Calphad, Vol. 27, No.1, pp.

27-37,2003
Pergamon 0 2003 Published by Elsevier Science Ltd
0364-5916/03/$ - see front matter
PII:SO364-5916(03)00028-2
DOI: 10.1016/S0364-5916(03)00028-2

Thermodynamic Reassessment of the Au-In Binary System

H.S. Liu’, Y. Cui’, K. Ishida2, and Z.P. Jin’*

1. School of Materials Science & Engineering, Central-South University, Chang-Sha, Hunan, 410083,
P.R.China.
2. Department of Materials Science, Graduate School of Engineering, Tohoku University, Sendai 980-8579,
Japan
*. Corresponding authour’s e-mail: jin@mail.csu.edu.cn

(Received October 30,2002)

Abstract. Through CALPHAD method, the Au-In binary system has been thermodynamically reassessed. The
excess Gibbs energies of the solution phases, liquid, fee, c 1, and hcp were formulated with Redlich-Kister
expression, while the y and ‘Ir phases with narrow homogeneity ranges were described with sublattice models,
and other intermetallic phases were treated as stoichiometric compounds, A set of self-consistent parameters has
been obtained, which can reproduce most experimental data of thermodynamic properties and phase diagram of
this binary system. Additionally, the standard formation enthalpies of all intermediate phases have also been
calculated. 0 2003 Published by Elsevier Science Ltd.

Introduction
Au-In alloys are of importance as candidate materials in electronic packaging. Phase diagram and the
related thermodynamic property of this system may play an important role in developing new Au-base alloys.
The Au-In binary system was previously assessed by Ansara and Nabot [l]. The assessed results [ 1] were
reasonably consistent with most experimental data of phase boundaries and thermodynamic properties of this
binary system. However, the calculated solubility of In in fcc(Au) [l] trends to increase when temperature is
lowered to about 180°C as shown in Fig. 1. Such tendency is not reasonable. Moreover, v and I, which have
homogeneity ranges, were treated as stoichiometric compounds [ 11. Such simplifications may bring about some
problems when extrapolation is undertaken to high-order diagrams involving the Au-In binary system, e.g.
Au-In-Sn ternary system. In view of this, thermodynamic reassessment of the Au-In binary system is performed.

Evaluation of Experimental Data

Figure 2 is the phase diagram of the Au-In binary system reviewed by Okamoto and Massalski [2] on the
basis of the boundary data reported by Hiscocks and Hume-Rothery [3], Owen and Roberts [4], Kubaschewski
and Weibke [5], Nikitina et a1.[6] and Schubert et a1.[7]. The boundaries in the field where liquid and fcc(Au)
coexist, and the In-rich region measured by Nikitina et al.[6] show obvious difference from those reported by
Hiscocks and Hume-Rothery [3], Owen and Roberts [4] and Kubaschewski and Weibke [5]. Especially, the
boundary data for liquid+fcc two-phase region reported by Nikitina et al.[6] show much disparity, and were

27
28 H. S. LIU et al.

given up by Okamoto and Massalski [2]. The experimental data in other parts of the Au-In system in all
references agree well. Temperatures for the invariant reactions involving liquid reviewed by Okamoto and
Massalski [2] were in agreement with those lately measured by Mikler et al.[8] using DSC. In the present work.
all the liquidus and the solidus of fee in Ref.[3-5,7] are given higher weight durmg optimization while the
boundaries concerning the o 1, -1 and Y phases and the invariant reactions adopted in this optimization arc
taken from Ref.[2] and Ref.[8]. Although the i ‘# E order-disorder transformation at about 340-C was
reported 121, it will not be taken into account in the present work due to lack of other experimental information
on this transformation. t ’and E are treated as A& considering its composition range Compositions and
crystal structures of all phases in the Au-In system are listed in Table 1.

