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Thermodynamic description of the Cu-Sn system

Article · November 2007

DOI: 10.1557/jmr.2007.0396

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 Thermodynamic description of the Cu–Sn system
Wojcieh Gierlotka
Department of Chemical Engineering, National Tsing Hua University, Hsin-Chu 300, Taiwan; and
Non-Ferrous Metals Department, Akademia Górniczo-Hutnicza (AGH) University of Science and
Technology, Mickiewicza 30, 30-059 Krakow, Poland
Sinn-wen Chena) and Shih-kang Lin
Department of Chemical Engineering, National Tsing Hua University, Hsin-Chu 300, Taiwan

(Received 2 January 2007; accepted 25 July 2007)

The Cu–Sn binary system is important for various applications, especially for recent
developments in the electronics packaging industry. The ⑀-Cu3Sn and ␩-Cu6Sn5
(␩⬘ phases) phases are frequently encountered in electronics products. However, the
two phases have been described as line compounds in previous thermodynamic
modeling, and their compositional homogeneities were not considered. In this study,
the thermodynamic properties of the Cu–Sn binary system are modeled and the phase
diagram is calculated by the CALPHAD method, using experimental information
reported in the literature. The ⑀ and ␩ (␩⬘) phases are described using compound
energy models with two and three sublattices, respectively, so that their compositional
homogeneities could be calculated. Good agreement was observed between the
calculated result and the existing experimental data.

I. INTRODUCTION descriptions of the Cu–Sn-based multicomponent sys-

The binary Cu–Sn system is the basis for various
emerging Pb-free solders and for most of the important
solder-related materials systems.1–3 With the increasing
demand for Pb-free solders and more advanced applica-
tions of soldering technology in electronic products, the
Cu–Sn system has become one of the most important
material systems.4–6 There are seven intermetallic phases
in the Cu–Sn system. Of these, the ⑀-Cu 3 Sn and
␩-Cu6Sn5 (␩⬘-Cu6Sn5) phases are on the more Sn-rich
side and are most frequently encountered in the soldering
studies. These two compounds are also observed in other
solder-related systems, such as Sn–Ag–Cu, Sn–Cu–Ni,
and Sn–Ag–Cu–Ni systems.1–10 The compositional ho-
mogeneity ranges of these two intermetallic compounds
are significant in some of the Cu–Sn-based higher-order
systems.7–10
Phase diagrams of multicomponent systems are valu-
able for a basic understanding of materials processing
and materials properties. However, thorough experi-
mental determinations of the phase diagrams of multi-
component systems are very time-consuming; it is much
more feasible to determine the phase diagrams with the
CALPHAD approach.11,12 To have good thermodynamic
a)
Address all correspondence to this author.
e-mail: swchen@che.nthu.edu.tw
DOI: 10.1557/JMR.2007.0396
tems, a sound description of the Cu–Sn binary system is
necessary. The binary Sn–Cu system has been assessed
by various investigators.13,14 However, in the previous
literature,13,14 the ⑀-Cu3Sn and ␩-Cu6Sn5 phases are de-
scribed using the line compound models without compo-
sitional homogeneity. In contrast, the current study ther-
modynamically models the Cu–Sn system using the
CALPHAD approach. For accurate descriptions of the
binary system and the higher-order systems, the interme-
tallic compounds are described as phases with solubili-
ties using compound energy models.
II. THERMODYNAMIC DESCRIPTION OF
THE PHASES
The following phases are considered in this work:
FCC_A1, BCT_A5, BCC_A2, liquid, ␥, ␨, ␦, ⑀, ␩, ␩⬘.
Detailed information about these phases is given in Table
I and below.
A. Substitutional solution—FCC_A1, BCC_A2,
BCT_A5, liquid
The Gibbs free energies of pure elements with respect
to temperature oGi(T) ⳱ Gi(T) − HSER
i are represented by
Eq. (1):
o
Gi共T兲 = a + bT + cT ln共T兲 + dT2 + eT −1 + fT 3 + iT 4
+ jT7 + kT −9 . (1)

3158 J. Mater. Res., Vol. 22, No. 11, Nov 2007 © 2007 Materials Research Society
 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system

