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Conductive Adhesives containing Ag-Sn Alloys as Conductive Filler

Gou Toida*, Yukio Shirai*,, Noritsuka Mizmura*, Michinon Komagata* and Kenichi Suzuki Business Planing Division, NAMICS Corporation * Business Division, NAMICS Corporation 3993 Nigorikawa, Niigata-shi 950-3131, Japan E-mail:go(knamics.cojp

Abstract Ag filled isotropic conductive adhesives (ICA) have been investigated as promising altenatives for lead containing solders in surface mount technology (SMT) applications; however, one serious concern is the ionic-mgration of the silver filled in the ICA, especially when used in high density interconnection assemblies. In his study, ionic-gration resistance and the contact resistnce of the ICA containing Ag-Sn alloy conducfive fillers were evaluated It was found that ionic-migrabon resistance depended on the Ag-Sn ratio and that Ag-Sn alloys containing 25 to 75 mol% of Sn had excellent ionic-migration resistance though their contact resistance was rather high, compared with silver. For the compatibility of the ionicn-migration resistance with lower contact resistance, and to undastand the effect of a Sn-Bi alloy powder mixture, several additives and polymer matrixes were also stxdied. New ICAs including these additives and a conventional ICA (as reference) werex evauated for SMT. Chip components with Sn plated termintions for stability in both contact resistance and adhesion strength were monitored during reliability tests. From the test results, it can be concluded that the new ICA is a potenfial material for SMT applications. Moreover, if mount loading was not sufficient and/or mount alignmient was not suitable, initial contact resistance was unstable. Therefore, we selected materials with reduction effect and we dereased the Sn ratio as low as we could The filler content rate was also increased. As a result the loading dependence was decreased. We were sucessful in keeping contact resistance more stable while maintning good ionic-migration resistance.
1. Introduction

advantages from environmental manufacturing process and physical property points of view [3-7]. Some manufactures, mainly in the automotive electronics industry, have put ICAs to use as a solder replacement Silver as a conductive filler has excellent electrical conductivity. However, one serous concem is the ionic-migration of the silver filler in the ICA, especialy when it is used in high density interconnection assembly. The ionic-migration is very likely to cause a short circuit between the interconnections when voltage is applied under high humidity and high temperature. Nickel and copper as conductive fillers provide good ionic-migraion resistance, compared with silver, but have low electrical conductivity, especially when exposed to a high temperature. Therefore, te ionicmigration resistance and the contat resistance (for electrical conductivity) of the ICA with Ag-Sn alloy conductive fillers were mvestigated. As a result, it was found that the Ag-Sn alloys containing specific mol% of Sn gave excellent ionic-migration resistance though their conlta resistance was rather high, compared with silver. To improve contt resistance, more investigation was done on the effect of usmg a mixture of Ag-Sn alloy and Sn-Bi alloy as conductive fillers. We also investigated the new ICAs for their stabiity for both contact resistance and adhesion strength dung reliabiity tests, using chip components with Sn/Pb plated and Sn plated tenunations. 2. Materials 2.1 Ag-Sn ALloy Powders Ag-Sn alloy powders with several different Ag/Sn mol% ratios were fabncated with a gas atomized method as shown in Table 1.
TABLE I AGSNALLOYPOwDERS

important role in the electronics manufactuing industy. From an environmental point of view, the demand for lead free materials is greatly increasing year by year. There are two grouPs of matrials as possible altenafives for lead-containing solders (i.e. lead free solders and electrically conductive adhesives.) [1,2]. Among electricaly condutxive adhesives, isotropic conductive adhesives (ICA) are one of the more promising materials to replace lead-containing solders. Compared with lead-containing solders, ICAs have several
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Lead-contining solders have been widely used and play an

Average Particle
Diameter lmin

1 mol RatiO Ag Sn

Sn [mol

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0-7803-9553-0/05/$20.00 ©2005 IEEE. Polytronic 2005 - 5th International Conference on Polymers and Adhesives in Microelectronics and Photonics

