电子组装用高温无铅钎料的研制

Bi-Ag合金是一种替代高铅钎料的芯片封装无铅焊料。研制了Bi-2.5Ag、Bi-2.5Ag-0.1RE、Bi-5Ag-0.1RE、Bi-7.5Ag-0.1RE、Bi-10Ag、Bi-10Ag-0.1RE钎料。结果表明,该合金系钎料的熔化温度范围随Ag含量的增加而增大,而且其润湿性能良好,润湿角都处于30o～40o。不同Ag含量的Bi-Ag/Cu接头在界面处发生断裂,剪切强度差别不大,都略大于30MPa。Bi-Ag/Cu界面没有金属间化合物形成,结合强度较弱。     

Effect of flux on the wetting characteristics of SnAg, SnCu, SnAgBi, and SnAgCu lead-free solders on copper substrates

The effect of flux on the wetting characteristics of four lead-free solders, Sn-3.5Ag, Sn-0.7Cu, Sn-3.5Ag-4.8Bi, and Sn-3.8Ag-0.7Cu (wt.%), on copper substrates have been studied at 240, 260, and 280°C. The fluxes investigated were rosin (R), mildly activated rosin (RMA), and activated rosin (RA). The wetting tests were conducted using the sessile-drop method. Results showed that fluxes significantly affect the wetting properties of the solders. Contact angles ranging from 10° to 30° for RMA, 20° to 30° for RA, and 35° to 60° for R were obtained. The effect of temperature on contact angle depended on the type of flux used. The contact angle decreased with increasing temperature; however, in some cases the contact angle was independent of temperature. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles indicating improved wettability with addition of bismuth. The microstructure of the solder/copper interface was analyzed by scanning electron microscopy.     

Contact angle measurements of Sn-Ag and Sn-Cu lead-free solders on copper substrates

In this study, the contact angles of four lead-free solders, namely, Sn-3.5Ag, Sn-3.5Ag-4.8Bi, Sn-3.8Ag-0.7Cu, and Sn-0.7Cu (wt.%), were measured on copper substrates at different temperatures. Measurements were performed using the sessile-drop method. Contact angles ranging from 30° to 40° after wetting under vacuum with no fluxes and between 10° and 30° with rosin mildly activated (RMA) and rosin activated (RA) fluxes were obtained. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles, indicating improved wettability with the addition of bismuth. For all soldering alloys, lower contact angles were observed using RMA flux. Intermetallics formed at the solder/Cu interface were identified as Cu₆Sn₅ adjacent to the solder and Cu₃Sn adjacent to the copper substrate. The Cu₃Sn intermetallic phase was generally not observed when RMA flux was used. The effect of temperature on contact angle was dependent on the type of flux used.     

Wetting Behavior of Ternary Au-Ge-X (X = Sb, Sn) Alloys on Cu and Ni

Au-Ge-based alloys are potential substitutes for Pb-rich solders currently used for high-temperature applications. In the present work, the wetting behavior of two Au-Ge-X (X = Sb, Sn) ternary alloys, i.e., Au-15Ge-17Sb and Au-13.7 Ge-15.3Sn (at.%), in contact with Cu and Ni substrates has been investigated. Au-13.7Ge-15.3Sn alloy showed complete wetting on both Cu and Ni substrates. Total spreading of Au-15Ge-17Sb alloy on Cu was also observed, while the final contact angle of this alloy on Ni was about 29°. Pronounced dissolution of Cu substrates into the solder alloys investigated was detected, while the formation of Ni-Ge intermetallic compounds at the interface of both solder/Ni systems suppressed the dissolution of Ni into the solder.     