TABLE I. Phase of the Cu–Sn system. The oGi(T) functions are taken from Dinsdale16 and from
Phases Models Structure/space group SGTE Unary (Pure elements) TDB v.4.17 The thermo-
dynamic functions of pure elements are listed in Table II.
Liquid Substitional, RKP
The main differences between the functions by Dinsdale
FCC_A1 Substitional, RKP A1 Fm3̄m
BCT_A5 Substitional, RKP A5 I41/amd and SGTE Unary TDB v.4 are the descriptions of tin in
BCC_A2 Substitional, RKP A2 Im3̄m the FCC structure. It was decided to use the newest in-
␥ Two sublattice model D03 Fm3̄m formation taken from the SGTE database. Solid- and liq-
␨ Stoichiometric compound P63 uid-solution phases (FCC_A1, BCC_A2, BCT_A5, Liq-
␦ Stoichiometric compound F43m
uid) are described by the regular solution model11:
⑀ Two-sublattice model Cmcm
␩
␩⬘
Three-sublattice model
Three-sublattice model
B81 P63/mmc
⭈⭈⭈
Gm共T兲 = 冱x G 共T兲 + RT 冱x ln共x 兲
i
o
i i i

冉 冊
i i

RKP, Redlich–Kister polynomial for binary substitutional solutions. + 冱 冱x x 冱 L 共x − x 兲 i j

␯
ij i j
␯
, (2)
i j⬎i ␯

The oGi(T) data are referred to the constant enthalpy

where the
value of the standard element reference HSER at 298.15 K
冱 冱x x 冉 冱 L 共x − x 兲 冊
i
and 1 bar as recommended by Scientific Group Thermo- ␯ ␯
data Europe (SGTE).15,16 The reference states are: i j⬎i
i j
␯
ij i j

FCC_A1 (Cu), BCT_A5 (Sn). The oGi(T) expression

may be given for several temperature ranges, where the part is the Redlich–Kister polynomial for excess Gibbs
coefficients a, b, c, d, e, f, i, j, and k have different values. free energy.

TABLE II. Gibbs free energies of pure elements.16,17

Function Temperature range Expression

GHSERCU 298.15 < T < 1357.77 −7770.458 + 130.485235*T − 24.112392*T* ln(T) − 0.00265684*T**2 + 1.29223E-07*T**3
+ 52,478*T**(−1)
1357.77 < T < 3200.00 −13,542.026 + 183.803828*T − 31.38*T* ln (T) + 3.64167E + 29*T**(−9)
GHSERSN 100.00 < T < 250.00 −7958.517 + 122.765451*T − 25.858*T* ln (T) + 5.1185E-04*T**2 − 3.192767E-06*T**3 +
18440*T**(−1)
250.00 < T < 505.08 −5855.135 + 65.443315*T − 15.961*T* ln (T) − 0.0188702*T**2 + 3.121167E-06*T**3 −
61,960*T**(−1)
505.08 < T < 800.00 +2524.724 + 4.005269*T − 8.2590486*T* ln (T) − 0.016814429*T**2 + 2.623131E-06*T**3
− 1,081,244*T**(−1) − 1.2307E + 25*T**(−9)
800.00 < T < 3000.00 −8256.959 + 138.99688*T − 28.4512*T* ln (T) − 1.2307E + 25*T**(−9)
GCUBCC 298.15 < T < 1357.77 −3753.458 + 129.230235*T − 24.112392*T* ln (T) − 0.00265684*T**2 + 1.29223E
−07*T**3 + 52,478*T**(−1)
1357.77 < T < 3200.00 −9525.026 + 182.548828*T − 31.38*T* ln (T) + 3.64167E + 29*T**(−9)
GSNBCC 100.00 < T < 250.00 −3558.517 + 116.765451*T − 25.858*T* ln (T) + 5.1185E − 04*T**2 − 3.192767E −
06*T**3 + 18440*T**(−1)
250.00 < T < 505.08 −1455.135 + 59.443315*T − 15.961*T* ln (T) − 0.0188702*T**2 + 3.121167E − 06*T**3 −
61960*T**(−1)
505.08 < T < 800.00 +6924.724 − 1.994731*T − 8.2590486*T* ln (T) − 0.016814429*T**2 + 2.623131E −
06*T**3 − 1,081,244*T**(−1) − 1.2307E + 25*T**(−9)
800.00 < T < 3000.00 −3856.969 + 132.99688*T − 28.4512*T* ln (T) − 1.2307E + 25*T**(−9)
GSNFCC 298.15 < T < 505.08 −345.135 + 56.983315*T − 15.961*T* ln (T) − 0.0188702*T**2 + 3.121167E − 06*T**3 −
61,960*T**(−1)
505.08 < T < 800.00 +8034.724 − 4.454731*T − 8.2590486*T* ln (T) − 0.016814429*T**2 + 2.623131E −
06*T**3 − 1,081,244*T**(−1) − 1.2307E + 25*T**(−9)
800.00 < T < 3000.00 −2746.959 + 130.53688*T − 28.4512*T* ln (T) − 1.2307E + 25*T**(−9)
GCULIQ 298.15 < T < 1357.77 +5194.277 + 120.973331*T − 24.112392*T* ln (T) − 0.00265684*T**2 + 1.29223E −
07*T**3 + 52,478*T**(−1) − 5.8489E − 21*T**7
1357.77 < T < 3200.00 −46.545 + 173.881484*T − 31.38*T* ln (T)
GSNLIQ 100.00 < T < 250.00 −855.425 + 108.677684*T − 25.858*T* ln (T) + 5.1185E − 04*T**2 − 3.192767E − 06*T**3
+ 18,440*T**(−1) + 1.47031E − 18*T**7
250.00 < T < 505.08 +1247.957 + 51.355548*T − 15.961*T* ln (T) − 0.0188702*T**2 + 3.121167E − 06*T**3 −
61960*T**(−1) + 1.47031E − 18*T**7
505.08 < T < 800.00 +9496.31 − 9.809114*T − 8.2590486*T* ln (T) − 0.016814429*T**2 + 2.623131E − 06*T**3
− 1,081,244*T**(−1)
800.00 < T < 3000.00 −1285.372 + 125.182498*T − 28.4512*T* ln (T)