Table 1. Phases in the Au-In Binary System and Their Models Adopted in This Work
Composition Structural
Phase Prototype Model
at.% In Designation
Fcc(Au) 0 to 12.7 Al cu (AuJn)
ul 12 to 14.3 DO24 NijTi (AuJn)
Hcp 13 to23 A3 Mg (AuJn)
p 21.5 to 22.2
I
R '
r
1317tn775
-_. ._ --.. I - ..,“__, \----I" ,!~.",..lh22222
____
E" 24.5 to 25 (Au)0 -is( 1
25
E >a 24.5 to 25 DOa p CuxTi (Au)o.7s(In)o 25 ]
hi 28.8 to 31.‘I D83 Cu9A14 (Au)0 6923i(Au,In)o 23077(In)O
07692 /
t
Y’ 29.8 to 30.t i Au&i, (Au)0 7(In)o 3 i
Y 35.3 to 39.5 D513 1NizAI? 1Muh c(Au,In)o ~~~~~(In)6 16667
AuIn 50 to 50.1 (.W~s(Wos

AuIn2 66.7 Cl CaF2 (AU)0.33333(In)0.66667

TetrlTn) 100 Ah In IIn~

‘: F and E ’are regarded as one phase in this paper.

Only thermodynamic properties of liquid in this system were reported. Kameda et a1.[9] measured
activity of In in liquid Au-In alloys. Itagaki and Yazawa [lo] measured the mixing heats of liquid at 1100°C.
which differ much from those lately reported by Castanet[ 1l] who measured the enthalpies of mixing of liquid
Au-In alloys at different temperatures. According to the discussion by Wasai and Mukai (121, the enthalpies
obtained in Ref.[ 1l] were more reliable, thus were given larger weight in the present optimization. Additionally,
mixing enthalpy of liquid alloys measured by Castanet [l l] show its dependence on temperature.

Thermodynamic Models
Solution Phase: Liquid, fcc(Au), ~1I and hcp
Gibbs energies of the solution phases in the,Au-In system are expressed as following:

Gm = ~x,‘G,‘+RT Cx~In(r,)+x,,x,~~“‘L:,,,~(x,” -x,~)’ .._....

i=,&.,n ,=Au,,fl ,=6

where 4 denotes all the solution phase, and

O’L”
,~“,,”= A, + B,T + C,Tln(T) . ... .... .... ...._.................................................................... (2)

and XA”and XI, are the mole fraction of component Au and In, respectively. “G,’ is the molar Gibbs energy of
 THERMODYNAMIC REASSESSMENT OF Au-In BINARY SYSTEM

pure element i in status of 4. “‘&,~ is the interaction parameter of the solution, where A,, Bj, and C, are

constants to be optimized. And m is a non-negative integer, always taking a value smaller than 3. Because
mixing enthalpies of liquid Au-In alloys were reported to depend on temperature [ 111, C, is introduced for liquid,
but not for fcc(Au), cr 1and hcp.

The y and B phase

The 7 phase has Al&us-type structure. Considering the radius of the elements and the location of atoms
in this kind of lattice, the thermodynamic model of y is denoted by a 3-sublattice model:
and the Gibbs free energy of y is formulated as:
(Auk, 69231(Au,In)a23077(In)O.O76s2,

GY = Y::GL AuLn+ Y/l:G:, In:,,,+ 0.23077RT{Yi ln(Yl:) + Yi ln(Yl)}

+ Y”AuY”LY
,n A” Ru,,“:,n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(3)

where

G;, A“.,” = 0.92308’G,/t’ +O.O7692’Gr + E, + F,T ... ..... .... .... ......... ....... ..... ....... ... .... ... ....(4)

,n = 0.6923l’Gz
G:u:,n + 0.30769’GF + E, + FJ . ...... ........ .... .... ... ..... ... .... ... ..... ....... .....(5)

and

=Cx+&T. . ..__....................__...........__................_............,.
LYAuAu.,n.,n ..__._(6)

where E, ,F,, CJ, D3 are parameters to be optimized, and ‘Gc and ‘Gr are the molar Gibbs energies of

standard pure elements, respectively.

