Transcript Document

Transient Liquid Phase Bonding as a Potential Substitute for Soldering with High-Lead Alloys A.A. Kodentsov

Laboratory of Materials and Interface Chemistry, Eindhoven University of Technology, The Netherlands

There is still no obvious (cost-effective) replacement for high-lead , high melting ( 260 320

C) solder alloys • It is not possible to adjust (to increase above 260

C) liquidus temperature of any existing Sn based solder alloys by simple alloying with environmentally friendly and inexpensive elements • Therefore, in the quest for (cost-effective) replacements of the high-lead solders , attention has to be turned towards different base metals as well as the exploration of alternative joining techniques !

Liquidus projection of the Zn-Al-Mg system Ternary eutectic at ~ 343

C

The binary Bi – Ag phase diagram

solid Transient Liquid Phase (TLP) Bonding solid interlayer(s) solid • The interlayers are designed to form a thin or partial layer of a transient liquid phase (TLP) to facilitate bonding via a brazing-like process in which the liquid disappears isothermally • In contrast to conventional brazing, the liquid disappears, and a higher melting point phase is formed at the bonding temperature

solid Transient Liquid Phase (TLP) Bonding solid T = const liquid solid solid solid T = const Diffusion, Reaction solid solid product solid Any system wherein a liquid phase disappears by diffusion, reaction (amalgamation), volatilization, or other processes is a candidate for TLP bonding !

The effect of Ni additives in the Cu-substrate on the interfacial reaction with Sn

The binary Cu – Sn phase diagram

The binary Cu – Sn phase diagram 215

C

Diffusion zone morphology developed between Cu after reaction at 215

C in vacuum for 225 hrs and Sn

In the

-Cu

6

Sn

5

:

J Sn J Cu

D Sn D Cu

 

V Cu V Sn

1.6

Reaction zone developed between Sn and Cu 1at.% Ni alloy after annealing at 215

C for 400 hrs

pores !!!

Reaction zone developed between Sn and Cu 5at.% Ni alloy after annealing at 215

C for 400 hrs No pores !!!

No

-Cu 3 Sn was detected!

Isothermal sections through the Sn-Cu-Ni phase diagram P. Oberndorff, 2001 C.H. Lin, 2001 235

C 240

C

215

C; 1600 hrs; vacuum

The binary Cu – Sn phase diagram

Part of the Cu-Sn phase diagram in the vicinity of the

  

/ transition Simple Superlattice Long-Period Superlattice

Cu5Ni Sn Cu5Ni Sn Ag Sn Cu5Ni 250

C 250

C Cu5Ni Cu5Ni (Cu,Ni) 6 Sn 5 Kirkendall plane (s) Cu5Ni (Cu,Ni) 6 Sn 5 (Cu,Ni) 6 Sn 5 Cu5Ni

Binary phase diagram Ni-Bi 250

C

250

C; 200 hrs; vacuum

250

C; 200 hrs; vacuum

Ni Bi Ni Bi Ag Bi Ni 280

C 280

C Ni Ni NiBi 3 Kirkendall plane (s) NiBi 3 Ni NiBi 3

Concluding Remarks

• It is not possible to adjust and inexpensive elements (to increase above 260

C) liquidus temperature of any existing Sn-based solder alloys by simple alloying with environmentally friendly • Therefore, in the quest for (cost-effective) substitutes high-lead solders , attention has to be turned towards different base metals as well as the exploration of alternative joining techniques !

for • Through the judicious selection of Sn- or Bi-based interlayer between under bump metallization and substrate pad, (cost-effective) Transient Liquid Phase (TLP) Bonding can be achieved at ~ 250-280

C, and the resulting joints are capable of service at elevated temperatures !

• The TLP Bonding should be taken into further consideration as substitute for the high-lead soldering !

Diffusion zone morphology developed between Cu after reaction at 215

C in vacuum for 225 hrs and Sn

Parabolic growth of the Cu-Sn intermetallic layers in the binary diffusion couples at 215

C 1.58 x 10 -16 m 2 /s 7.55 x 10 -17 m 2 /s

Diffusion zone morphology developed between Cu after reaction at 215

C in vacuum for 225 hrs and Sn

N B

Determination of the ratio of intrinsic diffusivities species in line-compounds

of S

N i

 

N B

 

P R

N i

 

N B J B J A

x

x K

D B V A D A V B

 

N B

N

A

 

P V m

  

P V m

  

R V m

R V m

      

N B

N

A

 

S V m

  

S V m

    

Diffusion zone morphology developed between Cu after reaction at 215

C in vacuum for 225 hrs and Sn

In the

-Cu

6

Sn

5

:

J Sn J Cu

D Sn D Cu

 

V Cu V Sn

 1 .

6

The Cu 3 Ti – type lattice ( oP 8 ), the basic structure of the long-period superstucture of the

-Cu 3 Sn The hexagonal analog of L1 2 -structure of Cu 3 Au !

Ti Cu View down [010] Cu Ti

The basic structure ( oP 8 ) The hexagonal analog of the Cu 3 Au!

• Sn has 12 Cu NN c 0 b 0 • Cu has 4 Sn and 8 Cu NN a 0 • There are no Sn - Sn NN • In the Long-Period Superstructure of

-Cu 3 Sn ( ( a=2a 0 ; b=10b 0 ; c=c 0 ) oC80 ) antiphase shifts occur at every fifth period along the b 0 -axis Projection onto (001) plane

“The ordered Cu 3 Au rule”

L1

2 - type structure ( A 3 B ) • The nearest neighbour (NN) arrangement of A -atoms • The nearest neighbour arrangement of B -atoms

Reaction zone developed between Sn and annealing at 215

C for 400 hrs Cu after

markers !!!

