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
7

Lead-contining solders have been widely used and play an

Average Particle
Diameter lmin

1 mol RatiO Ag Sn

Sn [mol

~~~~J~~T11
17.5

STZ ST3_
25.0

ST4 [

51
75.0
1.0 3.0 25

3 0.7
25

3.0 1.0
25

32.5

;2.7 1.3
25

50.0
2
I

2.0 .
25

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

2.2ICA Tible 2 shows the comosion of ICAs conning the silvr and IheAg-Sn alloypowders tat are sbown inTable 1. TAa3LE2Cc%eo vsoFICA
ClAIfeU

In the case of using a 0 ohm chip resistor with Sn/Pb (90(10) plated terminations, the contact reistamc was measured as shown in Fig.3.
Glas epoxy substrate 20 U1 " 0 ohm chip ,edltor

-FlEW

Sph

Sh1v

STI
<

sr2
_

ST3

ST4

STS

Sue Red

Ren
Amino

.<

C-g AgePeno
Acedadator

_
<-

<

<_

<R

<-

<--

16L''.
,_

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.
3. bTtMedhod 3.1 IonIc-Mgrlbon An invse electnde pattn with 1.5mm 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.

anAl0 substratebyscreen pintingandcuredat 1500Cfor30 mimL A drop of pure wate was put bdwom the eklecrodes as shown in Fig1. The fime was meared for lekage acnent at 100 p-Awhen darged with SOV.

Cu eletrode

Fig Icandbethod

(Rw wahSWbpMOWedmhadw) (Ohim chipesis and MLCC

34 RelabUty Test -40 C to +125 C thamal cycling. (30min*30min: 1000 cycl) 85 "C/850/RH storage. (1000hours) (1000hors) 125 C tmal aging.
4. Reslt and Disusion

Fig4 Adhesion siruig tes method

3.2 Conltac Redbotne Conact reistance between te copper clad and dte Sn plated terinatio ofMLCC was nmas as shown in Fig2

NIhUMW

Cu d.drgds.4,tar*laoiino

4.

ritam stmetod Fig.2 Caonut (MLCC with Sanplaled enmhatio)

Coat Resitce As shown in Fig5, imic-migr n occred easily in the case ofAgP and STIP. Whik, the ots ICAs did not promote ionic-migration and en was no growth ofdxis,

lonk4elgratlon an

100
_ 80
0
*

Table 3 shows the compositions of conventional ICA, Adhesive A(contiing ST3) andAdhesive B (containg ST3 flake).
TABLE 3 CoMPosmoNs OF ICA

34540
as

60

3 20;

IConventnal Adhesive A Adhesive B

Conductive
Filler

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.5 Ioninimgration test at 50V

Frm the test result, it was found that Ag-Sn alloy powde with 25 to 75 mol % of Sn gave excellent ionic-migration
resistance, even

thugh they

were

inside the range of

our

test

contion.

It is thought that an alloy powder with a high silver content prevents a stable structure between the Sn and the Ag.
1.E+04
I?
,-' c

4.2.1 Contact Resistance Fig.7 and 8 show the test results for contact resistance, usig MLCCs witi Sn plated termnations and 0 ohm chip resistors with Sn/Pb plated tnninations resctively.
1.E+03

Conven
Thermal Cycle

X+02

53C/5%Ahe im-40 C-ted Su

Adhesive A

ilol RA

Subtrate C la R Termingtion

*S 1.E+03 V L.E+02
9: 0

AF _

s!r-a

Substrate Cu Clad FR4 Termination IPlated Sn _ r--j

_

-40C-125C {~~~~

ST3 IT
_

__

__

,_-_-___ _

20

40 60 80 Sn Content [It/o I

100

Fig.7 Contact r csisce (Sn plaed

I.E-+03
--

eminafion)

231s
Q I.E+02

--o

X Convendonal ICA
Adhesive B

Adbesiw

Fig.6 E ct of Sn Content to Conwt Resisae

(Sn Plated Tenmination)

ci

As shown

in

Fig.6, 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, while Ag-Sn alloy powders that have lower silver content gave lower contact
resistance.

c
VS0
I
0

c i

IG

in a -

oI ,

Thermial Cycle 14OC-125C

85C/85%/RH

125C Aging

The reason ST3, ST4, and ST5 have lower contact resistance is thought to be due to a more stable and better regulated structure of the Ag-Sn alloy. In the case of STT and ST2, their random sftucture may prevent free electrons from moving easily.
4.2 Reliability Test Cbnsidering the oxidation of Sn in Ag-Sn alloy powder, we chose ST3 alloy powder as the condcwtive filler m the ICA at tiis point In addition, we prepared ST3 flake that was broken into flake pieces mechanically to get a lower contact resistance.

Fig.8 Conact sice (Sn/Pb platd termination)

Though adhesives A and B have high minial contact resistance (in the case of Adhesive B, it was somewhat lower)
conventional ICA, the stability of contact better than conventional ICA m all of the reliability tests. 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. There is a greater potential differnce between the Sn plated terination andAg in conventional ICA.
