er/Cu和Sn58Bi0.5Er/Cu的IMC层的生长速率常数分别为3.42×10–16 m2/s和2.84×10–16 m2/s。     

电迁移对Ni/Sn63Pb37/Cu焊点界面反应的影响

研究了在125℃,1×103 A/cm2条件下电迁移对Ni/Sn63Pb37/Cu BGA焊点界面反应的影响.回流后,在焊料/Ni界面处形成Ni3Sn4、在焊料/Cu界面处形成Cu6Sn5的金属间化合物.随着电迁移时间增加,芯片侧金属间化合物转变为(Cu,Ni)6Sn5类型化合物,印制板侧Cu6Sn5金属间化合物类型保...     

倒装芯片封装中多层铜互连结构的界面分层

芯片封装过程中,较高的机械热应力易导致多层铜互连结构发生分层甚至断裂失效。运用三级子模型技术建立了倒装芯片10层铜互连结构的有限元分析模型,通过计算不同界面裂纹尖端能量释放率对多层铜互连结构的界面分层展开研究。结果表明：第10层Cu/SiN和金属间电介质(IMD)/SiN界面,以及第9层Cu/SiN界面的裂纹尖端能量释放率远大于其他界面,是易发生分层失效的关键界面;总体互连线介电材料的弹性模量和热膨胀系数对关键界面能量释放率都有影响。基于此分析,对总体互连线介电材料的选取进行优化,发现第10层选择弹性模量与热膨胀系数乘积最大的非掺杂硅玻璃(USG),第9层选择弹性模量与热膨胀系数乘积最小的有机硅酸盐玻璃(OSG)时更有利于提高多层铜互连结构界面可靠性。     

Sn-9Zn/Cu 焊点界面反应及其化合物生长行为

通过扫描电镜(SEM)等手段研究了Sn-9Zn/Cu在不同浸焊时间与时效时间等条件下的界面反应及其金属间化合物(IMC)生长行为。结果表明:在浸焊后,Sn-9Zn/Cu钎焊接头界面形成了扇贝状的界面化合物Cu5Zn8,IMC层厚度随着浸焊时间与时效处理时间的增加而增加,未时效处理的焊点界面IMC与铜基板接触的一面较为平直,而与钎料接触的一侧呈现出锯齿状,随着时效时间的增加,界面变得越来越不平整;另外在IMC层与焊料之间产生裂缝现象,分析认为是由于钎料与IMC之间的热膨胀系数差异导致热应力形成裂缝。浸焊600 s后的试样在时效15 d后IMC层与Cu基板接触侧产生了与初始金属间化合物Cu5Zn8不同的三元化合物Cu6(Sn,Zn)5。     

基板稀土微合金化对Sn3Ag0.5Cu/Cu钎焊界面反应的影响

研究了在Cu基板中加入质量分数1%的稀土元素Ce、Er后,与Sn3Ag0.5Cu(SAC305)无铅钎料进行钎焊并时效处理后的界面反应及其化合物(IMC)生长行为。结果表明:钎焊完成后,在SAC305/Cu钎焊界面只观察到Cu_6Sn_5,而SAC305/Cu-1Ce及SAC305/Cu-1Er界面还有Cu_3Sn形成;在时效处理过程中,纯Cu基板上的金属间化合物生长速率最快,Cu-1Ce基板次之,Cu-1Er基板最慢,且形成的IMC厚度也是依次递减;加入质量分数1%的Ce、Er元素对IMC生长均有抑制作用,且Er的抑制作用较Ce强。     

Sn晶粒取向对微焊点元素迁移及界面反应的影响

随着先进电子封装技术的不断发展,电子产品在服役时无铅微焊点内的元素迁移问题引起了广泛关注。由于先进封装互连尺寸的逐步缩小,微焊点扩散的各向异性问题日益凸显,即Sn晶粒取向显著影响元素的迁移行为,进而影响微焊点的界面反应。综述了在热时效、热循环、电流加载与温度梯度等条件下,Sn晶粒取向对焊点中元素迁移及界面反应的影响。现有研究结果表明,在热时效及热循环条件下,Sn晶粒取向对微焊点元素迁移及界面反应的影响较小,而Sn晶粒取向对微焊点的电迁移和热迁移有着相似的影响规律,并由此产生了界面金属间化合物（IMC）的非对称及非均匀生长现象。此外,还综述了基于数值模拟方法开展的微焊点元素扩散各向异性的相关研究,并对不同条件下的研究进展进行了总结。     

