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A Review of Mechanical Properties of Lead-free Solders for Electronic Packaging

A Review of Mechanical Properties of Lead-free Solders for Electronic Packaging

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A review of mechanical properties of lead-free soldersfor electronic packaging
Hongtao Ma
Jeffrey C. Suhling
Received: 1 July 2008/Accepted: 20 November 2008/Published online: 27 January 2009
Springer Science+Business Media, LLC 2009
The characterization of lead-free solders,especially after isothermal aging, is very important in orderto accurately predict the reliability of solder joints. How-ever, due to lack of experimental testing standards and thehigh homologous temperature of solder alloys (
even at room temperature), there are very large discrep-ancies in both the tensile and creep properties provided incurrent databases for both lead-free and Sn–Pb solderalloys. Some recent researches show that the room tem-perature aging has significant effects on mechanicalproperties of solders. This paper is intended to review allavailable data in the field and give rise to the possiblefactors including room temperature effects which causesthe large discrepancies of data. This review of the researchliteratures has documented the dramatic changes that occurin the constitutive and failure behavior of solder materialsand solder joint interfaces during isothermal aging. How-ever, these effects have been largely ignored in mostprevious studies involving solder material characterizationor finite element predictions of solder joint reliabilityduring thermal cycling. It is widely acknowledged that thelarge discrepancies in measured solder mechanical prop-erties from one study to another arise due to differences inthe microstructures of the tested samples. This problem isexacerbated by the aging issue, as it is clear that themicrostructure and material behavior of the samples usedin even a single investigation are moving targets thatchange rapidly even at room temperature. Furthermore, theeffects of aging on solder behavior must be better under-stood so that more accurate viscoplastic constitutiveequations can be developed for SnPb and SAC solders.Without such well-defined relationship, it is doubtful thatfinite element reliability predictions can ever reach theirfull potential.
General review of lead-free soldersand the mechanical properties of lead-free solders
Lead-free solders in electronicsThe use of solder alloys as metal joint materials can bedated back to thousands of years. With the emergence of the modern electronic packaging technology over the lastfew decades, solder alloys have been used as the inter-connecting material in electronic packaging. Solder jointsprovide both the electrical connection and mechanicalsupport in electronic packaging modules.Eutectic or near eutectic tin/lead (Sn–Pb) solder (melt-ing temperature
C) has long been thepredominant choice of the electronics industry due to itsoutstanding solderability and reliability. However, legisla-tion that mandates the removal of lead from electronics hasbeen actively pursued in the European Union and world-wide during the last 15 years due to environmental andhealth concerns regarding the high lead content in eutecticSn–Pb solder. Lead is a proven toxic substance which cancause a range of negative impacts to both the environmentand the human body [1]. Due to the current rapidimprovements in electronic technology and the high cost of recycling processes, the recycling rate of electronic devicesis very low, especially for high technology products, suchas computers. It has been reported that less than 2% of thecomputers produced were recycled in 1998 [2]. Themajority of the used electronics will end up in landfills
H. Ma (
J. C. SuhlingAuburn University, Auburn, AL 36849, USAe-mail: hongtaoma@hotmail.com
J Mater Sci (2009) 44:1141–1158DOI 10.1007/s10853-008-3125-9
where the lead content will eventually leach out into thesoil and hence the local ecosystem.The European Union is particularly aggressive in pur-suing the banning of lead from electronics. In June 2000,the EU adopted two directives, the Waste of Electrical andElectronic Equipment (WEEE) and the Directive of theRestriction of the Use of Certain Hazardous Substances(RoHS) [3]. The WEEE directive requires that lead has tobe removed from any end-of-life electrical or electroniccomponents. The RoHS specifically bans lead from elec-trical and electronic components manufactured after July 1,2006. As a result of the enforcement of the directives, allelectrical or electronic equipment and devices produced inor imported to EU member states must comply with theselead-free standards except those items that are exemptedfrom the bans.In Japan, although there is no specific government banof lead in electronic components, in 1998, the advisorycommittee of Japan Institute of Electronics IndustryDevelopment Association (JEIDA) put forward a roadmapfor the commercialization of lead-free solders (http://www. jeita.or.jp/english/press/2002/1217/attached.htm), and rec-ommended lead-free alternatives for industry. The elec-tronic industry in Japan is very active in pursuing lead-freeproducts and many companies have brought their lead-freeproducts into the market much earlier than the EU direc-tives’ effective dates [1,4], including Panasonic in 2001, Sony in 2001: Toshiba in 2000, NEC in 2002, and Hitachiin 2001.In the United States, there is again no specific govern-ment ban of lead from electrical and electronic devices.However, the U.S. Environmental Protection Agency(EPA) has listed lead among the top 17 chemicals that posethe greatest threat to human health [1]. The IPC (formerlyknown as the Institute of Interconnecting and PackagingElectrical Circuits) has also developed a roadmap for thelead-free movement in the U.S. [5]. The roadmap isdesigned to encourage both industry and academic insti-tutes to actively research and develop lead-free assemblyprocesses and to be prepared to respond to the worldwidelead-free movement. In recent years, many U.S. compa-nies, including Motorola, Cisco, and Intel, have also beenactively pursuing lead-free products in order to protecttheir world-wide market shares. Many universities havealso been actively funding lead-free related research.Other countries, such as China and South Korea, whichare emerging electronic manufacturing bases, have alsoadopted directives similar to those of the European Union.Although the implementation deadlines and products cov-ered by such legislation continue to evolve worldwide, it isclear that laws requiring the conversion to lead-free elec-tronics are becoming a reality worldwide. Other factors thatare affecting the push towards the elimination of lead inelectronics are the market differentiation and advantagebeing realized by companies producing so-called ‘‘green’’products that are lead-free. The companies that first suc-cessfully move into lead-free products will have a definite‘‘first move’’ advantage over their competitors, which intoday’s competitive markets translates to profits andsurvival.Lead-free solders