Comparative study of interfacial reactions of Sn-Ag-Cu and Sn-Ag solders on Cu pads during reflow soldering

The interfacial reaction in soldering is a crucial subject for the solder-joint integrity and reliability in electronic packaging technology. However, electronic industries are moving toward lead-free alloys because of environmental concerns. This drive has highlighted the fact that the industry has not yet arrived at a decision for lead-free solders. Among the lead-free alloys, Sn-3.5Ag and Sn-3.5Ag-0.5Cu are the two potential candidates. Here, detailed microstructural studies were carried out to compare the interfacial reaction of Sn-3.5Ag and Sn-3.5Ag-0.5Cu solder with a ball grid array (BGA) Cu substrate for different reflow times. The Cu dissolution from the substrate was observed for different soldering temperatures ranging from 230°C to 250°C, and the dissolution was found to increase with time and temperature. Dissolution of Cu in the Sn-3.5Ag solder is so fast that, at 240°C, 12 μm of the Cu substrate is fully consumed within 5 min. Much less dissolution is observed for the Sn-3.5Ag-0.5Cu solder. In respect to such high dissolution, there is no significant difference observed in the intermetallic compound (IMC) thickness at the interface for both solder alloys. A simplistic theoretical approach is carried out to find out the amount of Cu₆Sn₅ IMCs in the bulk of the solder by the measurement of the Cu consumption from the substrate and the thickness of the IMCs that form on the interface.     

Evaluation of Lead- Free Solder Joints in Electronic Assemblies

The feasibility of printed circuit board assembly with lead-free solder alloys was investigated. Studies were conducted with two baseline eutectic binary alloys, SnBi and SnAg, and three new lead-free solder formulations: (1) 91.8Sn-4.8Bi-3.4Ag (wt%) developed at Sandia Laboratories, (2) 77.2Sn-20In-2.8Ag developed at Indium Corp. of America, and (3) 96.2Sn-2.5Ag-0.8Cu-0.5Sb provided by AIM Inc. The basic physical properties (melting temperature, wetting, mechanical strength) pertinent to each of the newly developed alloys are described. The feasibility of 0.4 mm pitch assembly was established with each of the lead-free solder alloys investigated, although the processing windows were generally found to be narrower. All solder joints exhibited good fillets, in accordance with the workmanship standards. Wetting of the lead-free solders was significantly improved on immersion tin vs imidazole finished circuit boards. The laminates did not suffer thermal degradation effects, such as warpage, delamination, or severe discoloration (reflow was performed under an inert atmosphere). It is thus concluded that the manufacturability performance of the new solder formulations is adequate for surface mount applications.     

The thermal property of lead-free Sn-8.55Zn-1Ag-XAl solder alloys and their wetting interaction with Cu

The wetting behaviors between the quaternary Sn-8.55Zn-1Ag-XAl solder alloys and Cu have been investigated with the wetting balance method. The Al contents, x, of the quaternary solder alloys investigated were 0.01–0.45 wt.%. The results of differential scanning calorimeter (DSC) analysis indicate that the solders exhibit a solid-liquid coexisting range of about 7–10°C. The solidus temperature of the quaternary Sn-8.55Zn-1Ag-XAl solder alloys is about 198.2°C, while the liquidus temperatures are 205–207°C. The experimental results showed that the wettability of the Sn-8.55Zn-1Ag-XAl solder alloys is improved by the addition of Al. The mean maximum wetting force of the solders with Cu is within 0.75–1.18 mN and the mean wetting time is around 1.0–1.1 sec, better than the ∼1.3 sec of eutectic Sn-9Zn and Sn-8.55Zn-1Ag solder alloys. The addition of Al also depresses the formation of ε-Ag-Zn compounds at the interface between Sn-8.55Zn-1Ag-XAl solders and copper.     

Properties of Sn3.8Ag0.7Cu Solder Alloy with Trace Rare Earth Element Y Additions