J. Mater. Res., Vol. 22, No. 11, Nov 2007 3159

 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system

B. Stoichiometric compounds ␦ and ␨ E. ␩ and ␩ⴕ phases

Binary stoichiometric compounds ␦-Cu41Sn11 and The ␩⬘ phase is hexagonal and has a superstructure
␦-Cu10Sn3 are described as the line compound using the based on a NiAs-type structure. The ␩⬘ transforms to the
following: ␩ phase, which has the NiAs structure between 459 and
502 K.16,19 Similar to the ⑀ phase as mentioned previ-
Gm共T兲 = a + bT + 冱x GHSER
i
i i . (3) ously, although the compositional homogeneities of the
␩ and ␩⬘ phases are small in the binary Cu–Sn binary
system, thermodynamic models describing their com-
C. ␥ phase positional homogeneities are important since their
The ␥ (D03) phase is formed by an ordering process of compositional homogeneities might be significant in
the BCC_A2 phase. A description of the Gibbs free en- the Cu–Sn-based higher-order systems. Both phases
ergy of this phase was proposed by Shim13 as a two were modeled using a three-sublattice model
sublattice model, (Cu,Sn)0.75(Sn,Cu)0.25, and is repre- (Cu)0.3333(Cu,Sn)0.3334(Sn)0.3333. This kind of model was
sented by Eq. (4): used by Liu et al.20 for modeling the Ni3Sn2 high-
temperature phase. Ghosh21 used a different sublattice
G␥m共T兲 = YCu
I II o ␥
YCu GCu:Cu + YCuI II o ␥
YSn GCu:Sn model for the description of the same Ni3Sn2 phase. In
II o ␥ II o ␥ his work, ␩-Ni3Sn2 phase was described by using a three-
+ YSnYCu GSn:Cu + YSnYSn GSn:Sn
I I
sublattice model (Ni)1:(Sn)1:(Ni,Va). Take into account
+ 0.75RT共YCu I I
ln YCu + YSnI I
ln YSn 兲 the existence of the ␩ phase in a larger composition range
+ 0.25RT共YSn ln YSn + YCu ln YCu兲 +
II II II II xs
G␥m , and the more recent literature information, the model
(4) proposed by Liu et al.20 is adopted. The Gibbs free en-
ergies of both phases are given by the following equa-
where xs
G␥m represents excess Gibbs free energy: tions:
xs
G␥m = YCu
I I
YSn II ␥
YCu LCu,Sn:Cu + YCu
I I
YSn II ␥
YSn LCu,Sn:Sn G ␩m共T兲 = YCu
I II IIIo ␩
YCu YSn GCu:Cu:Sn + YCu
I II IIIo ␩
YSn YSn GCu:Sn
II II ␥ II II ␥
+ YCu
I
YSn YCuLCu:Sn,Cu + YSnI
YSn YCuLSn:Sn,Cu + 0.3334RT共YCuII II
ln YCu + YSn
II II
ln YSn 兲
II II ␥ xs ␩
+ YCu
I I
YSn YSn YCuLCu,Sn:Sn,Cu , (5) + Gm , (7)

