Database for Calculation of Phase Equilibria in Systems

for Lead-Free Solders Aleš Kroupa1, Jiří Vízdal1,2, Adéla Zemanová2, Jan Vřešťál2

1Institute of Physics of Materials Academy of Sciences of Czech Republic Žižkova 22, 616 62 Brno, Czech Republic

2Institute of Theoretical and Physical Chemistry Faculty of Science, Masaryk University

Kotlářská 2, CZ-611 37 Brno, Czech Republic

Thermodynamic modelling of phase equilibria in systems for perspective lead-free solders represents first necessary step for development of new lead-free soldering materials being the basis for estimation of surface tension and viscosity of this materials and the starting point in evaluation of interaction between solder material and substrate.Database created in this work in the Thermo-Calc database format based on SGTE G-values for pure elements represents reliable consistent base for further tests and extension. Database contains data for phase equilibria of metals Ag, Bi, In, Pd, Sb, Sn and Zn in 17 binary systems: Ag-In, Ag-Bi, Ag-Sb, Ag-Sn, Ag-Pd, Ag-Zn, Bi-Sn, Bi-Sb, Bi-In, Bi-Zn, In-Sb, In-Sn, In-Zn, Sn-Sb, Sn-Zn, Pd-Sn, Pd-In and in 4 ternary systems: Ag-Sn-Bi, In-Sn-Zn, Bi-Sn-Zn, Bi-In-Sb.Binary systems (Bi-Pd, Pd-Zn, Zn-Sb, Pd-Sb) are not included because for these binary systems no thermodynamic parameters are available.For ternary system Ag-In-Pd, the ternary phase data and thermodynamic assessment do not exists. The experimental work is in progress in Univesität Wien (prof. Ipser) and relevant thermodynamic assessment will be carried out. Similarly, Ag-In-Sb system is currently studied in GP8 of COST 531(prof. Fitzner).Ternary systems Ag-In-Sn and Ag-Sn-Sb will be reoptimized for discrepancies in thermodynamic data for binary system Ag-Sn. This work is supported by the COST projects Nos. OC 531.001 and OC 531.002 of Ministry of Education of Czech Republic

Phase diagram Bi-Zn (calculated according to [1])

C .T . H eyco ck an d F .H . N ev ille : Jo urn a l o f the C h em ica lS ocie ty . 7 1 , 3 83 (1 89 7 ).

Z . K o zuk a , J . M oriy am a and I. K o sh im a : D enki K a ga ku . 3 0 , 5 91(1 9 62 )0 0.2 0.4 0.6 0.8 1

x Z n

200

400

600

Tem

per

atu

re /

°C

Z nB i

L IQ U ID 2 L 1

L IQ U ID 1 + L IQ U ID 2

L IQ U ID + H C P

H C P + R H O M B O

R H O M B O

Our experimentAs-cast structure

Composition:

0.842 atomic. % Zn

99.158 atomic. % Bi

Structure after 14th days of annealing (245 °C)

Composition:

0.73 atomic. % Zn

99.27 atomic. % Bi

All experimental data are in agreement with the phase diagram calculated

by use of the data published in Malakov et al. [1]

Phase diagram Bi-Sn

P h a s e d ia g r a m B i - S n ( c a l c u la t e d a c c o r d in g to [ 2 ] )

0 0.2 0.4 0.6 0.8 1

x S n

0

100

200

300

Tem

per

atu

re /

°C

L IQ U ID

RH

OM

BO

B C T

S nB i

B C T + LL + R H O M B O

B C T + R H O M B O

P h a s e d ia g r a m B i - S n ( c a l c u la t e d a c c o r d in g to [ 3 ] )

H . O h ta n i a n d K . I s h id a : J . E l e c t r o n . M a te r . 2 3 , 7 4 7 ( 1 9 9 4 ) .

S . N a g a s a k i a n d E . F u j i t a : J . J p n . I n s t . M e t . 1 6 , 3 1 7 ( 1 9 5 2 ) .

