Sn-Zn-Bi-Ag系钎料物理性能研究

通过成分设计形成了Sn-Zn-Bi-Ag系钎料合金。针对微电子产业的应用要求研究了钎料的物理性能,分析了Sn-Zn-Bi-Ag系钎料中合金元素对钎料物理性能的影响。发现:Sn-Zn-Bi-Ag系钎料的合金元素中Bi、Ag含量(质量分数)的增加会使钎料的密度增大,而Zn含量对钎料的密度影响不大。Zn含量5.0%~6.5%,Bi含量1.5%~3.0%,Ag含量0.5%~0.8%范围的Sn-Zn-Bi-Ag钎料具有较好的润湿性能。Sn-Zn-Bi-Ag系钎料中Bi含量不高时,钎料的电阻率均比传统Sn-37Pb钎料小。随着Bi含量的增加,钎料的电阻率有明显增大的趋势。     

纳米压痕法分析Sn-9Zn/Cu焊点力学性能

通过对Sn-9Zn/Cu焊点进行纳米压痕实验发现:在保载阶段,体钎料产生了明显的蠕变特征,蠕变深度随着加载速率的增加而增加.基于压痕做功概念确定了Sn-9Zn/Cu焊点中体钎料的蠕变应力指数n约为5.128.硬度和弹性模量测试结果表明:金属间化合物Cu5Zn8的压痕硬度(5.152±0.224) GPa约是体钎料压痕硬...     

Sn-8Zn无铅钎料性能的研究

研究了不同微量合金元素(Bi、Ag)对Sn-8Zn无铅钎料高温抗氧化性能及接头剪切强度的影响,采用氧化质量增加△m值的方法,在高温下观察钎料表面氧化膜形状和颜色的变化并对氧化膜进行X射线衍射分析,探讨了钎料的高温抗氧化性能的机理,通过对钎料的金相显微组织观察和对热处理后钎焊接头的剪切强度试验,分析了提高接头剪切强度的原因.试验结果表明:在Sn-8Zn钎料中加入适量的合金元素(Bi、Ag)均可以改善和提高钎料的高温抗氧化性能和接头的剪切强度.     

Sn-0.3Ag-0.7Cu-xBi低银无铅钎料的润湿性

以Bi为添加剂对低银型Sn-0.3Ag-0.7Cu无铅钎料进行改性,应用SAT—5100型润湿平衡仪对Sn-0.3Ag-0.7Cu-xBi(x=0,1,3和4.5)钎料的润湿性能作了对比分析。结果表明:适量Bi元素的加入可以改善Sn-0.3Ag-0.7Cu钎料合金的润湿性能,且在240℃下Sn-0.3Ag-0.7Cu-3.0Bi无铅钎料具有最佳的润湿性能,在250℃其润湿力达到最大值3.2×10–3N/cm。     

Ag对Sn-9Zn合金钎料组织及性能的影响

用莱卡显微镜、XRD研究添加元素Ag对Sn-9Zn钎料组织及性能的影响。结果表明:Ag与Zn形成AgZn3化合物,能抑制粗大针状富Zn相的形成,可使Sn-9Zn钎料合金的润湿性提高20%,并明显改善Sn-9Zn的耐蚀性。     

Sn基钎料与Cu和Al基板的润湿性比较研究

采用润湿平衡法测量了四种Sn基钎料(Sn-37Pb、Sn-3.OAg-0.5Cu、Sn-0.7Cu与Sn-9Zn)分别在250,260和270℃与Cu、Al两种基板的润湿性能.结果表明:钎料与Al基板的润湿时间均比Cu基板长,除Sn-9Zn外,其他三种钎料与Cu基板的润湿力比Al基板大,并且随着温度升高,润湿性能提高,...     

无铅电子钎料合金蠕变性能研究

设计制作了一种简单可靠的弯折蠕变测量装置,比较了两种无铅电子钎料合金Sn-9Zn和Sn-3.5Cu-0.7Ag与传统电子钎料合金Sn-40Pb的常温蠕变性能,以及冷却条件对其蠕变强度的影响。结果表明:两种无铅钎料的抗蠕变性能大大优于传统锡铅钎料;Sn-3.5Ag-0.7Cu合金的抗蠕变性能优于Sn-9Zn合金;冷却速率对Sn-9Zn合金和Sn-3.5Ag-0.7Cu合金组织的影响类似,然而对蠕变强度的影响却相反:水冷使两种合金的组织相对于空冷都明显细化,Sn-9Zn合金的蠕变强度因之降低,而Sn-3.5Ag-0.7Cu合金的蠕变强度却因之提高。对可能产生的原因进行了讨论。     