with

compared

resistance was

42.2 Adhesion Strength Fig.9 and 10 show the test results for adhesion strength, using MLCCs with Sn plated terminations, 0 ohm chip resistors with Sn/Pb plated teinadons rsectively. Regading MLCCs, the ICAs have mor stable adhesion strength mithe themal cycle test (TCT) when compared with conventional ICA. With the Sn/Pb plated teminations, the was a greater degradation of adhesion strength durng TCT. And there was almost the same result awong all t cases, 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.
60

i.50
=
44

& 30
0 20
v U

= 10

'50

lD 40
0

O
60

MLCC bonded with ICAs containing several different conductive fillers. (Ag, Ag-Sn alloy, Sn-Bi alloy and the mixtr ofAg-Sn and Sn-Bi alloy as shown in Table 3 and 4.)
TABLE4 CoMosnoNsoFICA
Conductive Adhesive C
Adhesive D

Fig. 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=-

1.R+04
1.X+03

_W
4

40

COaWntio.nI
ICA

--%mI

0-

1.5+02 I.E+s-S

Adbive A
Adhesive B

.u1

Adhesiwe C

Fig.ll Contact resistance (Sn platedtnnination)

Fig&9 Adhesion srngth (Sn plated tmination)

-]- Conventional ICA ._
_ _

100
_ 80
so

--- Adhesive C -o- Adhesive D

,.

60

30
0 20

x
-

-0- Adhesiw A --s--- AdhesiaeB

U 40
,

X 4z~-X
I I

X.'
3| z
u

20

x'

)e--X X-X
-T
.0
0

0I
,
e

Substrate Cu Clad FR4 Terminadon Pated Sn/Pb

10

Time [mini

20

30

-4

2,

1:

.0

-A

Fig.12 Ionic-migmtion estalt50V

Sn-58Bi alloy gave the highest contact resistance. While the mixue of Ag-35Sn and Sn-58Bi gave the lowest contat resistance, 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.12, using the mixue of the alloys as a conductive filler is more promisig. Fig. 13 shows contact resistance shifts and Fig.14 shows the degradation of adhesion strength in the reliability test, using MLCC s with Sn plated trminaons. In all of the reliability tests, the stability ofthe ICA containing the mixture ofAg-35Sn and Sn-58Bi alloy is beter than that of Ag filled ICA.

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, vety stable contat resistance and good adhesion strength in the reliability tess. Bu as mentioned above, their contact resistance is rathehigh, compared with Ag.

10

--

If

E+0

--- Conventional ICA -C--- Adhesive C

a)
]LE+

12

__I

01

.~

11 ,~~~~~~~~~~~~~~~N1 ,'
__ _
_

In

Ao

Jo

In

e-

Ije

Thermal

-40C-125C

Cycle

85C/85%RH

125SiC Aging

'll,

Fig.13 Conta
O
60

eistance (Sn plated tmnination)

--X- Conventonal ICA |Adheslve C

unstable. This unstable initial contact resistance also had an influence on reliability. Not only Ag-Sn filed ICAs but also Ag filled ICAs had the same tendency, moreover chip conponents withAg/Pd fired ternairtions had low ladng dependence. From the results above, we assumed tht the oxidation of Sn might give some influence, as one of the rasons for unstable miial contct resistmce. To rdce the loadig dependence, we tried to connect much filer with Sn surface of less oxidation. We evaluated a selecdon of materials with reduction effect such as "additive a' (Adhesive E, F), content ratio reducton of Sn which was easy to be oxidized (Adhesive E, F) and high filler content (Adhesive F) in this rspect Table 5 shows the compositions ofAdhesive C, Adhesive E and Adhesive F.
TABLE5 COMPOSrTnsoFFICA
IC

-0-

as

-X
2z0
to

-0[.z.z.

X ---)e X n" S0-s.

a

c}-E

<d~O
.

Conductive
Filler Base Resin

Adhesive C] Adhesive E I Adhesive F ST3 Flake ST2

Sn-58Bi Flake Epoxy Resin

I; a *0.0.
B

Curing Agent Phenolic Resin Accelarator Amine

22

Flake <=

high content

g'

.0

Il CD

.0

.0

4WD

CD a

0A

1;

c E

Additive

c--__
a
_

cAmine 2
a

c--

Thermal Cycle -40C-125C

W/I 1 85C/85%RWH

12SC Aging

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. For hat purpose, sufficient mount loading is necesary. As Fig.15 shows tha the loading dependence relied on the initial contact resistance. Our standard loading is 150g /chip as usual.
20
X

MA Fig.16 shows that the loading dependence relied on the initial conWt resistance. We were able to keep the initia contact resistance more stable and the loading dependence much lower.
20

g 15
I?
i

10
0 co

1.0 e i5
Cl
c

xi
0
Fig. 15 Cont

