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(Workshop on Pb-Free Solders, UCLA, 9/5-6/2002)

Recent Progress in Lead (Pb)-Free Solders and Soldering Technology

Sung K. Kang IBM T. J. Watson Research Center P.O.Box 218, Yorktown Heights, NY 10598, USA (T) 914-945-3932 (email) kang@us.ibm.com

Outline
Introduction Pb-Free Candidate Solders Technical Issues in Pb-Free Solders Review on Bulk Properties Review on Solder Joint Properties Thermal Fatigue Properties Interfacial Reactions Other Reliability Issues Summary

(5/02, SKK)

Introduction
Plastic Ball Grid Array (PBGA)
100 m 600 m Si C4 BGA Solder Ball

BT

PCB

Desirable Properties of Solder Joints


Soft Solder to relax the stress/strain caused by thermal fatigue Slow growth of intermetallic compound (IMC) at the solder joints

Pb Consumption
Worldwide Pb Consumption: 5 M tons Primary uses;
Electric batteries (80 %) Ammunition Electronic applications (less than 1 %)

Electronic Applications Board assemblies (~40K tons)


PIH, SMT, HASL (surface finish) Sn-37Pb

Components (~10K tons)


SOP, QFP, DIP, BGA, FC Sn-10Pb, Sn-37Pb, 97Pb-3Sn

(01/01)

Recent Development
Europe
Legislation banning Pb in electronics proposed by WEEE* pushed to 2007 Product take-back proposed

Asia
No legislation pending Japanese companies driving Green consumer products by 2003

US
No legislation on horizon Renewed interest by electronic industry EIA, IPC, NEMI demonstrated technical initiatives Push back of WEEE date + lack of other legislation has taken immediate pressure off drive to implement (NEMI, Jan. 2002)

(* WEEE = Waste in Electrical & Electronic Equipment)

(09/02)

US Patents on Pb-Free Solders


US Pat # Assignees Harris Engelhard Willard Motorola IBM IBM IBM IBM IBM IBM Indium Co. Indium Co. Motorola Touchston Ford Lucent Lucent Lucent Seelig Seelig US Army Iowa St. U. Mitsui Mitsui Toyota IBM Lucent Ford Ford Johnson Samsung KIMM Ford IBM Delco H-Tech Mitsui Hitachi Matsushita Alpha Fry Murata Fuji Elec

7/88 4758407 7/93


4778733 4806309 5229070 5328660 5344607 5393489 5411703 5368814 5414303 5455004 5580520 5410184 5435968 5429689 5538686 5569433 5698160 5352407 5405577 5520572 5527628 5658528 5718868 5733501 5730932 5762866 5755896

5/95

6/96

Sn (wt %) 87-93 92-99 90-95 90 78 90 93 94 42 70-90 82-90 71-92 92-97 79-97 80 86 40-60 59-82 93-98 90-99 86-97 89 90 90 65-95 80 76-98 37-57 48-58 43-58 95 77-89 80 91-97 70-74 84-90 >75 91-95 72-87 81-91 >90 92-96 40-70

Bi (wt %)

Ag 0.1-0.5 0.05-3 0.1-0.5

In

Sb 4-6 3-5 5

Cu 3-5 0.7-6

Zn

Others Ni(1)

1-4 5 10 2 2 2 56 2-10 1-5

2 3

10 8 1 3 2 8-20 3-6 4-26 3-8 3-15 5-15 5 9 16-30 0.2-2 0.2-2 0-9.3 3-4 0.5 7-9 0.1-9.5 5 0.2-6 6-10 2-5 0.1-10 0.2-6 0.2-2 0.1-3 0-5 1-4 1 1

4-6

2-4 0-1 4-15 40-60 0-4 0.5 0.2-0.5 2-11 1.5-3.5 0.5-3.5 0.3-4.5 3.5-7.7 1-4 0.8-5 3 1-6

Se(1)

0-5 0.5-1.5 2-3 0.1-9.5 12 0.2-6 37-57 40-50 38-52 6-14 1-20

interm

Major Composit'n Sn Sb Cu Sn Cu Ag Sn Sb Bi Sn Bi In Sn Bi In Ag Sn In Bi Sn Ag Bi Sb Sn Sb Bi Cu Bi Sn In Sn In Bi Sn In Ag Bi Sn In Ag Sn Cu Sn Cu Ag Sn Bi In Sn Zn Ag Sn Bi Ag Sn Zn Ag Sn Ag Sb Cu Sn Ag Sb Cu SnAg BiInCu Sn Ag Cu Sn In Ag Bi Sn Zn Bi SnSbBiInAg Sn BI In Ag Sn Ag BiInZn Bi Sn In Sn Bi In SnBiSbCuIn Sn Sb Ag Sn Bi Ag In Sn Bi In Zn