稀土改性的Sn-58Bi低温无铅钎料

研究了微量稀土对Sn-58Bi低温钎料的改性作用.试验添加质量分数为0.1 ?组混合稀土的无铅材料,并对比Sn-58Bi和Sn-58Bi0.5Ag合金.观察了钎料显微组织的变化并做了定量分析,采用DSC测试了钎料的熔化温度,同时测量了钎料的润湿性能、接头强度与硬度.结果表明,微量稀土添加细化了Sn-58Bi钎料合金的显微组织,对钎料的熔化温度几乎没有影响,能显著改善Sn-58Bi钎料的润湿性能和接头剪切强度,而且改善的程度优于添加微量Ag对Sn-58Bi钎料的作用.     

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。     

无铅制程导入面临的问题及解决方案(续)

(上接2006年第5期第55页)3.4.6杂质元素控制表8为无铅钎料中污染元素含量上限要求。实际生产过程中,对钎料槽中Cu、Pb、Fe等杂质要进行严格控制。钎料中的Cu主要来源于电路板镀层和元件镀层,SAC合金更趋向于溶解铜,速度是SnPb合金表8无铅钎料中污染元素含量上限上限/%现象Pb0.100法律规定Bi0.250无光泽,与铅使用会增加剥离Cu0.300会随钎料槽的使用而增加Cd0.002氧化增加粘度Zn0.005氧化排流不良,乳化锡渣Al0.002增加锡渣率0.0005?0.020造成焊点砂质In0.100降低熔点As0.030产生半润湿Au0.010钎料变得不活波,焊点无光泽的2倍,是SnC…     

Effect of thermal cycling on the adhesion strength of Sn-9Zn-xAg-Cu interface

The effect of thermal cycling on the adhesion strength of the Sn-9Zn-xAg-Cu interface has been investigated by using pull-off tester, X-ray diffractometer, scanning electron microscope and energy dispersive spectrometer. The Sn-9Zn-xAg lead-free solders offer a better thermal cyclic resistance than the 63Sn-37Pb and Sn-9Zn solder alloys. The adhesion strength of the Sn-9Zn-Cu interface increases from 4.4 /spl plusmn/ 0.4 MPa to 13.8 /spl plusmn/ 0.9 MPa with increasing the thermal cycles from zero to three times but it decreases to 8.5 /spl plusmn/ 0.8 MPa for five cycles. The Sn-9Zn-xAg solder alloys (x=0.5, 2.5, and 3.5 wt%) have a similar tendency and the maximum adhesion strength of 21.41 /spl plusmn/ 1.5 MPa for the Sn-9Zn-2.5Ag solder alloy has been obtained after three thermal cycles. The adhesion strength of the Sn-9Zn-1.5Ag-Cu interface increases from 7.8 /spl plusmn/ 0.6 to 16.6 /spl plusmn/ 0.9 MPa with increasing the thermal cycles from 0 to 5 times.     

Comparative study of wetting behavior and mechanical properties (microhardness) of Sn-Zn and Sn-Pb solders

In this paper the solder balling, wetting, spreading, slumping and microhardness testing of the Sn-Zn based solders have been compared with the Sn-Pb solder. Two types of solders (Sn-9Zn and Sn-8Zn-3Bi) have been investigated along with Sn-37Pb solder for reference. The variation of these tests has been done as a function of reflow temperature from 220-250 °C. Solder balls of these three solder pastes after 15 min heating at 230 °C show no ball formation surrounding the central ball. Spread test shows that above 240 °C Sn-9Zn is very good and can be comparable to Sn-37Pb. The wetting angle of Sn-9Zn (39°) at 250 °C is even lower than the Sn-37Pb solder (41°). In case of Sn-8Zn-3Bi, the wetting angle is very high (77°) at 220 °C, which is unacceptable but it drops down to 48° at 250 °C. Line profiles of slump test show that after preheating at 160 °C, Sn-9Zn behaves similar to Sn-37Pb with better distinction in the finer pitch (120 μm). Microhardness shows two different characteristics for eutectic and non-eutectic solder pastes. Hardness of Sn-37Pb and Sn-9Zn (eutectic) decreases with increasing reflow temperature while the microhardness of Sn-8Zn-3Bi (non-eutectic) increases with increasing reflow temperature. Microstructural characterization at 220 and 250 °C shows grain coarsening in Sn-37Pb and Sn-9Zn solders, which cause the hardness to drop a little. For Sn-8Zn-3Bi, with increasing temperature the amount of hard Bi segregation increases which is the main cause of the rise in hardness. SEM images show the formation of Pb rich islands in Sn-37Pb, formation of Zn rod from spheroids in Sn-9Zn and precipitation of Bi-rich phase in Sn-8Zn-3Bi are the important features that contribute to different hardness nature.     