~~~~~Adhesive C

IP^R o - 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. 16 Conactr sistance (Sn plated tmeniaion)

5. 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, 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. In addition, an ICA filled with Ag-Sn powders have very stable contact resistance and good adhesion stregh in reliability testing, even when used with chip components with Sn plated termination. Using the mixue of an Ag-Sn alloy with a higher Sn content and a Sn-Bi alloy as a

conductive filler was effective for the compatibility of ionic-migration resistance with low contact resistance. Finally the three methods below were more effective on keeping initial contact resistance stable. 1. Selection of materials with reduction effect 2. Decrease of the Sn ratio as low as possible 3. Increase the filler content rate From these test results it can be concluded that the new ICA is potential material for SMT application.
References [1] T. Kawaguchi, "Present and Future of Pb-Free Solders", J. of SHM, vol. I 1, No.3, pp. 10- 14, 1995. [2] T. Nakamura, "Lead Free Assemble Technology by Conductive Adhesives", Jof SHM, vol.11, No.3, pp.30-35, 1995. [3] S. Nemoto, "Conductive adhesive for SMT,", J SHM,

vol.12, No.3, pp.15, 1996. [4] J.C. Bolger, J.F. McGovern, and J.M. Sylva, "Conductive epoxy surface mount adhesives for solder replacement," in Proc. Tech. Program Nat. Electron. Packag. Prod Conf:, pp.1995, 1991. [5] M. Komagata, K. Yokoyama, Y. Tanaka, and K. Suzuki, "Nickel filled adhesives,", Japan IEMT Symp., pp.429, 1995. [6] M. Ono, Y. Tomura, Y. Bessyo, T. Shiraishi, K. Eda, and T. Ishida, "Bonding resistance of SBB technique," in Proc. Pan Pasific Microelectron. Symp., pp.355,
1997. [7] L. Li, H. Kim, C. Lizzul, I. Sacolick, and J.E. Morris, "Electrical, mechanical, structural, and processing properties of electrically conductive adhesives," IEEE Trans. Comp., Packag., Manufact. Technol., vol.16, pp.843, 1993.

12