D i f f e r e n t v a lu e o f t i n s o lu b i l i t y i n b i s m u t h i s p r e s e n t e d .

0 0.2 0.4 0.6 0.8 1

x S n

0

100

200

300

Tem

per

atu

re /

°C

B i S n

B C T + R H O M B O

L + R H O M B O

B C T + L

L I Q U ID

B C T

RH

OM

BO

B i - S n G m f o r 2 9 0 ° C ( c a lc u la te d a c c o r d in g to [ 2 ] )

G ib b s e n e r g ie s o f p h a s e s d i f f e r in b o th a s s e s s m e n t s o f p h a s e d ia g r a m s .

N a m e l y m e t a s t a b i l e p h a s e B C T _ A 5 a n d R H O M B O _ A 7 a r e

d i f f e r e n t ly a p p r o x im a t e d .0 0.2 0.4 0.6 0.8 1

x S n

-36000

-32000

-28000

-24000

-20000

Gm

/J.m

ol-1

1

2

3

1: x (S n ), G M (L IQ U ID )2: x (S n ), G M (B C T _A 5 )3 : x (S n ), G M (R H O M B O _A 7 )

B i - S n G m f o r 2 9 0 ° C ( c a l c u l a t e d a c c o r d i n g t o [ 3 ] )

0 0.2 0.4 0.6 0.8 1

x sn

-40000

-36000

-32000

-28000

-24000

-20000

Gm

/J.m

ol-1

1

2

3

1 : x (S n ), G m (L IQ U ID )2 : x (S n ), G m (B C T _ A 5 )3 : x (S n ), G m (R H O M B O _ A 7 )

B i- S n e n t h a lp y o f f o r m a t io n fo r e u t e c t ict e m p e r a t u r e ( c a lc u la te d a c c o r d in g to [ 2 ] )

E n th a lp y o f f o r m a t io n o f p h a s e c a lc u la te d in [ 2 ] i s p re s e n te d

a b o v e . T h e a p p ro x im a t io n o f e x p e r im e n ta l v a lu e s in [ 2 ] y ie ld s

lo w e r s u m o f s q u a re s th e n a p p ro x im a t io n in [ 3 ] .

0 0.2 0.4 0.6 0.8 1

x S n

0

1000

2000

3000

4000

5000

En

thal

py

of f

orm

atio

n /J

.mol

-1

a t eu tec tic tem p e ra tu re (1 4 0 ,6 7 6 °C ) W . O e lsen a n d K .F . G o lu ck e : A rch . E isenh u ffenw . 2 9 , 6 8 9 (1 9 5 8 ).

B i-S n e n th a lp y o f fo r m a t io n fo r e u te c t icte m p e r a tu r e (c a lc u la te d a c c o rd in g to [3 ])

O w n e x p e r im e n ts a re in p ro g re s s .

0 0.2 0.4 0.6 0.8 1

x S n

0

1000

2000

3000

4000

5000

En

thal

py

of f

orm

atio

n /J

.mol

-1

a t e u te c tic tem p era tu re (1 3 8 ,8 °C ) W . O e lse n an d K .F . G o lu ck e : A rch . E isen h u ffen w . 2 9 , 6 8 9 (1 9 5 8 ).

P h a s e d ia g r a m B i- I n ( c a lc u la te d a c c o r d in g to [ 4 ] )

- - - - - P .- Y . C h e v a l i e r : C A L P H A D . 1 2 , 3 8 3 ( 1 9 8 8 ) . ( c a l c u la t e d )

0 0.2 0.4 0.6 0.8 1

x In

0

40

80

120

160

200

240

280

Tem

per

atu

re /

°C

B i In

L IQ U ID

TE

TR

AG

ON

AL

BiI

n

Bi 3I

n5

BiI

n2

P h a s e d i a g r a m A g - I n ( c a l c u l a t e d a c c o r d i n g t o [ 5 ] )

Z . M o s e r , W . G a s i o r , J . P s t r u s , W . Z a k u l s k i , I . O h n u m a , X . J . L i u , Y . I n o h a n a , K . I s h i d a : J . E l e c t r o n .