in which YN i denotes the site fraction of element i on

xs
G ␩m = YCu
I II II III ␩
YCu YSnYSnLCu:Cu,Sn:Sn . (8)
sublattice N, a colon (:) indicates separation of elements
on the different sublattices, and a comma (,) indicates III. EXPERIMENTAL INFORMATION
separation of elements on the same sublattice.
A. Phase diagram data
D. ⑀ phase A phase diagram of Cu–Sn system was recently sug-
gested by Saunders and Miodownik18 and assessed by
The ⑀ phase in the Cu–Sn binary system is character- Shim et al.13 and Liu et al.14 Various investigations on
ized by a low solubility limit; however, experimental re- phase equilibria were conducted22–30 by using x-ray
sults show that this limit is not neglected.18 More impor- analysis, micrographic analysis, thermal analysis, etc.
tantly, the ⑀ phase is frequently encountered in the Cu– Most of the earlier works are summarized by Hansen and
Sn-based systems, such as in the Sn–Ag–Cu, Sn–Cu–Ni, Anderko,31 while a more recent work on the ␩⬘ phase is
and Sn–Ag–Cu–Ni systems,4–10 and its compositional by Larsson et al.32 Most of the experimental results are in
homogeneities are usually significant in these systems. good agreement, although inconsistencies were found in
Two sublattices could be assumed for the phase, with Cu the boundaries of the ␥ phase.
atoms occupying the first sublattice and second sublattice
is occupied by Sn atoms. To model the stoichiometric B. Thermochemical data
range, it is assumed that Sn atoms occupy Cu sites and
The enthalpies of mixing of liquid Cu–Sn alloys were
Cu atoms occupy Sn sites as antisite defects. The
obtained using calorimetry by Kleppa,33 Hultgren et
⑀-Cu3Sn phase is thus described by two-sublattice com-
al.,34 Takeuchi et al.,35 Yazawa and Itagaki,36 Iguchi et
pound energy formalism [Eq. (6)]:
al.,37 Pool et al.,38 and Lee et al.39 Kleppa33 determined
the enthalpy of solutions of Cu in liquid alloys at 723 K.
G⑀m共T兲 = YCu
I II o ⑀
YCu GCu:Cu + YCuI II o ⑀
YSn GCu:Sn
II o ⑀ II o ⑀ Hultgren et al.34 measured the enthalpy of mixing at
+ YSnYCu GSn:Cu + YSnYSn GSn:Sn
I I
1400 K and analyzed earlier works. Takeuchi et al.,35
+ 0.75RT共YCu I I
ln YCu + YSnI I
ln YSn 兲 Yazawa and Itagaki,35 and Iguchi et al.37 made calori-
+ 0.25RT共YSn ln YSn + YCu ln YCu兲 +
II II II II xs
G⑀m . metric investigation at 1363, 1373, and 1393 K, respec-
(6) tively. Pool et al.’s work described the application of the