10/98
5833921 5837191 5843371 5851482

1-2 0.6 3-4

2 2-5 0.1-3

5-15 0.75-2

1-4 0.6 0.013 0-3

Ni(0.6) Al,Mg,

2/99
5863493 5874043 5938862 5985212 5993736 5942185 6077477 6086687 6139979 6156132 2-5 6.5-7.5 2.5-3.5 12-24 7-11 0-6 2-3 10-23 5-10 0-9.25 2-4 3-6 0-9.25 0.1-1.0 0-0.25 0.1-2 0-9.25 0.7-2.0 0-1 0.5-1.5 0.1-9.5

Ni(0-3) Sn AgCuNi Sn In Ag Sn In Ag Cu Ga(<5 0.5-2 3-5 Sn Cu In Ga Sn Ag Bi Zn Sn Bi Zn Sn Bi Ag Cu Sn ++ Sn Sb Cu Ni Sn Bi Ag Sb

12/00

0-9.25 3-5 0-5

0-0.2

Ti(0.2) Ni(0.5) Ni(0.2)

30-58

0-5

Ge

(01/01, SKK) (09/02)

US PATs on Pb-Free Solders (II)


US Pat # Assignees

1/01 6176947 H-Tech


6179935 6180055 6184475 6187114 6229248 Fuji Elec Nihon Supr Fujitsu Matsushita Murata Mfg

Sn (wt %) bal bal bal 34-40 bal bal bal bal bal bal bal 30 bal bal bal bal

Bi (wt %) (0.5-5)

Ag 2.5-4.5 0-4.0

In 6-12

Sb (0.5-2) (0-3.5)

Cu 0.5-2.5 0-2.0 0.3-07 (0.1-5) 0.5-1.0 (0.5-5) 0.1-5.0 0.5-4 0.1-3

Zn

Others

Major Composit'n Sn In Ag Cu Sn Ag Cu Ni Sn Cu Ni Bi Sn In Sn Pd Cu Ni Sn Sb Ag Cu SnBiAgSb++ Sn Bi Ag Cu SnAgCuFeCo Sn Zn Ag Cu Sn Bi Zn Ag In Sn Ag Cu Sn Bi Zn Ag Sn Cu Ni (Ga) SnAgCuZnAl SnBiAgCuIn

46-55

(Ag) 1.0-2.0

5-20 1.0-3.0 (0.5-10) 1-10

(Zn) (Ni)

Ni, Ge Ni(0.1 Ge Pd(3.0

6224690 IBM 6228322 Sony 6231691 Iowa St. U. 6241942 Matsushita 6253988 Antaya Tec

1-20 0.5-8.0

1-5 1.5-6.0 3.0-7.7 0.1-3.5 0.05-2 4.5 2-3.5

(0.5-5 Sm,Gd Fe(0.5 7-10 2-10 (<10) (Ga<1) 0.1-3

(Ni,Co La,Ce, Co(0.5 P(<1) P(<1)

12/01 6267823 Matsushita


6296722 Nihon Supr 6319461 Nippon Gls 6325279 Matsushita

(0.2-6) 10-30 (0.25) 5-18

(0.5-3) 65 (0.1-1.5 (0.75)

0.5 (<0.7) 0.1-2 0.1-6 0.1-2.0

Ni(<1) Al,Ti

(<10) 5-10

0.1-6 3.0-6.0

(<10) 0.1-1.0

(09/02) (02/02, SKK)

Pb-Free Candidate Solders


Composition (wt %) 58Bi-42Sn Melting Point (C) 139 Applications Concerns

PTH Low temp SMT, Flip chip SMT

Poor wetting Low mp phase (BiPbSn) Cu dissolution, IMC, Fillet lift in PTH Low mp phase, OSP wetting, Voiding, IMC Poor wetting, Cu dissolution, IMC Pb- environ

Sn-3.5Ag

221

Sn-3.5Ag-5Bi

208-215

Sn-3.5Ag0.7Cu Sn-0.7Cu

217

SMT, PTH,

227

PTH, Flip chip, PTH, SMT, BGA Flip Chip, C4,

63Sn-37Pb

183

95Pb-5Sn, 97Pb-3Sn,

314, 317,

Pb- environ

(5/02, SKK)

Technical Issues in Pb-Free Solders


(5/02, SKK) What are the candidate Pb-free solders? What are the selection criteria? Can we make reliable Pb-free joints? What are the implications of higher reflow temp req. for the new solders? Are the new surface finishes needed? What is the Pb-free solder for flip chip? Are the new UBM(BLM) needed? Can we maintain the solder hierarchy? What are the reliability issues? What are the solidification mechanisms? Microstructure-property relations? Thermal fatigue mechanisms? Corrosion behavior of the new solders? Tin pest (transformation to gray tin)? Tin whisker growth? Electromigration of Pb-free solders?