In the current research, trace rare earth (RE) element Y was incorporated into a promising lead-free solder, Sn3.8Ag0.7Cu, in an effort to improve the comprehensive properties of Sn3.8Ag0.7Cu solder. The range of Y content in Sn3.8Ag0.7Cu solder alloys varied from 0 wt.% to 1.0 wt.%. As an illustration of the advantage of Y doping, the melting temperature, wettability, mechanical properties, and microstructures of Sn3.8Ag0.7CuY solder were studied. Trace Y additions had little influence on the melting behavior, but the solder showed better wettability and mechanical properties, as well as finer microstructures, than found in Y-free Sn3.8Ag0.7Cu solder. The Sn3.8Ag0.7Cu0.15Y solder alloy exhibited the best comprehensive properties compared to other solders with different Y content. Furthermore, interfacial and microstructural studies were conducted on Sn3.8Ag0.7Cu0.15Y solder alloys, and notable changes in microstructure were found compared to the Y-free alloy. The thickness of an intermetallic compound layer (IML) was decreased during soldering, and the growth of the IML was suppressed during aging. At the same time, the growth of intermetallic compounds (IMCs) inside the solder was reduced. In particular, some bigger IMC plates were replaced by fine, granular IMCs.     

Substrate Dissolution and Shear Properties of the Joints between Bi-Ag Alloys and Cu Substrates for High-Temperature Soldering Applications

The present study investigated interfacial reactions between Cu substrates and Bi-Ag alloys during soldering. Without forming intermetallic compounds (IMCs), the molten solder grooved and further penetrated along the grain boundaries (GBs) of the Cu substrate. An increase in Ag content enhanced GB grooving, raised the dissolution rate and also the amount of dissolved Cu in molten Bi. A stoichiometric Cu-Bi phase formed isothermally in liquid solders and considerably affected the Cu dissolution kinetics. The results also show that Bi-Ag/Cu joints possessed a better shear strength than the Pb-Sn/Cu, which implies that mechanical bonding by grain-boundary grooves was strong enough to withstand shear deformation.     

Effects of Trace Amounts of Rare Earth Additions on Microstructure and Properties of Sn-Bi-Based Solder Alloy

The effect of trace amounts of rare earth additions on the microstructure and properties were studied for the Sn-58Bi and Sn-58Bi-Ag solder alloys. At the same time, the intermetallic compounds (IMCs) in the solder alloys and intermetallic layer (IML) thickness at the solder/Cu substrate interface were investigated, both as-reflowed and after high-temperature aging. The results indicate that adding trace amounts of rare earth (RE) elements has little influence on the melting temperature and microhardness of the solders investigated, but adding RE elements improves the wettability and shear strength of the Sn-58Bi and Sn-58Bi-Ag solder alloys. In addition, it was found that the addition of RE elements not only refines the microstructure and size of the IMC particles, but also decreases the IML thickness and shear strength of the Sn-58Bi solder joint after high-temperature aging. Adding trace amounts of RE elements is superior to adding trace amounts of Ag for improving the properties of the Sn-58Bi solder. The reason may be related to the modification of the microstructure of the solder alloys due to the addition of trace amounts of RE elements.     

Sb掺杂对SnAgCu无铅焊点电迁移可靠性的影响

向Sn3.8Ag0.7Cu无铅焊膏中添加质量分数为1%的Sb金属粉末,研究了其焊点在电流密度为0.34×104A/cm2、环境温度150℃下的电迁移行为。通电245h后,阴极处钎料基体与Cu6Sn5IMC之间出现一条平均宽度为16.9μm的裂纹,阳极界面出现凸起带,钎料基体内部也产生了裂纹。结果表明:1%Sb的添加使焊点形成了SnSb脆性相,在高电流密度和高温环境下产生裂纹,缩短了焊点寿命,降低了电迁移可靠性。     

Sn-Zn系钎料研究及应用现状

随着钎料无铅化的发展,Sn-Zn钎料以其低廉的成本,与SnPb钎料相近的熔点成为无铅钎料研究的重点.但是Sn-Zn钎料存在易氧化,抗腐蚀性差,润湿性差的问题,通常在SnZn钎料中加入不同元素,改善其性能.主要阐述不同添加元素Bi、Al、In、Re(稀土元素)、Ag、Cu、P和多元合金对SnZn钎料自身性能和钎料与Cu结合性能的影响,概述SnZn系钎料的工业应用现状.     