TheI phase has isotypical structure of NizA13, which has recently been modeled as (Al)s(Al,Ni)@i,Va)
by Ansara et al [ 131. Considering the fact that the misfit of atoms between Ni and Al does not differ so much
from that between Au and In, a similar model (Au)s(Au,In)a(In,Va) may be adopted to describe rP However, the
atomic radius of In is very large compared with that of Ni, so substitution of vacancy for In may be much
difficult. Accordingly the above model is simplified to (Au)o.s(Au,In)o.~333s(In)o.i6667in the present work, of
which the Gibbs energy is:

n + YlG,W,,,,,.,”+ 0.33333RT{YL ln(Yl:) + YL ln(Y,f )}

G’ = YltG,Yu-Au:‘

+ Y;;Y,;L;u:,” ,“,n.,...,..__.................................................................................................., (7)

where

G,W,:,,.,”= 0.83333’GE +O.l6667’GF +E, + F,T ...... ... ...... ... ...... ... ..... ... .... ... .... ........ .(8)

G,‘.,n ,n = OS’GZ +0.5’Gr + E, + F,T .. .... ..... ... ..... .... .... .... ...... .... .... .... ... ..... .... .... ... ....(9)

and LLAu.ln
I,,
has the same form as that for the Y phase.

Stoichiometric Compounds: fi , fi ‘, y ‘, Au&, AnIn, Au&

Because the homogeneity ranges of these phases are no more than 2at.% In, they were simplified to be
30 H. S. LIU et al.

stoichiometric compounds. By using Neumann-Kopp rule, Gibbs energies of all these compounds are expressed
as:

G”,,R”=a’G,/:’ +b’G,‘,“’+ E, + F,T .__._..........._.............. ..(lO)

where A(, B,, represents all the compounds, a and b are the ratios in the formula, and Es and Fs are parameters to

be optimized.

Results and discussion

By CALPHAD method and by using the lattice stabilities given by Dinsdale [14], the thermodynamic
parameters of the Au-In binary system have been reassessed as listed in Table 2. Compared with the assessment
by Ansara and Nabot [l] listed in Appendix, the parameters of liquid in the present work have been changed
much and one more parameter has been introduced to describe fee, while the parameters for most stoichiometric
compounds varied slightly. Meanwhile, improvement on assessment in the present work is evident as indicated
later.

Phase Diagram Evaluation

Figure 3 shows the calculated phase diagram, and comparison of the calculated diagram with
experimental boundaries is shown in Fig. 4. In combination to Table 3, which gives all invariant reactions, it is
clear that reasonable agreement has been realized between the calculated and experimental data of phase diagram.
The present work are in agreement with those by Ansara and Nabot [I] in the part from 50 to 100 at.96 In of the
phase diagram, while improvement on the other part of the phase diagram in the present work is also noticeable
as analyzed below.

(1) In the Au-rich comer, the phase diagram assessed in the present work is more reasonable as it is much
closer to that proposed by Okamoto and Massalski [2]. Due to different crystal structure, large misfit between
atomic radius, and due to different electronegativities of Au and In, it may be more acceptable that the solubility
of In in fcc(Au) should decrease steadily with temperature. The presently assessed diagram reproduces such
tendency but that by Anssra and Nabot [ 1] does not.

(2) Not only the composition ranges of y and y have been reasonably modeled, but also the
differences of crystal structures between 13 and 0 ‘, and Y and y ’are taken into account.

(3) Temperatures of invariant reactions, L-*fcc+ a 1 and L+ a i+hcp calculated by Ansara and Nabot
[I] differ more than 5K from the reviewed values [2] and the lately measured data [8], whereas the
corresponding values in the present work show deviations no more than 2K.