Ag-Cu-Ti合金与ZrO_2陶瓷的润湿性及界面特征

通过改良座滴法研究了Ag-Cu-Ti/ZrO2陶瓷体系的润湿行为和界面特征[1]。采用ADSA(axisymmetric drop shape analysis)-SESDROPD分析软件,X射线衍射仪(XRD),场发射扫描电镜(FESEM)以及配有能谱仪(EDS)的扫描电镜(SEM)测量表征了温度变化下,不同Ti含量的Ag-Cu-Ti合金在ZrO2陶瓷基板上的润湿性及其界面微观结构的影响规律。结果表明:Ag-Cu-Ti/ZrO2陶瓷体系的润湿机制为反应性润湿。Ag-Cu-Ti合金在ZrO2陶瓷基板上的润湿性随Ti含量的增加逐渐改善。Ag54Cu43Ti4合金熔体在ZrO2陶瓷基板上的润湿性对温度具有明显的反常依赖性,Ag53Cu41Ti6合金的润湿性较好。随温度的升高,Ag54Cu43Ti4/ZrO2和Ag53Cu41Ti6/ZrO2界面反应产物TiO反应层逐渐增厚,Cu3Ti3O反应层有逐渐变薄的趋势。Ag50Cu40Ti10/ZrO2的界面,出现大块状的金属间化合物Cu3Ti3O,容易使合金和陶瓷界面发生剥离。     

Interfacial Reactions of Sn-58Bi and Sn-9Zn Lead-Free Solders with Au/Ni/SUS304 Multilayer Substrate

The liquid/solid interfacial reactions of Sn-58Bi (SB) and Sn-9Zn (SZ) lead-free solders with Au/Ni/SUS304 multilayer substrates have been investigated in this study. In the SB/Au/Ni/SUS304 couple, only the Ni₃Sn₄ phase with needle-like grains was formed at the SB/Au/Ni/SUS304 interface. The Ni₅Zn₂₁ phase with a column structure was formed at the SZ/Au/Ni/SUS304 interface. The thickness of both intermetallic compounds (IMCs) increased with increasing reaction temperature and time. Meanwhile, the growth mechanism of these two IMCs is seen to follow a parabolic law and is diffusion controlled.     

Interfacial Reactions Between Pb-Free Solders and In/Ni/Cu Multilayer Substrates

This study investigates the interfacial reactions between Sn-3.0wt.% Ag-0.5wt.%Cu (SAC) and Sn-0.7wt.%Cu (SC) on In/Ni/Cu multilayer substrates using the solid–liquid interdiffusion bonding technique. Samples were reflowed first at 160°C, 180°C, and 200°C for various periods, and then aged at 100°C for 100 h to 500 h. The scalloped Cu₆Sn₅ phase was formed at the SAC/In/Ni/Cu and SC/In/Ni/Cu interfaces. When the reflowing temperatures were 160°C and 180°C, a ternary Ni-In-Sn intermetallic compound (IMC) was formed when the samples were further aged at 100°C. This ternary Ni-In-Sn IMC could be the binary Ni₃Sn₄ phase with extensive Cu and In solubilities, or the ternary Sn-In-Ni compound with Cu solubility, or even a quaternary compound. As the reflow temperature was increased to 200°C, only one Cu₆Sn₅ phase was formed at the solder/substrate interface with the heat treatment at 100°C for 500 h. Mechanical test results indicated that the formation of the Ni-In-Sn ternary IMC weakened the mechanical strength of the solder joints. Furthermore, the solid–liquid interdiffusion (SLID) technique in this work effectively reduced the reflow temperature.     

镍金表面上LP封装中央焊盘焊点空洞控制

随着产品小型化的发展,微小LP封装器件的应用越来越广泛,其中中央焊盘焊点空洞率成为影响产品功能的关键因素.主要研究镍金表面处理印制电路板上LP封装器件中央焊盘锡铅焊点空洞问题.介绍了焊点空洞的产生机理、焊接工艺难点及空洞控制方法,提出了优化焊盘设计、优化模板开孔设计、强化焊膏使用控制、控制焊膏印刷精度、控制贴装精度和优化焊接工艺参数等六大保证措施.经试验验证,同时采取6项措施后,有效地控制了镍金表面处理的PCB上LP封装器件的中央焊盘焊点空洞问题.     