M a t e r . 3 0 , 1 1 2 0 ( 2 0 0 1 ) . F . W e i b k e : A . A n o r g . C h e m . 2 2 2 , 1 4 5 ( 1 9 3 5 ) . A . N . C a m p b e l l : C a n . J . C h e m . 4 8 , 1 7 0 3 ( 1 9 7 0 ) .

0 0.2 0.4 0.6 0.8 1

x In

0

200

400

600

800

1000T

emp

erat

ure

/ °

C

A g In

F C C

L IQ U ID

H C P

Ag 2I

n

AgI

n 2

P h a s e d ia g r a m A g -P d (c a lc u la te d a c c o rd in g to [6 ])

R . R u e r : Z . A n o rg . A llg . C h e m . 5 1 , 3 1 5 (1 9 0 6 ) .0 0.2 0.4 0.6 0.8 1

x P d

800

1000

1200

1400

1600

Tem

per

atu

re /

°C

P dA g

L IQ U ID

F C C

P h a s e d i a g r a m A g - S n ( c a l c u l a t e d a c c o r d i n g t o [ 7 , 8 ] )

I . K a r a k a y a a n d W . T . T h o m p s o n : B u l l . A l l o y P h a s e D i a g r a m s . 8 ( 4 ) , 3 4 0 ( 1 9 8 7 ) . F . V n u k , M . H . A i n s l e y a n d R . W . S m i t h : J . M a t e r . S c i . 1 6 , 1 1 7 1 ( 1 9 8 1 )

0 0.2 0.4 0.6 0.8 1

x S n

0

200

400

600

800

1000

Tem

per

atu

re /

°C

A g S n

Ag 3

Sn

H C P

F C C

L I Q U ID

L +

BC

T

P h a s e d ia g r a m A g - Z n ( c a lc u la te d a c c o r d in g to [ 9 ] )

- - - - K . W . A n d r e w s , H .E . D a v ie s , W . H u m e - R o th e r y a n dC .R . O s w in : P r o c . R o y . S o c . ( L o n d o n ) . A 1 7 7 , 1 4 9( 1 9 4 1 ) .0 0.2 0.4 0.6 0.8 1

x Z n

400

600

800

1000

1200

Tem

per

atu

re /

K

A g Z n

F C CB C C

A gZ n 3

AgZ

n

L IQ U ID

H C P

A g 5Z n 8

P h a s e d ia g r a m A g - B i ( c a lc u la te d a c c o r d in g to [ 7 ,1 0 ] )

M .W . N a th a n s a n d M . L e id e r : L a w r e n c e R a d ia t io nL a b o r a to r y . 6 6 , 2 0 1 2 ( 1 9 6 1 ) . 0 0.2 0.4 0.6 0.8 1

x B i

0

200

400

600

800

1000

Tem

per

atu

re /

°C

A g B i

F C C

L IQ U ID

R H O M B O

P h a s e d ia g r a m I n - P d ( c a l c u l a t e d a c c o r d in g to [ 1 1 ] )

E .E . S c h m id : P h .D . T h e s i s , U n iv e r s i t y S tu t t g a r t ,

S tu t t g a r t , 1 9 8 7 . H . F l a n d o r f e r : J . A l l o y s C o m p o u n d s . 3 3 6 , 1 7 6 ( 2 0 0 2 ) S .P . Y a t s e n k o a n d E .N . D ie v a : Z . F i z . K h im . 4 7 , 1 6 5 8 ( 1 9 7 3 ) .

0 0.2 0.4 0.6 0.8 1

x P d

200

400

600

800

1000

1200

1400

1600

1800

2000

Tem

per

atu

re /

K

In P d

L I Q U ID

F C C

T E T R A G O N A L

In P d

In7P

d3

In3P

d2

In3P

d5

In

Pd

2

In

Pd

3

In

Pd

2

In

Pd

3

P h a s e d ia g r a m I n - S n ( c a lc u la te d a c c o r d in g to [ 3 ] )

T . H e u m a n n a n d O . A lp a u t : J . L e s s - C o m m o n M e t . 6 ,

1 0 8 ( 1 9 6 4 ) .