3160 J. Mater. Res., Vol. 22, No. 11, Nov 2007

 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system

SETARAM high-temperature calorimeter to determine
the mixing enthalpies of liquid alloys, with the Cu–Sn
alloy was one of the examined systems.38 Lee et al.39
determined the enthalpy of mixing of liquid Cu–Sn sys-
tem at 997 K. Additionally, he suggested the existence of
associate Cu3Sn in melt, although this was not confirmed
by other authors. Kleppa33 also measured enthalpy of
formation of solid alloys for the compositions between
0.074 and 0.255 mol fraction of Sn at 723 K.
The activities of Cu and Sn were measured by Alcock
et al.,40 Hager et al.,41 Ono et al.,42 Oshi et al.,43 and
Sengupta et al.44 Of these studies, Alcock et al.,40 Hager
et al.,41 and Ono et al.42 used a Knudsen cell technique
and measured the activities at 1300, 1593, and 1573 K,
respectively. Electromotive force (EMF) measurements
with the electrochemical cell technique were used by
Oshi et al.43 between 1173 and 1373 K and Sengupta et
al.44 at 1073 K. All authors obtained activities of Cu and
Sn with negative deviation from Raoult’s Law. Alcock
and Jacob45 used a gas–solid equilibration technique to
measure the chemical potential of Sn in the terminal solid
solution of Cu-side at 1000 K. Sommer et al.46 and
Predel and Schallner47 used an EMF technique to meas-
ure the same variable at 1000 K.
C. Invariant reactions
The Cu–Sn phase diagram reported by Saunders and
Miodownik18 has three peritectics, two peritectoids, four
eutectoids, one metatectic, one congruent transformation,
and one eutectic reaction. All data concerning invariant
reactions used for the assessment procedure are listed in
Table III.
IV. MODELING PROCEDURE
The thermodynamic parameters for all phases in the
system were optimized using ThermoCalc software.48
TABLE III. Invariant reaction data and the calculated results.
For this optimization, thermodynamic data for the liquid
phase, invariant reactions, and liquidus/solidus were
used. Each piece of the selected information was given a
certain weight based on personal judgment. The optimi-
zation was carried out step by step. First, the optimiza-
tion of the liquid phase was performed, and then the solid
phases were assessed. All parameters were finally evalu-
ated together to provide the best description of the sys-
tem. The calculated interaction parameters are shown in
Table III.
V. RESULTS
Figure 1(a) shows the calculated Cu–Sn phase dia-
gram. Compared with the experimental data,22,25,28–30 as
shown in Fig. 1(b), the calculated diagram is in good
agreement with the experimentally determined phases
boundaries. In addition, the invariant reaction tempera-
tures calculated in this study are in good agreement with
the experimental data listed in Table III. As mentioned
previously, the ⑀-Cu3Sn and ␩/␩⬘-Cu6Sn5 phases are
relatively stable and are usually formed at Cu/Sn alloy
interfaces.1–10 However, in the previous optimizations of
the Cu–Sn system11–13,18 the important intermetallic
compounds, ⑀-Cu3Sn and ␩/␩⬘-Cu6Sn5, were treated as
line compounds. This brought certain difficulties in the
assessment of the corresponding higher-order systems
since those phases exhibit considerable ternary solubili-
ties in many systems.4–10 The Cu–Sn system was suc-
cessfully optimized with suitable homogeneous ranges in
the ⑀-Cu3Sn and ␩/␩⬘-Cu6Sn5 phases.
The liquidus line of Cu–Sn system was fitted well with
the previous optimization of liquid phase by Shim et al.13
and Liu et al.14 However, both proposed models have
independent on temperature enthalpy of mixing, and they
do not match the thermodynamic properties experimental
measured at different temperatures.33–44 Therefore, the

Experimental results Calculated results

Composition (at.%) Composition (at.%)
Reaction Type T(K) Cu Sn T(K) Cu Sn
FCC_Al + L ↔ BCC_A2 Peritectic 1071 87.6 12.4 1070.65 87.0 13.0
BCC_A2 + L ↔ ␥ Peritectic 1028 83.3 16.7 1024.46 82.6 17.4
⑀↔␥ Congruent melting 949 75.0 25.0 949.45 75.3 24.7
␥+⑀↔␨ Peritectoid 913 77.5 22.5 911.50 76.9 23.1
␥+⑀↔L Metatectic 913 57.5 42.5 914.08 57 43.0
␥+␨↔␦ Peritectoid 863 79.7 20.3 866.32 78.9 21.1
BCC_A2 ↔ FCC_A1 + ␥ Eutectoid 859 85.6 14.4 858.82 85.6 14.4
␨↔␦+⑀ Eutectoid 855 78.3 21.7 854.94 77.5 22.5
␥ ↔ FCC_A1 + ␦ Eutectoid 793 83.2 16.8 786.43 84.0 16.0
⑀+L↔␩ Peritectic 688 54.5 45.5 688.60 56.7 43.3
␦ ↔ FCC_A1 + ⑀ Eutectoid 623 79.6 20.4 623.90 78.9 21.1
L ↔ ␩ + BCT_A5 Eutectic 500 1.6 98.4 497.98 1.7 98.3
␩ ↔ ␩⬘ Simple/Long-range order 459–462 55.5–54.9 44.5–45.1 461.05–461.08 55.4–54.2 44.6–45.8

Source: Ref. 14.