To be considered an alternative to Sn–Pb solder, lead-freecandidates should have similar or better properties andreliability to those possessed by eutectic or near eutecticSn–Pb solders. According to recent reports [6,7], Pb in solders contributes outstanding properties to the overallreliability of the Sn–Pb solder, such as the following:Pb reduces the surface tension of pure tin to improvethe wetting ability.Pb enables tin and copper to rapidly form intermetalliccompounds by diffusion.Pb provides ductility to Sn–Pb solders.the addition of Pb prevents the transformation of 
-tin. If the transformation occurs, it will causedramatic volume increase and loss of structural integ-rity and hence a loss of reliability. The
-tin to
-tintransformation in lead-free solders is also called ‘‘tinpest’’ or ‘‘tin disease.’’ Karlya et al. observed signif-icant ‘‘tin pest’phenomena in their lead-free solderspecimens [8].Sn–Pb solders have a low melting temperature of 183
C for eutectic solder, which allows the use of alow reflow temperature in the electronic packagingprocess and ensures the reliability of the packages.Besides all of the above benefits of Pb, the cost of Pb isalso low and it is very abundant. However, Pb is toxic,which causes the pressure from legislations worldwide.Lee proposed some basic criteria for ‘‘perfect’’ lead-freealternatives [9]. The lead-free solder needs to have a sim-ilar melting temperature to existing Sn–Pb solders,particularly eutectic and near eutectic solders, in order tohave a similar reflow profile during the manufacturingprocess; good wetting ability to ensure good metallizationin the manufacturing process; the same or better electricalproperties to efficiently transmit the electrical signals; andadequate mechanical properties, such as creep and fatigue,to preserve the reliability of the electronic packagingproducts. The new lead-free solders also need to be non-toxic and relatively inexpensive.Agreatdealofresearchiscurrentlyunderwayinthelead-free solder area, including projects organized by consortia
1142 J Mater Sci (2009) 44:11411158
including the High Density Packaging Users Group(HDPUG), the National Center for Manufacturing Sciences(NCMS), the National Institute for Standard and Technol-ogy (NIST), the International Electronics ManufacturingInitiative (iNEMI), and the Japan Electronic IndustryDevelopment Association (JEIDA). Although no ‘‘drop in’’replacement has been identified that is suitable for allapplications, Sn–Ag, Sn–Ag–Cu (SAC), and other alloysinvolving elements such as Sn, Ag, Cu, Bi, In, and Zn havebeen identified as promising replacements for standard63Sn–37Pb eutectic solder. Several SAC alloys have beenproposed by industrial consortiums. These include 96.5Sn–3.0Ag–0.5Cu (SAC 305) in Japan, 95.5Sn–3.8Ag–0.7Cu(SAC 387) in the EU, and 95.5Sn–3.9Ag–0.6Cu (SAC 396)in the USA. In addition, 95.5Sn–4.0Ag–0.5Cu (SAC405)has been widely adopted as an alloy for use in BGA solder joints. The main benefits of the various SAC alloy systemsare their relatively low melting temperatures compared withthe 96.5Sn–3.5Ag binary eutectic alloy, as well as theirsuperior mechanical and solderability properties whencompared to other lead-free solders. A survey conducted bySoldertec shows approximately 70% of the market forreflowing lead-free solders are in the SAC series (Fig.1)[10]. There are some major challenges for the current seriesoflead-free solders. SACseries alloys have ahighermeltingtemperature, around 217
C, compared to 183
C for theeutectic Sn–Pb solders. They thus require higher reflowtemperatureduringthemanufacturingprocess,whichleadtoreliability problems. The excessive build up of intermetal-lics formed at the interface between the solder joints and thecopper pad can cause reliability problems. High costs areanother issue for lead-free solders. As shown in Table1[6], the price of Ag is 150 times higher than that of Pb, and Cu istwice the price of Pb. Even though the Ag and Cu content isvery low, the overall price of lead-free solders will inevi-tably be much higher than that of Sn–Pb. A typical SACsolder is reported to be over twice the price of the Sn–Pbeutectic solders [6]. The only good news about cost is thatusing SACalloys will reducethe recycling cost by$0.13/kg,which will also increase the overall electronics recyclingrate in the future [11]. Regardless all of these problems, theSAC series lead-free solders have been widely accepted byboth industry and academic institutions. However, unless a‘‘perfect’’ lead-free solder is found to replace the Sn–Pbseries solders, research into new lead-free solders will con-tinue for years to come.
Sn–Ag–Cu lead-free solders series
Of the many lead-free solder series proposed in the lastdecade or so, Sn–Ag–Cu (SAC) series alloys have emergedas the most widely accepted (Fig.1). Soldertec’s surveyshows that the most popular SAC are the near eutectic SACalloys [10], which consist of 3.0–4.0% of Ag and 0.5–1.0%of Copper (Fig.2). The melting point of these near eutecticSAC alloys is 217
C, which is lower than the 96.5Sn–3.5Ag binary eutectic alloy at 221
C. In the SAC system,the addition of Cu both lowers the melting temperature andimproves the wettability [12].Figure3shows a typical 3-D ternary phase diagram.The contours on the top surfaces of the figure represent the
Fig. 1
The market share of different lead-free solders [10]
Table 1
Cost of basic solder elements [6]Metal element Cost (US$/kg)Lead 1.10Zinc 1.08Copper 2.24Antimony 2.64Bismuth 7.15Tin 8.67Silver 153.19Indium 194.59
Fig. 2
Survey of the market share of different types of SAC alloys[10]J Mater Sci (2009) 44:11411158 1143

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