In addition, a: 1is calculated to be stable down to room temperature according to the present work, this is
in consistence with the reviewed relations in Ref.[2], while Ansara and Nabot [l] calculated the temperature for
eutectoid reaction (y.i+fcc+hcp to be 177’C. Whether o I can be stable down to room temperature or not
remains uncertain.

Evaluation of the Optimized Thermodynamic Data

Comparison between calculated and experimental mixing enthalpies of liquid at different temperatures is
shown in Fig.5. It can be seen that the calculated values of mixing enthalpy agree well with experimental data in
Ref.[ll] while deviate much to those reported in ReE[lO]. As mentioned earlier in Section 2, the enthalpies
 THERMODYNAMIC REASSESSMENT OF Au-In BINARY SYSTEM 31

obtained in Ref.[ 111 were more reliable than those in Ref.[lO]. Hence, the calculated enthalpy of mixing of
liquid is acceptable.

Table 2. Assessed Parameters of the Au-In System in This Work

Liquid: (AuJn)
,(11
L”,,,,,,=-76196.19+64.2914T-6.6375TLn(T)
“, U)LLlll =-31134.02+81.3582T-8,5134TLn(T)
A”.,”
FCC:(AuJn)
WLhCC (I)LFCC
,,,,,,,=-48493.65+46.6237T-6.8308TLn(T) AU,,”
=498.45

a 1 : (Au,In) * (lattice stabilities ofAu and In in a I status were cited from Ref.[l])

‘“‘L”’
,,,,,,,=-48238.66+5.355lT “‘L”’
Au,,n=-48.36-16.7932T

Hcp: (AuJn)

‘“‘L~;,,,=-55780.55+13.8198T “‘Lz,“=6788.95-32.8937T

Y : (Au)o.69231(Au,In)o.z3o77(In)o.o76g2
G i,UlU,,,=0.92308°Gi;l’+0.076920G~ -2830.47-2.519lT

G:, ,,,,n =0.69231 ‘G,/:‘+0.30769’GF -11992.16-3.65llT G:, Au.,n.,n

=2 144.6

rIr : (AU)o.5(AU,In)o.33333(In)o.16667

GYu 4" 6,=0.83333°G~+0.166670G~ +2153.38-8.039T

ii irr =0.5°G~+0.5”G~-18225.14+3.0T
GYt. G;U,U,,n,n=-15683.16

fl : (Au)o.m(In)o.zls GP=0.7850G/CC+0.2150GTe”
A” ,n -8980.42-3.3042T

s ‘: (AU)o.77778(In)o.zzz22 G” =0.77178°G,/:‘+0.222220G~ -9382.52-3.1015T

Au3In: (Au)o.75(In)o.2s GA”>‘=0.75OGe

” +0,25”Gp -10582.67-2.9323T

Y ‘: GWdWo.3 GY’=0.70GA/:C+0.30G~-12813.11-2.0538T

AuIn : (Au)o.s(In)o.s G A”‘“=0.5°G~+0.50G~ -20188.37+2.3786T

Auh : (AU)O.33333@)0.66667 G Auf+=0.33333 ‘Gfcc

Au+0.66667 ‘G=’
,” -26129.06+11.1133T

Gik =OGT
Tetragonal: (In)

Figure 6 illustrates activities of In in Au-In liquid. It is clear that the calculated activities of In in liquid
are reasonably consistent with experimental values measured by Kameda et al.[S].
32 H. S. LIU et a/.