Bulk Properties of Pb-Free Solders


Properties Melting point (C) UTS (MPa) Elongation (%) Hardness (HV) Elec resistivity ( -cm) Sn-37Pb 183 31-46 [1] 35-176 [1] 12.9 [6] 17.0 [7] Sn-3.5Ag 221 55 [2] 35 [2] 17.9 [7] 7.7 [7] Sn-5Sb 238 23-42 [3] 90-350 [3] 17.2 [7] 17.1 [7] Sn-0.7Cu 227 31 [4] 12 [4] 14.4 [8] 10-15 [10] Sn-9Zn 199 60-65 [5] 38 [5] 23 [9] 10-15 [10]

References: 1. H. Rack and J. Maurin, J. Testing and Eval. Vol.2, p.351, (1974). 2. M. McCormack, et. al., Appl. Phys. Lett., Vol.63(1), pp.15-17, 1993. 3. R.K. Mahidhara, et al., J. Mat's Sci. Lett., Vol.13, pp.1387-1389, 1994. 4. S. Huh, et al., Mater. Trans.(Japan I. Metals), Vol.42(5), pp.739-744, 2001. 5. C.M. Chuang, et al., J. Elec. Mat's, Vol.30(9), p.1232, 2001. 6. S. K. Kang, T. G. Ference, J. Mater. Res., Vol.8(5), pp.1033-1040, 1993. 7. S.K. Kang, et al, Proc. 49th ECTC, pp.283-288, (1999). 8. P. Lauro, private communication, November, 2001. 9. Y. Miyazawa, T. Ariga, Mater. Trans. (Japan I. Metals), Vol.42(5), pp.776-782, (2001). 10. J. Glazer, J. Elec. Mat's, Vol.23(8), p.693 (1994).

(2/02, SKK)

(09/02)

Shear Strength of Pb-Free Solder Joints (to Cu substrate)


Solder Alloy (wt %) 63Sn-37Pb Sn-3.65Ag Sn-0.7Cu Sn-3.8Ag-0.7Cu Sn-3.5Ag-3Bi Strain rate (mm/min) Solder joint Gap (mm) Test method Reference 0.10 175 Ring & plug J..Foley, et al, p.1258JEM, 2000 0.10 76 4 point bend B.Cook, et al, p.1214,JEM, 2001 15 100 ? Shear Strength (MPa) 32.7 37.2 27.0 35.1 47 (3.6Ag-1Cu) Shear Strength (MPa) 29 28 (Sn-3.5Ag) Shear Strength (MPa) 9.2 11.4 9.2 12.5 39 49.6 0.25 20 Presemt Study (MPa) 50 38 (Sn-3.5Ag)

Flip chip Shear test in shear D. Frear, et al S. Kang, et al, p.28, June TMS2002 JOM, 2001

(2/02, SKK)

(09/02)

Fabrication of Model Solder Joints

I
Copper

Vm
joint

A model solder joint made of two copper coupons of L-shape for electrical and mechanical evaluation.

(09/02) (SKK, 2/02)

Electrical -Free Solder Electrical Resistance Resistance of of Pb Pb-Free Solder Joints Joints
Cu Substrate
40 Resistance (x10-5, ohm)

30 SnAg 20 SnAgCu SnAgBi SnPb 10

0 2 12 52 1 day 7 day Reflow Time (min.)

Cu/Ni/Au Substrate
40 Resistance (x10-5, ohm)

30 SnAg SnAgCu SnAgBi

20

10

0 2 12 Reflow Time (min.) 52

(SKK, 2/02)

(09/02)

Shear -Free Solder Shear Strength Strength of of Pb Pb-Free Solder Joints Joints

Cu Substrate
60 Shear Strength (MPa) 50 40 30 20 10 0 2 12 52 1 day 7 day Reflow Time (min.) SnAg SnAgCu SnAgBi SnPb

Cu/Ni/Au Substrate
50 Shear Strength (MPa) 40 30 20 10 0 2 12 Reflow Time (min.) 52 SnAg SnAgCu SnAgBi

(09/02) (SKK, 2/02)