Mechanical Properties and Electrochemical Corrosion Behavior of Al/Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Ag/Cu Joints

The effect of Ag content on the wetting behavior of Sn-9Zn-xAg on aluminum and copper substrates during soldering, as well as the mechanical properties and electrochemical corrosion behavior of Al/Sn-9Zn-xAg/Cu solder joints, were investigated in the present work. Tiny Zn and coarsened dendritic AgZn₃ regions were distributed in the Sn matrix in the bulk Sn-9Zn-xAg solders, and the amount of Zn decreased while that of AgZn₃ increased with increasing Ag content. The wettability of Sn-9Zn-1.5Ag solder on Cu substrate was better than those of the other Sn-9Zn-xAg solders but worse than that of Sn-9Zn solder. The wettability of Sn-9Zn-1.5Ag on the Al substrate was also better than those of the other Sn-9Zn-xAg solders, and even better than that of Sn-9Zn solder. The Al/Sn-9Zn/Cu joint had the highest shear strength, and the shear strength of the Al/Sn-9Zn-xAg/Cu (x = 0 wt.% to 3 wt.%) joints gradually decreased with increasing Ag content. The corrosion resistance of the Sn-9Zn-xAg solders in Al/Sn-9Zn-xAg/Cu joints in 5% NaCl solution was improved compared with that of Sn-9Zn. The corrosion potential of Sn-9Zn-xAg solders continuously increased with increasing Ag content from 0 wt.% to 2 wt.% but then decreased for Sn-9Zn-3Ag. The addition of Ag resulted in the formation of the AgZn₃ phase and in a reduction of the amount of the eutectic Zn phase in the solder matrix; therefore, the corrosion resistance of the Al/Sn-9Zn-xAg/Cu joints was improved.     

Growth of intermetallic compounds in the Sn-9Zn/Cu joint

We have studied the microstructure of the Sn-9Zn/Cu joint in soldering at temperatures ranging from 230°C to 270°C to understand the growth of the mechanism of intermetallic compound (IMC) formation. At the interface between the Sn-9Zn solder and Cu, the results show a scallop-type ε-CuZn₄ and a layer-type γ-Cu₅Zn₈, which grow at the interface between the Sn-9Zn solder and Cu. The activation energy of scallop-type ε-CuZn₄ is 31 kJ/mol, and the growth is controlled by ripening. The activation energy of layer-type γ-Cu₅Zn₈ is 26 kJ/mol, and the growth is controlled by the diffusion of Cu and Zn. Furthermore, in the molten Sn-9Zn solder, the results show η-CuZn grains formed in the molten Sn-9Zn solder at 230°C. When the soldering temperature increases to 250°C and 270°C, the phase of IMCs is ε-CuZn₄.     

Sn-9Zn合金无铅钎料用助焊剂研究

通过测量润湿面积和润湿角,研究不同助焊剂对Sn-9Zn焊料润湿性的影响。结果表明:助焊剂对Sn-9Zn焊料润湿性影响很大,由乳酸、聚乙二醇和SnCl2所构成的助焊剂与Sn-9Zn焊料有很好适应性;同时扫描电镜和能谱分析也表明焊料与Cu基体界面的IMC为Cu5Zn8相,比Sn-37Pb焊料具有更高的剪切强度。     

Investigation of Dissolution Behavior of Metallic Substrates and Intermetallic Compound in Molten Lead-free Solders

This study investigates the dissolution behavior of the metallic substrates Cu and Ag and the intermetallic compound (IMC)-Ag₃Sn in molten Sn, Sn-3.0Ag-0.5Cu, Sn-58Bi and Sn-9Zn (in wt.%) at 300, 270 and 240°C. The dissolution rates of both Cu and Ag in molten solder follow the order Sn > Sn-3.0Ag-0.5Cu >Sn-58Bi > Sn-9Zn. Planar Cu₃Sn and scalloped Cu₆Sn₅ phases in Cu/solders and the scalloped Ag₃Sn phase in Ag/solders are observed at the metallic substrate/solder interface. The dissolution mechanism is controlled by grain boundary diffusion. The planar Cu₅Zn₈ layer formed in the Sn-9Zn/Cu systems. AgZn₃, Ag5Zn₈ and AgZn phases are found in the Sn-9Zn/Ag system and the dissolution mechanism is controlled by lattice diffusion. Massive Ag₃Sn phases dissolved into the solders and formed during solidification processes in the Ag₃Sn/Sn or Sn-3.0Ag-0.5Cu systems. AgZn₃ and Ag₅Zn₈ phases are formed at the Sn-9Zn/Ag₃Sn interface. Zn atoms diffuse through Ag-Zn IMCs to form (Ag, Zn)Sn₄ and Sn-rich regions between Ag₅Zn₈ and Ag₃Sn.     