化学沉镍金漏镀渗金的原因和措施

本文阐述了化学沉镍金工艺渗金和漏镀产生的原因以及预防改善措施。     

Au/Ge/Ni ohmic contacts to n-Type InP

The relationship between the electrical properties and microstructure for annealed Au/Ge/Ni contacts to n-type InP, with an initial doping level of 10¹⁷ cm^-3, have been studied. Metal layers were deposited by electron beam evaporation in the following sequence: 25 nm Ni, 50 nm Ge, and 40 nm Au. Annealing was done in a nitrogen atmosphere at 250-400‡C. The onset of ohmic behavior at 325‡C corresponded to the decomposition of a ternary Ni-In-P phase at the InP surface and the subsequent formation of Ni₂P plus Au₁₀In₃, producing a lower barrier height at the InP interface. This reaction was driven by the inward diffusion of Au and outward diffusion of In. Further annealing, up to 400‡C, resulted in a decrease in contact resistance, which corresponded to the formation of NiP and Au₉ln₄ from Ni₂P and Au₁₀In₃,respectively, with some Ge doping of InP also likely. A minimum contact resistance of 10^-7 Ω-cm² was achieved with a 10 s anneal at 400‡C.     

GaN MSM photodetectors with photo-CVD annealed Ni/Au electrodes

Thin Ni/Au (3/6 nm) bi-layer metal films annealed by photo-chemical vapor deposition (photo-CVD) were investigated. With proper annealing in oxygen by the photo-CVD systems, it was found that the transmittance of the deposited Ni/Au increased from 67 to 85% in the region between 350 and 450 nm. GaN metal-semiconductor-metal (MSM) ultraviolet (UV) photodetectors with photo-CVD annealed Ni/Au contact electrodes were also fabricated. It was found that dark current of the detector became significantly smaller after annealing. With a 1 V applied bias, it was found that we can achieve a photocurrent to dark current contrast ratio of 2.54×10³ from the photodetectors with 600 °C photo-CVD annealed Ni/Au contacts.     

Ni/Au与p-GaN的比接触电阻率测量

通过采用环形传输线方法(CILM),电流-电压(I-V)曲线、表面形貌等方法,研究不同的Ni/Au厚度比和空气气氛下合金退火温度对p型氮化镓欧姆接触特性造成的影响。根据Ni/Au与p型氮化镓欧姆接触的形成机制,采用合适的Ni/Au厚度比及退火温度,得到比接触电阻率(ρc)为1.09×10-5Ω.cm2的Ni/Au-p-GaN电极,并分析了Ni在退火过程中对形成良好的欧姆接触中所起到的作用。     

高可靠镀Ni／Au工艺及其在微波PTFE电路上的应用

介绍了高可靠电镀Ｎｉ／Ａｕ工艺在ＰＴＦＥ微波印制电路上的应用，并分析了氨基磺酸盐镀软镍和亚硫酸盐镀软金工艺的影响因素及提高Ｎｉ／Ａｕ镀层之间附着力的措施。通过实验及应用证明了与直接镀金工艺相比，在软基材ＰＴＦＥ敷铜箔板上镀Ｎｉ／Ａｕ工艺能大大提高微波电路的可焊性，高温稳定性和长期可靠性，并且用其所制作的微波器件的高频性能也优于直接镀金工业。     

The microstructure of eutectic Au-Sn solder bumps on Cu/electroless Ni/Au

In this work we studied the initial microstructure and microstructural evolution of eutectic Au-Sn solder bumps on Cu/electroless Ni/Au. The solder bumps were 150–160 m in diameter and 45–50 m tall, reflowed on Cu/electroless Ni/Au, and then aged at 200°C for up to 365 days. In addition, Au-Ni-Sn-alloys were made and analyzed to help identify the phases that appear at the interface during aging. The detailed interfacial microstructure was observed using a transmission electron microscope (TEM). The results show that the introduction of Au from the substrate produces large islands of-phase in the bulk microstructure during reflow. Two Au-Ni-Sn compounds are formed at the solder/substrate interface and grow slowly during aging. The maximum solubility of Ni in the—phase was measured to be about 1 at.% at 200°C, while Ni in the-phase is more than 20 at.%. The electroless Ni layer is made of several sublayers with slightly different compositions and microstructures. There is, in addition, an amorphous interaction layer at the solder/electroless Ni interface.     

氧化Au/Ni/p-GaN欧姆接触形成的机理

用卢瑟福背散射（RBS）和同步辐射X射线衍射（XRD）研究了p-GaN上的Ni/Au电极在空气下不同温度合金后的微结构的演化，并揭示这种接触结构的欧姆接触形成机制．研究不同温度下比接触电阻(ρc)的变化，发现从450℃开始Au扩散到GaN的表面在p-GaN上形成外延结构以及O向电极内部扩散反应生成NiO对降低ρc起到了关键的作用．在500℃时，Au的外延结构进一步改善，O进一步向样品内部扩散生成NiO,ρc也达到了最低值．但当合金温度升高到600℃时，金属-半导体界面NiO的大部分或全部向外扩散，从而脱离与p-GaN的接触，使ρc显著升高．