Percent -Free Solder Percent Elongation Elongation of of Pb Pb-Free Solder Joints Joints

Cu Substrate
Elongation (delta L/L x 100) (%) 50 40 SnAg 30 20 10 0 2 12 52 1 day 7 day Reflow Time (min.) SnAgCu SnAgBi SnPb

Cu/Ni/Au Substrate
Elongation (delta L/L x 100) (%) 30

20

SnAg SnAgCu SnAgBi

10

0 2 12 Reflow Time (min.) 52

(09/02) (SKK, 2/02)

(52nd ECTC, San Diego, May 2002)

Interfacial Reactions, Microstructure and Mechanical Properties of Pb-Free Solder Joints in PBGA Laminates

S. K. Kang, W. K Choi, D.-Y. Shih, P. Lauro, D. Henderson*, T. Gosselin*, D. N. Leonard** IBM Research Division Thomas J. Watson Research Center Microelectronics Endicott, NY **IBM Microelectronics East Fishkill, NY
*IBM

Scope of Study
Objectives Effect of Surface Finish Effect of Multiple Reflows

Materials BGA Solder Composition

Sn-3.8Ag-0.7Cu (SAC)
Surface Finishes

Cu/OSP Au/Ni(P) Au/Pd/Ni(P)


Joining Process Reflow up to 12 cycles at 260oC

Joining Process
Balled side surface finish layers

Ball side

BGA solder ball

BGA solder ball

12 cycles

surface finish layers Balled side

surface finish layers Laminated side

Laminate side

Reflow #1
Module # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Surface Finish (side B) Cu Cu Cu Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P)

Reflow #2
Surface Finish (side L) Cu Cu Cu Cu Cu Cu Au/Ni(P) Au/Ni(P) Au/Ni(P) Cu Cu Cu Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Reflow # at 260 oC 2,1 7,6 12,11 2,1 7,6 12,11 2,1 7,6 12,11 2,1 7,6 12,11 2,1 7,6 12,11

Interfacial Microstructure of Sn3.8Ag0.7Cu with Cu-Cu after 2/1 Reflows at 260C


Cu

Cu6Sn5

B (Initally balled laminate)

Ag3Sn

Sn3.8Ag0.7Cu

L(Attached laminate)
Cu6Sn5

Cu
(5/02, SKK)

Interfacial Microstructure of Sn3.8Ag0.7Cu with Au/Ni(P) -Cu after 2/1 Reflows at 260C
Cu Cu
Ni(P)

B (Initally balled laminate)

Ni3Sn4

L(Attached laminate)

Sn3.8Ag0.7Cu

Cu6Sn5 + Ni
Cu

Cu
(5/02, SKK) (5/02,SKK)

Interfacial Microstructure of Sn3.8Ag0.7Cu with Au/Ni(P) Au/Ni(P) after 2/1 Reflows at 260C
Cu Cu
Ni(P)

B (Initally balled laminate)

Ni3Sn4 + Cu

L(Attached laminate)

Sn3.8Ag0.7Cu
Ni3Sn4 + Cu

Cu Cu
(5/02, SKK)

Ni(P)

Interfacial Microstructure of Sn3.8Ag0.7Cu with Au/Pd/Ni(P)Cu after 2/1 Reflows at 260C


Cu Cu
Ni(P)

Ni3Sn4 + Cu

B (Initally balled laminate)


Sn3.8Ag0.7Cu

L(Attached laminate)
Cu6Sn5 + Ni

Cu Cu
(5/02, SKK)

IMC Growth as a Function of Reflow Cycle & Surface Finish


Balled side surface finish layers

Ball side

BGA solder ball

BGA solder ball

12 cycles

surface finish layers Balled side

surface finish layers Laminated side

Laminate side

Reflow #1
Mod ule # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Surface Finish (side B) Cu Cu Cu Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) IMC Thick. ( m) 5-7 7-12 9-17 3-4 7-10 6-10 3-4 4-5 4-6 3-5 5-8 5-12 3-5 5-7 4-6

Reflow #2
Surface Finish (side L) Cu Cu Cu Cu Cu Cu Au/Ni(P) Au/Ni(P) Au/Ni(P) Cu Cu Cu Au/Pd/Ni(P) Au/Pd/Ni(P) Au/Pd/Ni(P) IMC Thick. ( m) 4-5 7-9 9-15 10-12 10-11 8-12 3-4 5-6 4-6 5-7 5-8 8-10 2-5 3-5 3-5 Reflow # at 260 C 2, 1 7, 6 12, 11 2, 1 7, 6 12, 11 2, 1 7, 6 12, 11 2, 1 7, 6 12, 11 2, 1 7, 6 12, 11