imic-migr n occred easily in the case ofAgP and STIP. Reslt and Disusion Fig4 Adhesion siruig tes method 3. The fime was meared for lekage acnent at 100 p-Awhen darged with SOV. (1000hours) (1000hors) 125 °C tmal aging.2. lonk4elgratlon an 8 . 3.1 IonIc-Mgrlbon An invse electnde pattn with 1. Cu eletrode : c Fig Icandbethod (Rw wahSWbpMOWedmhadw) (Ohim chipesis and MLCC 34 RelabUty Test -40 C to +125 °C thamal cycling. TAa3LE2Cc%eo vsoFICA ClAIfeU In the case of using a 0 ohm chip resistor with Sn/Pb (90(10) plated terminations. (30min*30min: 1000 cycl) 85 "C/850/RH storage. the contact reistamc was measured as shown in Fig. 4.4.2 Caonut (MLCC with Sanplaled enmhatio) Coat Resitce As shown in Fig5.drgds.2 Conltac Redbotne Conact reistance between te copper clad and dte Sn plated terinatio ofMLCC was nmas as shown in Fig2 NIhUMW Cu d.edltor -FlEW Sph Sh1v STI < sr2 _ ST3 _ ST4 STS Sue Red Ren Amino . .5mm gap was fomied an ir-3 Cantratsme 33Adheuon S rangth The sha adhesion shtngth of a bonded MLCC and a 0 ohm chip resistr to copper cads on FR4 was measured as shown in Fig4.< C-g AgePeno Acedadator _ <- < <_ <R <- <-- 16L''. ritam stmetod Fig. Glas epoxy substrate 20 U1 " 0 ohm chip . bTtMedhod 3. anAl0 substratebyscreen pintingandcuredat 1500Cfor30 mimL A drop of pure wate was put bdwom the eklecrodes as shown in Fig1._ I 23 Rebto 2012 size 0 ohm chip nsistos widh Sn/Pb (90/10) plated tanmmtku wee used 23 Mulliayer Camlc Cip Caadtor (MLCC) 2012 size MTCCs with Sn plated temmination were used.2ICA Tible 2 shows the comosion of ICAs conning the silvr and IheAg-Sn alloypowders tat are sbown inTable 1.tar*laoiino 4. the ots ICAs did not promote ionic-migration and en was no growth ofdxis. Whik.3.

E-+03 -- eminafion) 231s Q I. we prepared ST3 flake that was broken into flake pieces mechanically to get a lower contact resistance. their random sftucture may prevent free electrons from moving easily. IConventnal Adhesive A Adhesive B Conductive Filler 0 0 10 lwime [min] 20 30 1Curing gent]j Phenolic Resin Accelarator Amine Base Resin Flake/Sphere Epoxy Resin Silver Sphere c-<=-- ST3 ST3 Flake ____<=_ I <=_ = c-= c= Fig.2. it was somewhat lower) conventional ICA.1 Contact Resistance Fig.E+02 9: 0 AF _ s!r-a Substrate Cu Clad FR4 Termination IPlated Sn _ r--j _ - _ -40C-125C {~~~~ ST3 IT ° _ __ __ . In the case of STT and ST2.6. It is thought that an alloy powder with a high silver content prevents a stable structure between the Sn and the Ag.E+03 Conven Thermal Cycle Q I X+02 53C/5%Ahe im-40 C-ted Su Adhesive A ilol RA Subtrate C la R Termingtion *S 1. with compared resistance was 9 .._-_-___ _ 20 40 60 80 Sn Content [It/o I 100 Fig. 1. 1 Thermial Cycle 14OC-125C 85C/85%/RH 125C Aging The reason ST3. while Ag-Sn alloy powders that have lower silver content gave lower contact resistance. Fig.6 E ct of Sn Content to Conwt Resisae (Sn Plated Tenmination) ci As shown in Fig. usig MLCCs witi Sn plated termnations and 0 ohm chip resistors with Sn/Pb plated tnninations resctively. even thugh they were inside the range of our test contion. c VS0 I 0 a c i . 1.E+03 V L. ST4.E+04 I? .E+02 I | --o X Convendonal ICA Adhesive B Adbesiw A Fig. There is a greater potential differnce between the Sn plated terination andAg in conventional ICA.-' c 4. IG O in a - oI . we chose ST3 alloy powder as the condcwtive filler m the ICA at tiis point In addition. it was found that Ag-Sn alloy powde with 25 to 75 mol % of Sn gave excellent ionic-migration resistance. Adhesive A(contiing ST3) andAdhesive B (containg ST3 flake). contact resistance depends on the Sn . 1 content m the Ag-Sn alloy Ag-Sn alloy powders with a higher silver content have higher contact resistance. and ST5 have lower contact resistance is thought to be due to a more stable and better regulated structure of the Ag-Sn alloy. the stability of contact better than conventional ICA m all of the reliability tests.7 and 8 show the test results for contact resistance. 4. It is thought that the stable contact resistance is due to less potential difference between the Sn plated tmination and the Ag-Sn alloy m the ICA and due to less formation of Sn oxide.100 _ 80 0 * Table 3 shows the compositions of conventional ICA.7 Contact r csisce (Sn plaed I.2 Reliability Test Cbnsidering the oxidation of Sn in Ag-Sn alloy powder.5 Ioninimgration test at 50V Frm the test result. TABLE 3 CoMPosmoNs OF ICA 34540 as 60 3 20.8 Conact sice (Sn/Pb platd termination) Though adhesives A and B have high minial contact resistance (in the case of Adhesive B.