Influence of Ag micro-particle additions on the microstructure, hardness and tensile properties of Sn-9Zn binary eutectic solder alloy

In this study, an addition of Ag micro-particles (8-10 μm) with a content in the range between 0 and 1.5 wt.% to Sn-9Zn eutectic solder, were examined in order to understand the effect of Ag additions as the particulate reinforcement on the microstructural and mechanical properties as well as the thermal behavior of the newly developed composite solders. Here, an approach to prepare a micro-composite solder alloy by mixing Ag micro-particles with a molten Sn-Zn solder alloy was developed. The composite solder was prepared by mechanically mixing Ag micro-particles into the Sn-9Zn alloy melt to ensure a homogeneous distribution of the reinforcing particles. The distribution of the Ag micro-particles in the matrix was found to be fairly uniform. The Ag particles reacted with the Zn and formed ε-AgZn₃ intermetallic compounds (IMC) in the β-Sn matrix. It was found that the more Ag particles added to the Sn-9Zn solder, the more Ag-Zn compound formed. In the Sn-9Zn/XAg composite solder, the microstructure was composed of AgZn₃ IMC and α-Zn phase in the β-Sn matrix. Interestingly, as the Ag particles in the composite solder increased, the α-Zn phase was found to be depleted from the matrix. The average tensile strength of the composite solders increased with the Ag micro-particles content up to a certain limit. Beyond this limit, the addition of Ag particles actually decreased the strength.     

Interfacial microstructure and bonding strength of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder BGA packages with immersion Ag surface finish

Although it has been verified that tin whiskers can be prevented by the addition of 0.5 wt.% Zn into a Sn-3Ag-0.5Cu-0.5Ce solder, no detailed studies have been conducted on interfacial reactions and mechanical properties of Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with an immersion Ag surface finish. The intermetallic compounds formed during the reflow and aging of Sn-3Ag-0.5Cu and Sn-3Ag-0.5Cu-0.5Ce-xZn solder ball grid array (BGA) packages were investigated. Because more heterogeneous nucleation sites, provided by CeSn₃ intermetallics and Zn atoms, formed in the Sn-3Ag-0.5Cu-0.5Ce-xZn solder matrix, and Cu and Zn have a stronger affinity than Cu and Sn, the Cu-Sn intermetallics growth in Sn-3Ag-0.5Cu-0.5Ce-xZn solder joints with Ag/Cu pads was suppressed. The 0.2% Zn addition for inhibiting rapid whisker growth in RE-doped Sn-Ag-Cu solder joints is more appropriate than 0.5 wt.% additions, as excess Zn addition causes poor oxidation resistance and inferior bonding strength.     

Effects of Ce and La Additions on the Microstructure and Mechanical Properties of Sn-9Zn Solder Joints

The effects of rare-earth elements on the microstructure and mechanical properties of Sn-9Zn alloys and solder joints in ball grid array packages with Ni/Au(ENIG) surface finishes have been investigated. Metallographic observations showed that (Ce_0.8Zn_0.2)Sn₃ and (La_0.9Zn_0.1)Sn₃ intermetallic compounds appeared in the solder matrix of Sn-9Zn-0.5Ce and Sn-9Zn-0.5La alloys, respectively. Both fiber- and hillock-shaped tin whiskers were inhibited in the Sn-9Zn-0.5Ce solder, while tin fibers were still observed on the surface of oxidized (La_0.9Zn_0.1)Sn₃ intermetallics in Sn-9Zn-0.5La after air exposure at room temperature. Mechanical testing indicated that the tensile strength of Sn-9Zn alloys doped with Ce and La increased significantly, and the elongation decreased, in comparison with the undoped Sn-9Zn. The bonding strengths of the as-reflowed Sn-9Zn-0.5Ce and Sn-9Zn-0.5La solder joints were also improved. However, aging treatment at 100°C and 150°C caused degradation of ball shear strength in all specimens. During the reflowing and aging processes, AuZn₈ intermetallic phases appeared at the interfaces of all solder joints. In addition, Zn-rich phases were observed to migrate from the solder matrix to the solder/pad interfaces of the aged specimens.