Spreading Behavior and Evolution of IMCs During Reactive Wetting of SAC Solders on Smooth and Rough Copper Substrates

The effect of surface roughness of copper substrate on the reactive wetting of Sn-Ag-Cu solder alloys and morphology of intermetallic compounds (IMCs) was investigated. The spreading behavior of solder alloys on smooth and rough Cu substrates was categorized into capillary, diffusion/reaction, and contact angle stabilization zones. The increase in substrate surface roughness improved the wetting of solder alloys, being attributed to the presence of thick Cu₃Sn IMC at the interface. The morphology of IMCs transformed from long needle shaped to short protruded type with an increase in the substrate surface roughness for the Sn-0.3Ag-0.7Cu and Sn-3Ag-0.5Cu solder alloys. However, for the Sn-2.5Ag-0.5Cu solder alloy the needle-shaped IMCs transformed to the completely scallop type with increase in the substrate surface roughness. The effect of Ag content on wetting behavior was not significant.     

铜铟铋硫对Sn-Ag基无铅焊料性能的影响

研究了Cu、In、Bi、S元素对Sn-Ag基无铅焊料熔点和铺展性的影响。结果表明:Sn-Ag-Cu三元合金成分为95.5%Sn3.5%Ag1%Cu时具有较低熔点(215℃)和好的铺展性;加入适量的In可降低Sn-Ag合金的熔点和改善铺展性能;随w(Bi)的增加Sn-Ag-Bi三元合金的熔点降低、铺展性变好;Sn-Ag合金的熔点随w(S)的增加而升高,加入少量S能改善Sn-Ag合金的铺展性。     

添加Sb和LaB6对Sn3.0Ag0.5Cu/Cu界面IMC生长的影响

研究了Sb和稀土化合物的添加对Sn3.0Ag0.5Cu无铅焊料焊接界面金属间化合物层生长的影响。研究结果表明,固态反应阶段界面化合物层的生长快慢排序如下:v(SAC0.4Sb0.1LaB6/Cu)v(SAC0.4Sb/Cu)v(SAC0.1LaB6/Cu)v(SAC/Cu)。计算各种界面IMC生长的激活能Q结果表明,Sn3.0Ag0.5Cu/Cu界面IMC生长的激活能最高,为92.789 kJ,其他焊料合金Sn3.0Ag0.5Cu0.4Sb0.1LaB6/Cu,Sn3.0Ag0.5Cu0.1LaB6/Cu和Sn3.0Ag0.5Cu0.4Sb/Cu界面IMC生长的激活能分别为85.14,84.91和75.57 kJ。在老化温度范围内(≤190℃),Sn3.0Ag0.5Cu0.4Sb0.1LaB6/Cu的扩散系数(D)最小,因而其界面化合物的生长速率最慢。     

Early Interfacial Reaction and Formation of Intermetallic Compounds in the Sn-3.5Ag/Cu Soldering System

The early interfacial reaction in the Sn-3.5Ag/Cu soldering system and the system’s premelting behavior were found and characterized by differential scanning calorimetry incorporated into the reflow process. The results show that the early interfacial reaction occurs by way of melting and wetting of the solder layer adjacent to the Cu substrate at a temperature nearly 4°C below the actual melting point of Sn-3.5Ag solder due to solid-state diffusion of Cu atoms into the Sn-3.5Ag binary solder. Consequently, the early interfacial reaction brings about formation of Cu-Sn intermetallic compounds (IMCs) at a temperature below the melting point of Sn-3.5Ag, and a prolonged early interfacial reaction can lead to change of the Cu-Sn IMC morphology from planar-like to scallop-like and promote excessive growth of IMCs at the interface.     

Wetting and Soldering Behavior of Eutectic Au-Ge Alloy on Cu and Ni Substrates

Au-Ge-based alloys are interesting as novel high-temperature lead-free solders because of their low melting point, good thermal and electrical conductivity, and high corrosion resistance. In the present work, the wetting and soldering behavior of the eutectic Au-28Ge (at.%) alloy on Cu and Ni substrates have been investigated. Good wetting on both substrates with final contact angles of 13° to 14° was observed. In addition, solder joints with bond shear strength of 30 MPa to 35 MPa could be produced under controlled conditions. Cu substrates exhibit pronounced dissolution into the Au-Ge filler metal. On Ni substrates, the NiGe intermetallic compound was formed at the filler/substrate interface, which prevents dissolution of Ni into the solder. Using thin filler metal foils (25 μm), complete consumption of Ge in the reaction at the Ni interface was observed, leading to the formation of an almost pure Au layer in the soldering zone.     