J. Mater. Res., Vol. 22, No. 11, Nov 2007 3161

 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system

TABLE IV. Interaction parameters obtained during optimization

procedure.

Phase Parameter

Liquid LCu,Sn ⳱ −15,583.768 + 40.6239T −

0 liquid
5.6172T ln(T)
LCu,Sn ⳱ −27,739.285 + 41.9270T −
1 liquid
4.4641T ln (T)
LCu,Sn ⳱ −13,228.943 + 0.906T
2 liquid

FCC_A1 LCu,Sn ⳱ −10,309.845 + 1.158T

0 FCC_Al

LCu,Sn ⳱ −16,190.032 + 6.495T

1 FCC_A1

BCC_A2 LCu,Sn ⳱ −41,774.195 + 47.877T

0 BCC_A2

LCu,Sn ⳱ −12,316.502 − 50.445T

1 BCC_A2

BCT_A5 0 BCT_A5
GSn ⳱ GHSERSN
0 BCT_A5
GCu ⳱0
LCu,Sn ⳱ 0
0 BCT_A5

␨ ⌬G␨m ⳱ −7080.194 − 0.955T

␦ ⌬G␦m ⳱ −6498.086 − 1.064T
0 ␥
␥ GCu:Cu ⳱ GCUBCC
0 ␥
GSn:Sn ⳱ GSNBCC
0 ␥
GCu:Sn ⳱ −5912.468 − 2.439T + .75 GHSERCU + .25
GHSERSN
0 ␥
GSn:Cu ⳱ 126,652.750 − 2.987T + .25 GHSERCU + .75
GHSERSN
0 ␥
LCu:Cu,Sn ⳱ −2672.875 − 1.792T
1 ␥
LCu:Cu,Sn ⳱ 57.375 − 3.767T
0 ␥
LCu,Sn:Sn ⳱ 46,820.857 − 42.261T
0 ⑀
⑀ GCu:Cu ⳱ 5534.454 − 0.241T + GHSERCU
0 ⑀
GSn:Sn ⳱ 14,564.708 + 0.100T + GHSERSN
0 ⑀
GCu:Sn ⳱ −8406.738 + 0.100T + .75 GHSERCU + .25
GHSERSN
0 ⑀
GSn:Cu ⳱ 15,470.377 + 7.731T + .25 GHSERCU + .75
GHSERSN
0 ⑀
L*:Cu,Sn ⳱ 217.494 − 1.831T
0 ⑀
LCu,Sn:* ⳱ 0.095 + 0.1T
0 ␩
␩ GCu:Cu:Sn ⳱ −5570.949 − 1.1108T + .6667 GHSERCU +
.3333 GHSERSN
0 ␩
GCu:Sn:Sn ⳱ 930.597 − .4804T + .3333 GHSERCU +
.6667 GHSERSN
0 ␩
LCu:Cu,Sn:Sn ⳱ −7841.425 − .7127T
0 ␩_prime
␩_prime GCu:Cu:Sn ⳱ −4297.175 − 3.9531T + .6667 GHSERCU + FIG. 1. (a) Calculated phase diagram of the Cu–Sn system. (b) Cal-
.3333 GHSERSN culated phase diagram of the Cu–Sn system and the superimposed
0 ␩_prime
GCu:Sn:Sn ⳱ 5334.887 − 10.2934T + .3333 GHSERCU + experimental data.
.6667 GHSERSN
0 ␩_prime
LCu:Cu,Sn:Sn ⳱ −21100.152 + 28.6728T