14 shows the degradation of adhesion strength in the reliability test. it is thought that the low contact resistance is due to the formabon of a tick conductive path partly by the melting of the Sn-58Bi alloy Considering the excellent ionic-migration resistance as shown in Fig. Bu as mentioned above. compared with Ag.Adhesive C -o. 11 shows the initial contact resistnce between the copper clad on FR4 and the Sn plated temimtion electrode of a Cuing Agent Accelarator Base Resin Filler Epoxy Resin Phenolic Resin Amine ST3 Flake Sn-58Bi Flake Sn-58Bi FlakeSn8BFlk c=- - a 1. using MLCCs with Sn plated terminations.5+02 I.) TABLE4 CoMosnoNsoFICA Conductive Adhesive C Adhesive D Fig. 0 ohm chip resistors with Sn/Pb plated teinadons rsectively. Sn-Bi alloy and the mixtr ofAg-Sn and Sn-Bi alloy as shown in Table 3 and 4. Regading MLCCs. 10 . (Ag. Fig.E+s-S Adbive A Adhesive B 0 . using the mixue of the alloys as a conductive filler is more promisig. 0t 40 Thermal Cycle 85C/85%RH 125C Aging -40C-125C Fig lO Adhesion sl ngdi(Sn/P platedterination) 43 Improvement of Contat Resistance Ag-Sn alloys contaning 25 to 75 mol % of Sn as a conductive filler in ICA have excellent ionic-migration resistance. the was a greater degradation of adhesion strength durng TCT.u1 0 Adhesiwe C Fig.12.AdhesiaeB U 40 . 13 shows contact resistance shifts and Fig. With the Sn/Pb plated teminations.Conventional ICA . the ICAs have mor stable adhesion strength mithe themal cycle test (TCT) when compared with conventional ICA.0 0 0I .12 Ionic-migmtion estalt50V Sn-58Bi alloy gave the highest contact resistance.nI ICA --%mI 0- t 1. their contact resistance is rathehigh. 60 i.0 -A t Fig.' 3| z u 20 t x' )e--X X-X -T . While the mixue of Ag-35Sn and Sn-58Bi gave the lowest contat resistance.R+04 1. In all of the reliability tests.X+03 _W 4 40 COaWntio.42.9 and 10 show the test results for adhesion strength.Adhesiw A --s--.2 Adhesion Strength Fig. altogh adheives A and B had somewhat higher adhesion stengthL It can be esfimated that the occwumce of micro cracks between the surface of the plated Sn/Pb and the adhesives reslted in the degraation.Adhesive D . using MLCC s with Sn plated trminaons.ll Contact resistance (Sn platedtnnination) Fig&9 Adhesion srngth (Sn plated tmination) -]. Ag-Sn alloy. e Substrate Cu Clad FR4 Terminadon Pated Sn/Pb 0 0 10 Time [mini 20 30 -4 2. And there was almost the same result awong all t cases. 60 30 0 20 x - -0. 1: c .50 = 44 & 30 0 20 v U = 10 '50 lD 40 0 O 60 MLCC bonded with ICAs containing several different conductive fillers. the stability ofthe ICA containing the mixture ofAg-35Sn and Sn-58Bi alloy is beter than that of Ag filled ICA. vety stable contat resistance and good adhesion strength in the reliability tess.. X 4z~-X I I X._ _ _ 100 _ 80 so --.