Lead-free Sn-Ag and Sn-Ag-Bi solder powders prepared by mechanical alloying

A mechanical alloying (MA) process was used to produce lead-free solder pastes of Sn-3.5Ag and the Sn-3.5Ag-4Bi system. Because of the high energy induced by repeated fracturing and welding, the grinding media played an important role during the MA process. A ceramic container was used to provide stronger impact force, which could induce phase transformation better than a Teflon container. In addition, it was found that 1-cm balls could fracture Bi particles and promote their dissolution into the Sn matrix. On the contrary, the milling process tended to achieve homogeneous mixing when using 3-mm balls. The MA powders, after milling with 3-mm balls, showed a small endothermic peak from the differential scanning calorimetry (DSC) profile at around 138°C, which was the eutectic temperature of Sn-Bi. The melting points of the MA powders in the ceramic container were measured to be 221°C and 203°C, respectively, for Sn-3.5Ag and Sn-3.5Ag-4Bi from the DSC curves. The reduced melting point ensured the complete melting during reflow with a peak temperature of 240°C. The formation of Ag₃Sn was also observed from the x-ray diffraction peaks, indicating successful alloying by MA. The solder pastes could, thus, be produced by adding flux into the MA powders. The wetting property of the solder joint was also evaluated. The as-prepared solder pastes on electroless Ni-P/Cu/Si showed good metallurgical bonding with a contact angle less than 20°.     

A comparative analysis of microstructural features,tensile properties and wettability of hypoperitectic and peritectic Sn-Sb solder alloys

Sn-Sb alloys are among the current alternatives for the development of alloys for high-temperature lead-free solders. The Sn-Sb alloys having 5.5 wt.% Sb or less are known to have good mechanical properties, and despite the quite low liquidus temperature have been considered adequate in the development of solder joints. The increase in the Sb content up to the limit of solubility in Sn at about 10 wt.% is supposed to be detrimental to the mechanical properties due to the extensive formation of an intermetallic compound. Investigations on the interrelation of microstructure of this alloy and the corresponding mechanical properties are fundamental to an appropriate evaluation of its application in solder joints. The present investigation analyses the relationship between microstructural features of the peritectic Sn-10 wt.% Sb alloy, solidified under a wide range of cooling rates, and the resulting mechanical properties. A cellular β-Sn matrix, typified by cellular spacings that decrease with the increase in the solidification cooling rate, and Sn₃Sb₂ particles are shown to characterize the alloy microstructure. The ultimate tensile strength is higher as compared with the corresponding values of the hypoperitectic Sn-5.5 wt.% Sb solder alloy, however the elongation is shown to decrease. A comparison with Bi-Ag alloys, considered good high temperature solders alternatives, has shown that the tensile properties of the Sn-10 wt.% Sb alloy, including elongation, are significantly higher. Wettability tests have been carried out and the experimental results, according to reports from the literature, are associated with good wettability.     

微量Co对低银无铅焊料润湿及界面反应的影响

利用润湿测量仪研究了加入微量Co对低银无铅焊料Sn1.00Ag0.70Cu和Sn0.50Ag0.70Cu润湿性能的影响,并与共晶无铅焊料Sn3.00Ag0.50Cu的润湿性能进行对比。结果发现,焊料Sn3.00Ag0.50Cu、Sn1.00Ag0.70Cu0.07Co和Sn0.50Ag0.70Cu0.03Co的润湿平衡力F分别为3.0850,3.0600和3.0275mN,润湿时间分别为0.64,0.88和1.01s。低银微钴无铅焊料显示了与共晶无铅焊料类似的润湿力,只是润湿时间略有增加。