temperature dependence of enthalpies in liquid phase

was considered in the current study. Figure 2 shows the
calculated and experimental determined enthalpies of
mixing in the liquid phase of the Cu–Sn system. The
experimental values obtained by Yazawa and Itagaki at
1373 K36 and Lee et al. at 997 K39 exhibit slight tem-
perature dependency and are well fitted by the proposed
model. Figures 3 and 4 show the liquid phase activities of
Sn and Cu, respectively. The experimental values ob-
tained from Ono et al. at 1573 K42 and Sengupta et al. at
1073 K44 show very little dependency on temperature
and are again well simulated by the calculation results.
Precise descriptions of the temperature dependency of
thermodynamic properties are of essential importance, FIG. 2. Calculated enthalpies of mixing of the Cu–Sn system at 997
since this precision not only improves the accuracy of and 1373 K and the superimposed experimental results. Both compo-
optimization for thermodynamic properties, but it is also nents referred to liquid.

3162 J. Mater. Res., Vol. 22, No. 11, Nov 2007

 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system
FIG. 3. Calculated activities of Sn at 1073 and 1573 K and the su-
perimposed experimental results. Both components referred to liquid.
FIG. 4. Calculated activities of Cu at 1073 and 1573 K. Both com-
ponents referred to liquid.
beneficial to have good descriptions of mixing enthalpies
in higher order systems.
The activities of Sn in solid state at 1000 K were
experimentally determined by Alcock and Jacob45 and
Sommer et al.46 As shown in Fig. 5, the activities calcu-
lated in this study, using the liquid phase and FCC_A1
structure as the reference states for Sn and Cu, are in
good agreement with the experimental values. Compared
with the calculations based on previous optimization
done by Shim et al.,13 the present calculation is better
fitted with the results of Alcock and Jacob,45 while the
former shows lower values toward both experimental re-
sults.45,46 The thermodynamic description of the Cu
phase was also assessed by Liu et al.14 following the
J. Mater. Res., Vol. 22, No. 11, Nov 2007
FIG. 5. Calculated activity of Sn in solid state at 1000 K where Sn
referred to liquid and Cu referred FCC_A1 structure and the superim-
posed experimental data.
FIG. 6. Calculated enthalpies of formation at 723 and 237 K where Sn
referred to BCT_A5 and Cu referred FCC_A1 structure and the su-
perimposed experimental data.
work of Shim et al.13 Liu et al.’s results shows similar
good simulation of activity of Sn in solid state as in the
present optimization. However, more parameters were
used in Liu et al.’s optimization.14 It is better to use as
few numbers of parameters as possible to fit every ex-
perimental result. The modification of thermodynamic
modeling in Cu phase in this study improved the simu-
lation of activity of Sn in solid state by limited param-
eters as shown in Fig. 5. In addition, this study adopts the
␤/␥ first-order transformation as suggested by most pre-
vious research groups,13,15,18 but not the A2–B2–D03
3163
 W. Gierlotka et al.: Thermodynamic description of the Cu–Sn system
two-stage ordering reaction by Liu et al.14 The ␤/␥ first-
order transformation mechanism agrees better with ex-
perimental data,49 and the proposed description is rela-
tively easier for extension to higher-order systems as
well. Figure 6 shows both the calculated and measured
formation enthalpies of various phases at 723 and 237 K.
The experimental data was obtained from Kleppa33 and
Gangulee et al.19 The calculation results are in good
agreement with the experimental data. The enthalpies of
formation were also calculated and well fitted by former
optimization at 723 K.13 However, the present calcula-
tion demonstrates very good simulation for both 723 and
273 K as shown in Fig. 6.
VI. CONCLUSIONS
Phase equilibria of the Cu–Sn binary system have been
modeled on the basis of experimental data taken from
literature. The Cu–Sn phase diagram was calculated with
suitable homogeneous ranges in the ⑀-Cu3Sn and ␩/␩⬘-
Cu6Sn5 phases. Thermodynamic descriptions of every
phase in the Cu–Sn system were reoptimized, and the
calculated properties are in good agreement with the ex-
perimental determined results. Especially for the liquid
phase, the temperature dependency was considered,
which improves the flexibility for assessments on higher-
order systems. The modifications result in very good
matching between calculated and experimental measured
thermodynamic values in both liquid and solid states.
ACKNOWLEDGMENT
The authors gracefully acknowledge financial support
from the National Science Council of Taiwan (NSC95-
2221-E-007-205).
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