A .B .K a p lu n : T e p lo f i z . S v o is tv a R a s tv o r o v . 6 5 ( 1 9 8 3 ) .

D .S . E v a n s a n d A . P r in c e : A l lo y P h a s e D ia g r a m s . 1 9 , 3 8 9 ( 1 9 8 3 ) .

0 0.2 0.4 0.6 0.8 1

x S n

5 0

1 0 0

1 5 0

2 0 0

2 5 0

Tem

per

atu

re /

°C

L IQ U ID

TE

TR

AG

ON

AL

BC

T

In S n

P h a se d ia g r a m In -Z n (c a lc u la te d a c c o rd in g to [1 2 ])

F .N . R h in e s a n d A .H . G ro b e : T ra n s . M e t. S o c . A IM E . 1 5 6 , 2 5 3 (1 9 4 4 ) .0 0.2 0.4 0.6 0.8 1

x Z n

100

200

300

400

Tem

per

atu

re /

°C

Z nIn

L IQ U ID

L IQ U ID + H C P

T E T R A G O N A L + H C P

P h a s e d ia g r a m P d - S n ( c a lc u la te d a c c o r d in g to [ 1 3 ] )

K . S c h u b e r t , H .L . L u k a s , H .G . M e is s n e r , a n d S . B h a n : Z . M e ta l l k d . 5 0 , 5 3 ( 1 9 5 9 ) .

J .R . K n ig h t a n d D .W . R h y s : J . L e s s - C o m m o n M e t . 1 , 2 9 2 ( 1 9 5 9 ) .

0 0.2 0.4 0.6 0.8 1

x S n

200

400

600

800

1000

1200

1400

1600

1800

2000

Tem

per

atu

re /

K

P d S n

L I Q U IDF C C

Pd

3Sn

Pd

2S

n

P

d3S

n2

Pd

Sn

Pd

Sn

2

Pd

Sn

3

Pd

Sn

4

P

d2S

n

Pd

20S

n13

P h a s e d ia g r a m S n - Z n ( c a lc u la te d a c c o r d in g to [ 8 ] )

B . D o b o v is e k a n d B . S t r a u s : R u d a r s k o M e t . Z b o r n ik . ( 3 ) , 2 7 3 (1 9 6 0 ) .

B .- J . L e e : C A L P H A D . 2 0 , 4 7 1 (1 9 9 6 ) .

0 0.2 0.4 0.6 0.8 1

x Z n

100

200

300

400

500

Tem

per

atu

re /

°C

S n Z n

L IQ U I D

L IQ U ID + H C P

B C T + H C P

V e r t i c a l s e c t i o n s o f t h e I n - S n - Z n t e r n a r y s y s t e ma t 9 w t . % Z n ( c a l c u l a t e d a c c o r d i n g t o [ 1 4 ] )

The In-Sn-Zn system was studied by twoauthors [14,15] and slightly different results were obtained. It is difficult to decide, whichassessment is better, as different regions are approximated with different success (see liquid and eutectic temperature in Figs. above)

This will be subject of further study

V e r t i c a l s e c t i o n s o f t h e I n - S n - Z n t e r n a r y s y s t e m a t 9 w t . % Z n ( c a l c u l a t e d a c c o r d i n g t o [ 1 5 ] )

S . W . Y o o n , J . R . S o h , B . J . L e e , H . M . L e e , i n : R . K . M a h i d h a r a , D . R . F r e a r , S . M . L . S a t y , K . L . M u r t y , P . K . L i a w , W . W i n t e r b o t t o m : D e s i g n a n d r e l i a b i l i t y o f s o l d e r s a n d s o l d e r s i n t e r c o n n e c t i o n s , T h e M i n e r a l , M e t a l s a n d M a t e r i a l s S o c i e t y , 1 2 1 ( 1 9 9 7 ) .