Table 3. Calculated and Experimental Data for Invariant Reactions

Reaction Composition (at% In) Temperature( % ) Reference
L-’ u ,+Fcc 642 I11
0.240 0.142 0.125 649 I2J
0.225 0.145 0.138 649 This work
L-r (Y,+Hcp 634 111
0.244 0.143 0.157 641 / 121, ~
0.228 0.147 0.159 641 This work
I. +Hcp+Au3In 493 ill
0.292 0.230 487 121
0.290 0.209 487 This work
L-+Au3In+ y 0.311 0.290 482 [21
0.296 0.288 479 This work /
4
L-+1, +Y 0.350 0.310 0.360 455 121
1459 181
0.340 0.302 0.361 450 This work
I,+ Y +AuJn 0.398 0.385 454 [iI -J
0.408 0.393 456 j
j I‘his work
l.+AuIn+AuIn2 0.553 495 lisl
121 !
497
I
0.542 496 I This work
!
L-‘AuIn2+Tetr(In) 0.998 156 PI
155 IX1
0.999 156 ’This work
L +w 0.383 458 121
0.379 461 This work
L+AuIn 509 I21
509 IX1
506 This work
L-+AuIn2 541 I21
539 / 1x1
539 1This work
Au3In+ y ---t y ’ 0.306 375 121
0.301 380 This work
I
y+y,+m 0.308 0.361 365 [21
0.306 0.371 361 This work ~
i
Au3In+Hcp + B 337 [21
337 This work
Au3In+ 13--t fi ’
‘P
PI
295 This work
fi -+ /3 ‘+Hcp 275 PI
275 This work
Y -+ y ‘+AuIn 0.390 224 PI
0.390 224 This work

Gibbs energies of formation of intermediate phases have been further calculated as listed in Table 4. In
combination to Table 2, it is interesting to note that Gibbs energies of intermediate phases at 25°C decreases
 THERMODYNAMIC REASSESSMENT OF Au-in BINARY SYSTEM 33

with increasing In while the formation entropies for linear compounds show opposite trend.

Table 4. Gibbs Energy of Formation of Intermediated Phases Calculated in This Work. Reference States are Pure
Solid Comnonents.

I Phase I Composition (at.%In)

I Temperature (Cc)
I nG(J/mol) I
B 0.215 25 -9965
0.215 277 -10798
0.22222 25 -10307
P’
0.22222 200 -10850

Conclusion
Phase diagram of the Au-In binary system has been reassessed on the basis of phase diagram and
thermodynamic data of liquid. With consideration of the homogeneity ranges of y and Y , and the structural
differences between y and y ’, fl and /3 ’, a set of parameters has been obtained which can satisfy both the
experimental data of thermodynamic and phase diagram.

Acknowledgment
This work was supported by the Grant-in-aids for Scientific Research from Ministry of Education,
Science, Sports and Culture, Japan. One of the authors, H.S. Liu thanks for the financial supports from Marubun
Research Promotion Foundation, Japan.

References
[l] I. Ansara, and J.-Ph. Nabot, CALPHAD, 16(1992), 13.
[2] H. Okamoto, and T.B. Massalski, Phase Diagrams of Binary Gold Alloys, ASM International, Metals Park,
OH, (1987),142.
[3] S.E.R. Hiscocks, and W. Hume-Rothery, Proc.Roy.Soc.(London), A282(1964),318.
[4] E. Owen,andE.A.O. Roberts, J. Inst. Met.71(1945),213.
[5] 0. Kubaschewski, and F. Weibke, Z. Metallkd., 44(1938),870.
[6] V.K. Nikitina, A.A. Babitsyna, and Yu.K. Lobanova, Izv.Akad.Bauk SSSR, Neorg. Mater., 7(1971),371.
[7] K. Schubert, H. Breimer, and R. Gohle, Z. Metallkd., 50(1959), 146.
[8] J. Mikler, A. Janitsch, and K.L. Komarek, Z. Metallkd., 75(1984), 719.
[9] K. Kameda, T. Azakami, and M. Kameda, J. Jpn. Inst. Met., 38(1974), 434.
 H. S. LIU eta/.

]lO] K. Itagaki, and A. Yazawa, J. Jpn. Inst. Met., 35(1971),383.