Conclusion 0 50 Load [g/chipJ 100 sistace (Sn pated telination) We confirmed that unless mount loading was sufficient and/or mount alignment was suitble.~~~~~~~~~~~~~~~N1 . 15 Cont ~~~~~Adhesive C | 0 IP^R o . Conductive Filler Base Resin Adhesive C] Adhesive E I Adhesive F ST3 Flake ST2 Sn-58Bi Flake Epoxy Resin I. Our standard loading is 150g /chip as usual. Not only Ag-Sn filed ICAs but also Ag filled ICAs had the same tendency.' __ _ _ In Ao Jo In e- Ije Thermal -40C-125C Cycle 85C/85%RH 125SiC Aging 'll. content ratio reducton of Sn which was easy to be oxidized (Adhesive E. X ---)e X n" S0-s. sufficient mount loading is necesary. as one of the rasons for unstable miial contct resistmce.15 shows tha the loading dependence relied on the initial contact resistance. c c E Additive c--__ a _ cAmine 2 a c-- Thermal Cycle -40C-125C W/I 1° 85C/85%RWH 12SC Aging Fig. we tried to connect much filer with Sn surface of less oxidation. Adhesive E and Adhesive F.0 . 20 X MA Fig. This unstable initial contact resistance also had an influence on reliability. 16 Conactr sistance (Sn plated tmeniaion) 5.R A 0 50 100 150 0 50 100 150 0 50 100 150 Load Ig/chipi Load Ig/chipi Load Ig/chipi -1t 0 Fig.14Adhesion srength (Sn pltd tmination) A mixtue of Ag-Sn and Sn-Bi powder is effective for the siultaneous purut of low contact resistance for chip compnents with Sn plated trminations and good ionic-migration resistce.Conventonal ICA |Adheslve C unstable. We evaluated a selecdon of materials with reduction effect such as "additive a' (Adhesive E. initial contact resistance was 11 Ag-Sn alloys containing 25 to 75 ml % of Sn as a conductive filler in ICAs have excellent ionic-migration resistance. To rdce the loadig dependence.3 -- If E+0 --. F) and high filler content (Adhesive F) in this rspect Table 5 shows the compositions ofAdhesive C. Fig. a c}-E <d~O . As Fig. a *0. moreover chip conponents withAg/Pd fired ternairtions had low ladng dependence.0 e i5 Cl c xi 0 Fig.z. From the results above.0. B Curing Agent Phenolic Resin Accelarator Amine 22 Flake <= high content g' g . 20 g 15 I? i 10 0 co | 1.Conventional ICA -C--.0 i 4WD CD a A 0A 1 1.~ 11 . F).Adhesive C a) ]LE+ 12 __I 01 .16 shows that the loading dependence relied on the initial conWt resistance.0 Il CD . even when used with chip components with Sn plated termination.z. Using the mixue of an Ag-Sn alloy with a higher Sn content and a Sn-Bi alloy as a .13 Conta O 60 eistance (Sn plated tmnination) --X. We were able to keep the initia contact resistance more stable and the loading dependence much lower. TABLE5 COMPOSrTnsoFFICA IC -0- as -X 2z0 to X o -0[. For hat purpose. In addition. we assumed tht the oxidation of Sn might give some influence. an ICA filled with Ag-Sn powders have very stable contact resistance and good adhesion stregh in reliability testing.

Y. "Electrical.429. 1995. Bolger.12. T. Yokoyama.3. Li..30-35. Comp. J SHM. Bessyo.15. pp. Technol. "Nickel filled adhesives. Shiraishi. and processing properties of electrically conductive adhesives.C. and J. 1991. [6] M. Komagata." in Proc. H. No. Pan Pasific Microelectron. 10. [2] T.. Sacolick. Finally the three methods below were more effective on keeping initial contact resistance stable. No. McGovern. References [1] T.". Tomura. pp. Manufact. Packag. "Bonding resistance of SBB technique. 12 . I 1. pp. mechanical. Kawaguchi. Suzuki. Program Nat. Tanaka. [7] L. K. Ono. and K. Electron. "Conductive epoxy surface mount adhesives for solder replacement. Kim. structural. J. [5] M. Y. Ishida. and J. Jof SHM.". "Present and Future of Pb-Free Solders". 1996. Y. Nakamura.1995.14. I. vol. Lizzul.E. 1995. pp. [4] J. Decrease of the Sn ratio as low as possible 3.. "Conductive adhesive for SMT. pp. and T.16. pp.3. J. No.843.355." IEEE Trans. Symp.F. vol. Increase the filler content rate From these test results it can be concluded that the new ICA is potential material for SMT application. Japan IEMT Symp. of SHM. Nemoto.M. Tech. Eda. K. Prod Conf:. Morris. 1995. 1997." in Proc. vol. "Lead Free Assemble Technology by Conductive Adhesives". [3] S. Sylva. 1. C. vol. Packag... 1993.conductive filler was effective for the compatibility of ionic-migration resistance with low contact resistance. Selection of materials with reduction effect 2.3.11. pp.