V e r t i c a l s e c t i o n s o f t h e B i - S n - Z n t e r n a r y s y s t e m a t 4 0 w t . % S n ( c a l c u l a t e d a c c o r d i n g t o [ 1 6 ] )

S . D . M u z a f f a r : J . C h e m . S o c . 1 2 3 , 2 3 4 1 ( 1 9 2 3 ) .

I s o t h e r m a l s e c t i o n o f t h e p h a s e d i a g r a m B i - S n - Z n a t 1 3 5 ° C ( c a l c u l a t e d a c c o r d i n g t o [ 1 6 ] )

V e r t i c a l s e c t i o n s o f t h e A g - B i - S n t e r n a r y s y s t e m a t 4 0 m o l % A g ( c a l c u l a t e d a c c o r d i n g t o [ 1 0 ] )

S . H a s s a m , E . D i c h i a n d B . L e g e n d r e : J . A l l o y s & C o m p . 2 6 8 , 1 9 9 ( 1 9 9 8 ) .

P h a s e d i a g r a m B i - S b ( c a l c u l a t e d a c c o r d i n g t o [ 3 ] )

E x p e r i m e n t a l p h a s e d i a g r a m B i - S b ( a c c o r d i n g t o [ 1 9 ] )

0 0.2 0.4 0.6 0.8 1

x S b

200

300

400

500

600

700T

emp

erat

ure

/ °

C

S n S b

L IQ U ID

R H O M B O

P h a s e d i a g r a m S n - S b ( c a l c u l a t e d a c c o r d i n g t o [ 2 0 ] )

E x p e r i m e n t a l p h a s e d i a g r a m S n - S b ( a c c o r d i n g t o [ 2 1 ] )

0 0.2 0.4 0.6 0.8 1

x S n

0

200

400

600

800

Tem

per

atu

re /

°C

S b S n

L IQ U ID

RH

OM

BO

Sn

Sb

Sn

3Sb

2

Phase diagram In-Sb (calculated according to [3])

T.A. Cam bell and J.N . koster: Cryst. Res. Technol. 33,717-731 (1998).

0 0.2 0.4 0.6 0.8 1

x S b

0

200

400

600

800

Tem

per

atu

re /

°C

L IQ U ID

InS

b

T E T R A G O N A LR H O M B O

In S b

P h a s e d ia g r a m A g -S b (c a lc u la te d a c c o rd in g to [2 0 ])

C . T . H e y c o c k a n d F . H . N e v il le : P h ilo s . T r a n s . R . S o c . L o n d o nS e r . A . 1 8 9 , 2 5 (1 8 9 7 ) .

P . W . R e y n o ld s a n d W . H u m e -R o th e ry : J . In s . M e t . 6 0 , 3 6 5 (1 9 3 7 ) . W . H u m e -R o th e ry a n d P . W . R e y n o ld s : P r o c . R . S o c . L o n d o n S e r .

A . 1 6 0 , 2 8 2 (1 9 3 7 ) . P . W . R e y n o ld s a n d W . H u m e -R o th e ry : J . In s . M e t . 6 0 , 3 6 5 (1 9 3 7 ) . M . H a n s e n a n d K . A n d e rk o : C o n s titu t io n o f B in a r y A llo y s .

M c G ra w -H ill N e w Y o rk (1 9 5 8 ) .

0 0.2 0.4 0.6 0.8 1

x S b

600

800

1000

1200

Tem

per

atu

re /

K

A g S b

L IQ U ID

FC

C

HC

P

Ag 3S

b

I s o t h e r m a l s e c t i o n o f t h e p h a s e d i a g r a mB i - I n - S b a t 1 2 0 ° C ( c a l c u l a t e d a c c o r d i n g t o [ 3 ] )

V e r t i c a l s e c t i o n s o f t h e B i - I n - S b t e r n a r y s y s t e ma t 1 0 w t . % S b ( c a l c u l a t e d a c c o r d i n g t o [ 3 ] )

E . A . P e r e t t i : T r a n s . A m . S o c . M e t . 5 4 , 1 2 - 1 9 ( 1 9 6 1 ) .