11I] R. Castanet, W. Ditz. K.L. Komarek, and E. Reiffenstein, Z. Metallkd.. 72( 1981 1. 176
[ 121 K. Wasai, and K. Mukai, Fluid Phase Equilibria, 125( 1996), 185.
[ 131 I. Ansara, N. Dupin, H.L. Lukas, and B. Sundman, J. Alloys and Comp.. 247( 1997). 20
114lA.T. Dinsdale, CALPHAD, 15(1991),317.

Appendix : Optimized Parameters of the Au-In System in Ref. 1I ]

Liquid: (Au,In)
““LL”’
,,,,n=-80027.7+89.7173T-9,5705TLn(T) “ILL”
,,,,“=-34977.3+117.2938T-13.0337TIn(T)

FCC:(Au&)
‘OILkC
,,,,,=-61378.5+174.9882T-23.185lTLn(T)

a, : (Au&) *

L&,,, =-54650.0+16.09T
i(li u
“‘L’;l,,n ==4460.9-23.64T

Hcp: (Au&)

“‘L::‘;<,=-60630.1+16.79641 “‘L;,‘;,n=7870.9-27.3128’1

y : (AU)o.6z(In)o.38 G”=0.62°G~+O+0.38”G;:“’ -14804.5-2.0931

b Or fl ‘: (AU)o.m(In)o.zz G”=0.78°G”c+0.~20G’
Au
“’ ,n -9762.0-2.38031

0
Y or Y ‘: (Auh7(Inh G’=0.7 G,,fit +0.3 0 G,ir” -12813.1-2.0538T

Au&: (AU)o.7Oh~ G %‘”~0.75 OG/Cc1-0.25 OG,,,r

,,, -11054.5-2.166-I
Ru

OG/”
AuIn : (Au)o.d~h GAuln =0,5

Au
+0,5 OGi,!
,,, -19639+1.84781

Auh : (.+0.3333(1@0.6667 G 4uh’=0.3333’

2 G~+0.6667”G;:‘” -26730.8tl2.0162T

id, _~” G;ne”

Tetragonal: (In) G

*: The lattice stabilities ofAu and In in Q 1status were expressed as:

G’;; = 125 + 0.79T+‘Gc Gz = 520 - 0.384T+%r

 THERMODYNAMIC REASSESSMENT OF Au-In BINARY SYSTEM 35

1200

1000

0P
; 800
5
sLs 600

2
g 400

200

0
0 0.2 0.4 0.6 0.8 1.o
Au MOLE-FRACTION IN In

Fig. 1 The calculated phase diagram of Au-In binary system by Ansara and Nabot 111

: i :. :c i.: ,: ,: .,, I
AU MOLE-FRACTION IN In

Fig.2 Phase diagram of the Au-In binary system reviewed by Okamoto and Massalski [2].
36 H. S. LIU et al.

600

400
1
I
200

I
0-l0 0.2 0.4 0.6 0.8
-!
1.0
AU MOLE-FRACTION IN In

Fig.3 The calculated phase diagram of Au-In binary system in the present assessment

AU MOLE-FRACTION IN In

Fig.4 Comparison of the calculated phase phase with experimental boundaries.

THERMODYNAMIC REASSESSMENT OF Au-in BINARY SYSTEM 37

0 I-

-2
2
2 -4
% -6
13
5 -8

!z -10
5
~ -12

2 -14

g -16
G
-18
cIl,,[Il
-20 I I I I
0 0.2 0.4 0.6 0.8 1.b
Au
MOLE-FRACTION I?d In
Fig.5 Calculated enthalpies of mixing of liquid in comparison with experimental data.

g 0.7 -

?: 0.6 -
5
i: 0.5 -

2 0.4 -

0.3 -

0.2 -

0.1 -

0 0.2 0.4 0.6 0.8 1.0

Au MOLE-FRACTION IN In

Fig.6 Calculated and experimental activity of In in liquid (Ref.state: liquid In).