Reaction zone developed between Sn and annealing at 215

C for 400 hrs Cu after

Reaction zone developed between Sn and Cu 1at.% Ni alloy after annealing at 215

C for 400 hrs

pores !!!

Reaction zone developed between Sn and Cu 5at.% Ni alloy after annealing at 215

C for 400 hrs No

-Cu 3 Sn was detected!

Isothermal sections through the Sn-Cu-Ni phase diagram P. Oberndorff, 2001 C.H. Lin, 2001 235

C 240

C

Reaction zone developed between Sn and Cu 1at.% Ni alloy after annealing at 215

C for 400 hrs

Isothermal section through the Sn-Cu-Ni phase diagram at 235

C.

(P. Oberndorff, Ph. D. Thesis, Eindhoven University of Technology, The Netherlands, 2001) Cu 1at.% Ni

Isothermal section through the Sn-Cu-Ni phase diagram at 240

C.

(C.H. Lin, Master Thesis, National Tsing-Hua University, Republic of China, 2001) Cu 1at.% Ni

Reaction zone developed between Sn and Cu 5at.% Ni alloy after annealing at 215

C for 400 hrs

Isothermal section through the Sn-Cu-Ni phase diagram at 235

C.

(P. Oberndorff, Ph. D. Thesis, Eindhoven University of Technology, The Netherlands, 2001) Cu 5at.% Ni

Isothermal section through the Sn-Cu-Ni phase diagram at 240

C.

(C.H. Lin, Master Thesis, National Tsing-Hua University, Republic of China, 2001) Cu 5at.% Ni

Diffusion zone morphology developed between Cu after reaction at 215

C in vacuum for 225 hrs and Sn

In the

-Cu

6

Sn

5

:

J Sn J Cu

D Sn D Cu

 

V Cu V Sn

 1 .

6

215

C; 1600 hrs; vacuum

The binary Cu – Sn phase diagram

The NiAs- type lattice the basic structure of the

-Cu 6 Sn 5 hP 4 tetrahedral hole octahedral hole trigonal hole

Ni As Pictorial view of the NiAs ( hP4 ) structure

A C A B A C A B A Pictorial view of the NiAs ( hP4 ) structure • Ni has 6 As NN • As is surrounded by 6 Ni • The As octahedra share faces normal to the c-axis • The Ni-atoms are direct neighbours along [001] direction

• The composition “Cu 6 Sn 5 ” is achieved by adding additional Cu-atoms in one tenth of the tetrahedral interstices in the hexagonal Sn-sublattice Cu Sn

1. Ordering of the excess Cu interstices results in the -atoms in the tetrahedral

/ - Long-Period Superlattice Cu Sn

Cu 2. The excess Cu-atoms occupy the tetrahedral interstices at random a 1 c a 2 Sn Type

A

c/

2 Type

B

• An arrangement of the unit cells along the three principle axes in the sequence

ABABAABABA

supercell of the

/ -phase … results in the

215

C

/ - Cu 6 Sn 5

Binary phase diagram Ni-Bi 250

C

250

C; 400 hrs; vacuum

250

C; 400 hrs; vacuum

0.9

Liquidus surface 1 Ag 0.7

0.8

0.5

x( A g) 0.3

0.4

0.6

LIQUID 0.2

0.2

Ni x(Bi) x(Bi) FCC_A1 LIQUID BINI BI3NI Bi

0.9

250 C 1 Ag 0.7

0.8

0.5

x( A g) R 0.3

O M B 0.2

O _ A 7 + B I3 N I+ FC C _ A 1 0.2

0.4

0.6

Bi BI3NI+BINI+FCC_A1 x(Ni) x(Ni) FCC_A1+BINI+FCC_A1 Ni

0.9

268 C 0.7

0.5

x( A g) B I3 N I+ F C C _ A 1 + LI Q U ID 0.6

0.8

0.3

0.4

1 Ag 0.2

LIQUID+BI3NI 0.2

BI3NI+BINI+FCC_A1 Bi LIQUID+BI3NI+RHOMBO_A7 x(Ni) x(Ni) FCC_A1+FCC_A1+BINI Ni

268 C LIQUID+FCC_A1+BI3NI LIQUID LIQUID+BI3NI LIQUID +RHOMBO_A7 LIQUID+BI3NI+RHOMBO_A7 Bi x(Ni) x(Ni)

Reaction zone developed between Sn and Cu 5at.% Ni alloy after annealing at 215

C for 400 hrs

The reaction zone developed in the incremental based on Cu and

Cu 6 Sn 5 (215

C; 225 hrs) couple “Unstable” Kirkendall plane ?

The Cu 3 Ti – type lattice ( oP 8 ), the basic structure of the long-period superstucture of the

-Cu 3 Sn The hexagonal analog of L1 2 -structure of Cu 3 Au !

Ti Cu View down [010] Cu Ti

The basic structure ( oP 8 ) The hexagonal analog of the Cu 3 Au!

• Sn has 12 Cu NN c 0 b 0 • Cu has 4 Sn and 8 Cu NN a 0 • There are no Sn - Sn NN • In the Long-Period Superstructure of

-Cu 3 Sn ( ( a=2a 0 ; b=10b 0 ; c=c 0 ) oC80 ) antiphase shifts occur at every fifth period along the b 0 -axis Projection onto (001) plane