I s o t h e r m a l s e c t i o n o f t h e p h a s e d i a g r a mA g - B i - S n a t 4 0 0 ° C ( c a l c u l a t e d a c c o r d i n g t o [ 1 0 ] )

H . O h t a n i , I . S o t a h , M . M i y a s h i t a a n d K . I s h i d a :M a t e r i a l s T r a n s a c t i o n s . 4 2 , 7 2 2 ( 2 0 0 1 ) .

P r e d i c t e d v e r t i c a l s e c t i o n o f t h e A g - I n - P d t e r n a r y s y s t e m a t 2 5 m o l % P d ( f r o m b i n a r y d a t a )

Y .C h . S u h , Z .H . L e e : J o u r n a l o f M a t e r i a l s S c i e n c e : M a t e r i a l s i n m e d i c i n e . 1 1 , 3 0 1 ( 2 0 0 0 ) .

P h a s e d i a g r a m p r e d i c t i o n

0 0.02 0.04 0.06 0.08

x I n

900

1000

1100

1200

Tem

per

atu

re /

°C

L I Q U I D + F C C

F C C

F C C + I n P d 3

P r e d ic te d iso th e r m a l s e c t io n o f th e p h a s e d ia g r a mA g -I n -P d a t 2 0 0 ° C ( fr o m b in a r y d a ta )

This ternary system is currently main subject of our interest, as no ternary phase data and thermodynamic assessment exist. The experimental work is under progressat Univesität Wien (prof. Ipser) and relevant assessmentwill be carried out in dependence on available data

LITERATURE for thermodynamic parameters:

[1] D. V. Malakhov: CALPHAD. 24, 1-14 (2000).

[2] H. Ohtani and K. Ishida: J. Electron. Mater. 23, 747 (1994)

[3] B.-J. Lee., Ch.-S. Oh, J.-H. Shim: J. Electron. Mater. 25, 983 (1996).

[4] Y. Cui, S. Ishihara, X. J. Liu, I. Ohnuma, R. Kainuma, H. Ohtani, K. Ishida: Mat. Trans.

43, 1879 (2002).

[5] Z. Moser, W. Gasior, J. Pstrus, W. Zakulski, I. Ohnuma, X. J. Liu, Y. Inohana, K. Ishida:

J. Electron. Mater. 30, 1120 (2001).

[6] G. Ghosh, C. Kantner, G. B. Olson: J. Phase Equil. 20, 295 (1999).

[7] U.R. Kattner and W.J. Boettinger: J. Electron. Mater. 23, 603–610 (1994).

[8] H. Ohtani, M. Miyashita and K. Ishida: J. Japan Inst. Metals. 63, 685–694 (1999).

[9] T. Gómez-Acebo: CALPHAD. 22, 203–220 (1998).

[10] H. Ohtani, I. Satoh, M. Miyashita, K. Ishida: Mat. Trans. 42, 722–731 (2001).

[11] Ch. Jiang, Z.-K. Liu: Metall. Mater. Trans. 33A, 3597 (2002).

[12] B.-J. Lee: CALPHAD. 20, 471 (1996).

[13] G. Ghosh: Metall. Mater. Trans. 30A, 5 (1999).

[14] Y. Cui, X. J. Liu, I. Ohnuma, R. Kainuma, H. Ohtani, K. Ishida: J. Alloys Comp. 320, 234–241(2001).

[15] Y. Xie, Z. Y. Qiao, A. Mikula: CALPHAD. 25, 3-10 (2001).

[16] D. V. Malakhov, X. J. Liu, I. Ohnuma, K. Ishida: J. Phase Equil. 21, 514 (2000).

[17] B. Sundman: Thermo-Calc, Royal Institute of Technology S-100 44, Stockholm, Sweden. 1997.

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