IMC Growth as a Function of Reflow Cycle & Surface Finish


Cu (B) - Cu (L)
30 IMC Thickness (micron) L side 25 20 15 10 5 0 2/1 7/6 Reflow # 12/11 B side

B (Initally balled laminate)

L (Attached laminate)

Au/Ni(P) (B) - Cu (L)


30 IMC Thickness (micron) 25 20 15 10 5 0 2/1 7/6 Reflow # 12/11 IMC Thickness (micron) Cu side Au/Ni side 30 25 20 15 10 5 0

Au/Ni(P) (B) - Au/Ni(P) (L)


L side B side

2/1

7/6 Reflow #

12/11

Au/Pd/Ni(P) (B) - Cu (L)


30 IMC Thickness (micron) 25 20 15 10 5 0 2/1 7/6 Reflow # 12/11 IMC Thickness (micron) Cu side Au/Pd/Ni side 30 25 20 15 10 5 0

Au/Pd/Ni(P) (B) - Au/Pd/Ni(P) (L)


L side B side

2/1

7/6 Reflow #

12/11

Composition Analysis of the Interfacial IMC after 12/11 Reflows


Cu side of Cu-Cu
Cu3Sn Cu Cu6Sn5 Cu Cu6Sn5 + 0.64Ni

Cu side of Au/Ni(P)-Cu

Au/Ni(P) side of Au/Ni(P)-Cu

Au/Ni(P) side of Au/Ni(P)-Au/Ni(P)

Cu6Sn5 + 2.88Ni Cu6Sn5 + 2.68Ni Ni(P) Cu Ni(P) Cu

IMC (wt%) Surface Finish Sn (wt%) Ag (wt%) 0.33 Cu (wt%) 36.95 35.1 Ni (wt%) 0.64

Cu-Cu Cu side CuAu/Ni(P)

63.05 63.93

Au/Ni(P) side

63.32 71.39

0.3 0.24

33.7 25.49

2.68 2.88

Au/Ni(P)-Au/Ni(P)

Composition Analysis in the Solder Matrix after 12/11 Reflow


Balled side
surface finish layers

x In the middle x

10 m away from IMC

surface finish layers

Laminated side

Surface Finish

Site

Sn (wt%) 97.71 94.81

Ag (wt%) 1.34 3.95

Cu (wt%) 0.95 1.24

Ni (wt%)

Near Cu side Cu-Cu In the middle

Near Cu side CuAu/Ni(P) In the middle Au/Ni(P) Au/Ni(P)) Near Au/Ni side In the middle

96.31

3.03

0.6

0.06

95.17 95.21 95.12

3.57 3.87 3.65

1.26 0.49 1.23 0.43

Microhardness Variations as a Function of Reflow Cycle


Average values in each BGA solder ball

Cu //Cu Au/Ni(P)//Cu

Au/Ni(P) //Au/Ni(P) Au/Pd/Ni(P)// Cu

Au/Pd/Ni(P)// Au/Pd/Ni(P)

25 24

Microhardness (Hv)

23 22 21 20 19 18 17 16 2 7 12

Reflow #

Microhardness Variations as a Function of Ball Location


Cu/Cu 25 24 Microhardness (Hv) 23 22 21 20 19 18 17 16 Au/Ni(B)//Cu(L) Au/Ni//Au/Ni

Ball Side
Ball Side

1/2

6/7
Reflow#

11/12

25

Middle
Microhardness (Hv)

24 23 22 21 20 19 18 17 16

Laminate Side

1/2

6/7
Reflow #

11/12

Laminate Side
25 24 23 Microhardness (Hv) 22 21 20 19 18 17 16

1/2

6/7
Reflow #

11/12

Microstructure of BGA Solder Balls as a Function of Surface Finish and Reflow Cycle
2/1 reflows 7/6 reflows 12/11 reflows

Cu-Cu

Au/Ni(P) I Cu

Au/Ni(P) I Au/Ni(P)

100 m

Conclusions
Surface finish plays a dominant role in determining the microstructure, mechanical properties, and possibly the reliability of BGA solder joints. IMC growth is faster on Cu than on Au/Ni or Au/Pd/Ni surface finish. Microhardness of solder joints is more affected by surface finish, and less affected by reflow cycle. Ni-Ni joint is harder than Cu-Cu joint, possibly resulting in reduced fatigue life. The microstructure of BGA joints changes with reflow cycles, affected by the dissolution of surface finish layers.

(5/02, SKK)