Ag,Al,Ga对Sn-9Zn无铅钎料润湿性能的影响

采用润湿平衡法测试了Sn-9Zn-X(X为Ag,Al,Ga)无铅钎料分别配合ZnCl2-NH4Cl钎剂和免清洗助焊剂,在空气和氮气保护的两种条件下的润湿性能,分析研究了合金元素Ag,Al,Ga的添加量对Sn-9Zn-X无铅钎料润湿性的影响规律.结果表明,合金元素Ag,Al,Ga在Sn-9Zn中的最佳添加量(质量分数)分别为0.3%,0.005%～0.02%,0.5%.采用氮气保护可以显著改善Sn-9Zn-X无铅钎料的润湿性,而Sn-9Zn-X无铅钎料配合ZnCl2-NH4Cl钎剂时具有较好的润湿性,甚至优于Sn-3.5Ag-0.5Cu在相同条件下的润湿性.这一研究结果表明,通过研发适合于Sn-Zn系无铅钎料的高性能助焊剂,从而改善Sn-Zn系钎料的润湿性能是完全可行的.     

Sn-0.3Ag-0.7Cu-xNd钎料显微组织及性能

研究了稀土元素Nd的添加量对超低银无铅钎料Sn-0.3Ag-0.7Cu的润湿性能、显微组织和力学性能的影响.结果表明,微量Nd元素的加入可以显著改善Sn-0.3Ag-0.7Cu超低银无铅钎料的润湿性能和焊点的力学性能,并且能够起到细化基体组织的作用.当钎料中Nd元素的质量分数达到0.1%时,钎料的综合性能最佳,基体组织最为均匀细化.虽然Ag元素含量的降低使钎料的性能有所下降,但是加入适量Nd元素后钎料的润湿性能已接近传统Sn-3.8Ag-0.7Cu钎料.     

微量RE对Sn-2．5Ag-0．7Cu钎料合金润湿性的影响

采用润湿平衡法,研究了水洗钎剂条件下Sn-2.5Ag-0.7Cu-xRE无铅钎料合金在1206片式元器件和Cu焊盘上的润湿性.结果表明,添加质量分数为0.1%的RE的Sn-2.5Ag-0.7Cu钎料合金在1206表面贴装元器件和Cu焊盘上有最大的润湿力和铺展面积及最小的润湿角,其润湿性最好,润湿力优于Sn-3.8Ag-0.7Cu钎料合金,满足微电子行业对润湿性能的要求.     

Ag、RE对Sn-Ag-Cu-RE无铅钎料润湿性的影响

采用商用水洗钎剂,以铺展面积和润湿角来表征钎料的润湿性能,研究了Ag、RE对Sn-Ag-Cu-RE系无铅钎料润湿性的影响。结果表明,添加微量RE有助于提高其润湿性。在无铅钎料中Sn-2.5Ag-0.7Cu-0.1RE钎料具有良好的润湿特性,其在铜板上润湿性接近Sn-Pb钎料的水平。     

Sn-07Cu-xAg-yBi无铅钎料润湿性试验

为降低Sn-Ag-Cu系无铅钎料中Ag的含量以减少钎料的成本,对Sn-xAg-0.7Cu(x=0.5,1.0,1.5,3.0)及Sn-0.5Ag-0.7Cu--yBi(y=1,3,5)无铅钎料在不同钎焊温度和不同钎剂活性条件下,进行了钎焊润湿性试验,分析了不同Ag含量、Bi含量对润湿性的影响.试验结果表明:在Sn-Ag-Cu系无铅钎料中,随着Ag含量的降低,钎抖的润湿性降低;随着Bi含量的增加,钎料的润湿性提高.     

稀土Pr对Sn-0.3Ag-0.7Cu钎料润湿性能和微焊点力学性能的影响

采用润湿平衡法研究了微量稀土Pr元素对Sn-0.3Ag-0.7Cu在Cu基板上润湿性能的影响规律,并借助STR-1000型微焊点强度测试对Sn-0.3Ag-0.7Cu-x Pr微焊点的力学性能。结果表明,随着稀土Pr含量的增加,钎料在Cu基板上的润湿力逐渐增加,润湿时间缩短。当Pr的质量分数在0.05%~0.1%时,Sn-0.3Ag-0.7Cu-x Pr钎料的润湿性能最好。在260℃的试验条件下,Sn Ag Cu-0.1Pr相比Sn Ag Cu钎料润湿力提高了5.0%,润湿时间降低了16.9%。且当Pr含量约为0.05%时,微焊点的力学性能最佳,焊点的剪切强度提高了8.5%。     

稀土Pr对Sn-0.3Ag-0.7Cu无铅钎料显微组织和润湿性能的影响

采用XJP-300型光学显微镜以及日立扫描电子显微镜S-3400N对Sn-0.3Ag-0.7Cu-x Pr无铅钎料的显微组织进行观察和分析,采用润湿平衡法,研究了钎料在Cu基板上的润湿性能。研究结果表明,微量稀土Pr可以改善Sn-0.3Ag-0.7Cu钎料的显微组织和润湿性能。当Pr的添加量约为0.05%时,Sn-0.3Ag-0.7Cu钎料的显微组织得到最大程度的细化以及均匀化,同时钎料具有最大润湿力。在260℃的钎焊温度下,SnAgCu-0.1Pr的润湿力与SnAgCu钎料相比,提高了5.0%,润湿时间降低了16.9%。当Pr含量继续增加时,钎料中出现大块的稀土相。同时钎料的润湿时间增长,润湿性能变差。     

不锈钢软钎焊用钎料和钎剂的研究

研究了304不锈钢软钎焊用钎剂和钎料,结果表明:氯化锌+氯化铵+盐酸钎剂可以较好的钎焊不锈钢;Sn-3.5Ag-0.7Cu无铅钎料对不锈钢的润湿性与Sn-Pb钎料相当,Sn-0.7Cu钎料次之,Sn-9Zn的润湿性较差。对Sn基钎料与不锈钢的界面金相分析表明:Sn基钎料与不锈钢的界面形貌较平坦,界面处仅有少量FeSn_2金属间化合物生成,不锈钢软钎焊接头的强度与所采用钎料密切相关。     

Sn-9Zn-xAl无铅钎料润湿性能

采用润湿平衡法测试了不同温度下Sn-9Zn-xAl无铅钎料在空气和氮气两种气氛下的润湿性能,研究探索了合金元素Al的添加量、气氛和温度对Sn-9Zn-xAl无铅钎料润湿性能的影响规律.结果表明,添加Al元素以后,Sn-Zn-xAl无铅钎料的润湿性得到明显改善,在使用ZnCl2-NH4Cl助焊剂时,Al的最佳添加量为0.02%(质量分数),在使用免清洗助焊剂时,Al的最佳添加量为0.005%(质量分数);采用氮气保护时,Cu基板表面张力提高,钎料的氧化减少、表面张力降低,明显改善了钎料在Cu基板上的润湿性能;在215～245℃时,温度升高使钎料的表面张力减小,提高了钎料的润湿性能.     

Ag、RE对Sn-Ag-Cu-RE无铅钎料润湿性的影响

采用商用水洗钎剂，以铺展面积和润湿角来表征钎料的润湿性能，研究了Ag、RE对Sn-Ag-Cu-RE系无铅钎料润湿性的影响。结果表明，添加微量RE有助于提高其润湿性。在无铅钎料中Sn-2．5Ag-0．7Cu-0．1RE钎料具有良好的润湿特性，其在铜板上润湿性接近Sn-Pb钎料的水平。     

Bi对Sn-0.3Ag-0.7Cu无铅钎料熔点及润湿性能的影响

研究了添加适量的Bi元素对低银型Sn-0．3Ag-0．7Cu无铅钎料合金性能的影响,应用差示扫描量热仪和SAT-5100型润湿平衡仪对Sn-0．3Ag-0．7Cu·xBi（x=0.1,3,4．5）钎料的熔点、润湿性能作了对比试验分析。结果表明,一定量Bi元素的加入可以降低Sn-0．3Ag-0．7Cu钎料合金的熔点,并改善其润湿性能。但过多的Bi元素会导致钎料的液固相线温度差增大,塑性下降,造成焊点剥离缺陷。综合考虑得到Sn-0．3Ag-0．7Cu-3．0Bi无铅钎料具有最佳的综合性能。     

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.     

Pb-free solders for flip-chip interconnects

A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag₃Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni₃Sn₄ formed and on copper, Cu₆Sn₅Cu₃Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu. Editor’s Note: A hypertext-enhanced version of this article can be found at www.tms.org/pubs/journals/JOM/0106/Frear-0106.html For more information, contact D.R. Frear, Interconnect Systems Laboratories, Motorola, Tempe, AZ 85284; (480) 413-6655; fax (480) 413-4511; e-mail darrel.frear@motorola.com.     

无铅焊料在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为

研究了Sn-3.5Ag-0.75Cu和Sn-0.75Cu焊料合金在NaCl-Na_2SO_4-Na_2CO_3模拟土壤溶液中的腐蚀浸出行为,并与Sn-37Pb焊料合金的腐蚀浸出行为对比分析。研究表明,这3种焊料合金中Sn的浸出量随时间的延长趋于平缓,且Sn-0.75Cu焊料合金中Sn的浸出量最高,添加Ag元素后明显抑制了Sn-3·5Ag-0·75Cu焊料合金中Sn的浸出;Ag,Cu,Pb的浸出量随时间的延长呈线性增加,且Ag,Cu的浸出量较少。3种焊料合金浸出后表面产物层较厚,主要由Sn_4(OH)_6Cl_2和SnO组成,其中Sn-0.75Cu焊料合金的表面产物层有裂纹和孔洞,Sn-3.5Ag-0.75Cu焊料合金的表面产物相对致密,而Sn-37Pb焊料合金的表面产物局部出现剥落现象。这3种焊料合金浸出动力学行为存在差异,主要与表面产物的相组成和形貌有关。     

Property alterations of Sn-0.6Cu-0.05Ni-Ge lead-free solder by Ag,Bi, In and Sb addition

The Sn-Cu-Ni-Ge solder is a strong challenger to the Sn-Ag-Cu (SAC) solders as a replacement for the Sn-Pb eutectic solder. This research investigated the effects of addition of Ag, Bi, In, and Sb on the physical properties of the Sn-0.6Cu-0.05Ni-Ge (SCNG) lead-free solder and the interfacial reaction with the Cu substrate. The melting behavior, microstructure, tensile strength, and wettability of the SCNG–x (x=Ag, Bi, In, Sb) solders were examined. The findings revealed that the introduction of Ag, Bi, In, and Sb minimally altered the solidus temperature, liquidus temperature, and tensile strength of the solder. However, the cooling behavior and solidified microstructure of the solder were affected by the concentration of the alloying elements. The wettability of the SCNG solder was improved with the doping of the alloying elements except Sb. The thickness of intermetallic layer was increased by the addition of the alloying elements and was related to the cooling behavior of the solder. The morphology of intermetallic layer between the SCNG–x solders and the Cu substrate was different from that of the typical SAC solders. In conclusion, alloying the SCNG solder with Ag, Bi, In or Sb is able to improve particular properties of the solder.     

Sn-Ag-Cu and Sn-Cu solders: Interfacial reactions with platinum

The interfacial reaction and intermetallic formation at the interface between tin solders containing a small amount of copper with platinum were investigated in this study. Sn-0.7Cu and Sn-1.7Cu solders were reacted with platinum by dipping Pt/Ti/Si specimens into the molten solder at 260°C. Sn-3.8Ag-0.7Cu solder was reacted with platinum by reflowing solder paste on a Pt/Ti/Si substrate at 250°C. PtSn₄ intermetallic formed in all specimens while Cu₆Sn₅ interfacial intermetallic was not observed at the solder/platinum interfaces in any specimens. A parabolic relationship existed between the thickness of the Pt-Sn intermetallic and reaction time, which indicates the intermetallic formation in the solder/platinum interface is diffusion controlled. For more information, contact Young-Ho Kim, Hanyang University, Department of Materials Engineering, Seoul, 133-791, Korea; e-mail kimyh@hanyang.ac.kr.     

Effects of Ga,Al, Ag,and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solder

An orthogonal method was used to evaluate the effects of Ga, Al, Ag, and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solders by wetting balance method. The results show that the optimal loading of Ga, Al, Ag, and Ce was 0.2 wt.%, 0.002 wt.%, 0.25 wt.%, and 0.15 wt.%, respectively. Intermetallic compounds (IMCs) formed at the interface between Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder and Cu substrate were investigated by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analysis. The SEM images illustrate that the IMCs can be divided into two portions from the substrate side to the solder side: a planar Cu₅Zn₈ layer and an additional continuous scallop-like AgZn₃ layer. The EDS analysis also shows that Ga segregates in the solder abutting upon the interface. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) of the surface components of Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder indicate that Al aggregates at the surface in the form of Al₂O₃ protective film, which prevents the further oxidation of the solder surface. On the other hand, Ce aggregates at the subsurface, which may reduce the surface tension of the solder and improve the wettability in consequence.     

稀土元素Ce对锡银铜无铅钎料显微组织的影响

研究了不同含量的稀土Ce对Sn-3．8Ag-0．7Cu无铅钎料的显微组织的影响，结果表明，微量稀土Ce的加入可以细化组织，抑制金属间化合物的生长。稀土Ce含量为0．03％（质量分数）时，组织均匀、细小，钎料润湿性能好，钎缝力学性能佳。当Ce含量为0．03％（质量分数）时，无铅钎料组织中开始出现黑色的富Ce相，并随Ce量的增加而增多。对显微组织的分析和理论计算表明，含稀土Ce锡银铜无铅钎料组织中的黑色的富Ce相为Ce与Sn的化合物。