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Contents lists available at ScienceDirect

CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Thermodynamic reassessment of Au–Ni–Sn ternary system

H.Q. Dong n, V. Vuorinen, T. Laurila, M. Paulasto-Kröckel
Department of Electronics, Aalto University School of Electrical Engineering, FIN-02601 Espoo, Finland

art ic l e i nf o a b s t r a c t

Article history: For having a better understanding on the formation and evolution of metal bonding interconnection
Received 6 June 2013 microstructures the Au–Ni–Sn ternary system was reassessed on the basis of experimental results and
Received in revised form the recently reported thermodynamical description for Au–Sn and Ni–Sn systems. In this paper, the
30 September 2013
thermodynamic parameters of Ni3Sn4 phase were modified in order to achieve a better agreement with
Accepted 6 October 2013
Available online 22 October 2013
experimentally determined phase boundaries. Further, a self-consistent set of thermodynamic para-
meters for the Au–Ni–Sn system were obtained, which were able to reproduce most of the available
Keywords: experimental data. The Ni|80Au20Sn (wt%) diffusion couples were annealed at 320 1C for 10,000 s and at
Thermodynamic modeling 150 1C for 2500 h. The microstructures of these samples were studied with SEMþ EDS technique. The
Au–Ni–Sn
reaction interface between Ni and near eutectic AuSn alloy consisted of Ni3Sn/(Ni, Au)3Sn2/AuSn/Au5Sn
Diffusion couples
layers. This experimentally observed diffusion path of Ni against Au–20 wt% Sn solder at 150 1C was
Diffusion path
rationalized on the basis of the thermodynamically calculated isothermal section.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Metal bonding method is becoming more popular in micro-
electro-mechanical systems (MEMS) wafer level packaging. It is now
gradually taking over the traditional glass based MEMS bonding pro-
cesses due to several advantages over other bonding methods: not
only significantly reducing products costs, but also capable of provid-
ing electrical interconnection and higher levels of hermeticity [1].
With respect to various metal bonding techniques, the transient
liquid phase bonding (TLP) is considered very promising due to
several advantages: (1) the final bond has a potential of having
closely related mechanical, electrical and thermal properties
to those of the base materials, owing to the formation of the
interlayer (i.e., alloys containing the base materials as a solvent and
a solute); (2) the bonding process can be performed at a low
temperature, which enables the integration of temperature sensi-
tive devices, and has the capability of reducing the cost and
minimizing the stresses induced by a thermal mismatch between
the materials; and (3) it permits higher processing temperatures for
further assembly steps as well as higher operational temperatures in
the end-application due to the higher melting point of the formed
interlayer tin comparison to the bonding temperature [2–4]. The
Au–20 wt% Sn alloy is continually used in TLP bonding technique
owing to its relatively low bonding temperature, low elastic mod-
ulus, high thermal conductivity and high strength. Here the Sn
element acts as the solder material, and Au is the base metal [5].
The element, Ni, just as in other bonding technologies [6,7], still
plays the role of diffusion barrier in Sn-related bonding systems
using TLP bonding [5]. Thus, it is essential to understand the
microstructure of the Au–Sn/Ni bonding joint which governs its
mechanical properties.
However, the microstructure after the bonding joint is determ-
ined not only by its composition and thermal history, but also by
the reactions that occur at the solder/substrate interface [8]. A comp-
rehensive understanding on the formation and evolution of the
interconnection microstructure requires obtaining a consistent ther-
modynamic description of the various metal bonding systems, in order
to gain better understanding on the changes occurring during
fabrication, reliability testing and field usage [9,10].
Therefore, in this work, the phase equilibria of Au–Ni–Sn ternary
were recalculated on the basis of the newly updated thermodynamic
description of two binary systems. Besides, microstructure of the
diffusion couple, Au–20 wt% Sn/bulk Ni, at 150 1C was also investi-
gated via different annealing period.
The paper is organized as follows: the experimental method
will be introduced in Section 2. A brief review of previous work is
presented in Section 3. The applied methods and models that were
used will be described in Section 4. The results obtained and the
related discussions can be found in Section 5. Finally, conclusions
drawn from this simulation are summarized in Section 6.
2. Materials and methods

n
Corresponding author. Tel.: þ 358 409311239. The reaction couples were manufactured by placing a 100 mm
E-mail address: hongqun.dong@aalto.fi (H.Q. Dong). thick near eutectic Au80/Sn20 (wt%) [Au70.7/Sn29.3 (at%)] alloy

0364-5916/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.calphad.2013.10.001
62 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70

foil between etched (1 min in dilute HCl þmethanol solution)
0.5 mm thick Ni foils (99,99þ , Goodfellow Ltd.). The sandwich
structure was then soldered at 320 1C for from 100 s up to 10,000 s
at air furnace by utilizing Rosin Mildly Activated (RMA) flux. After
the soldering a few samples were annealed in a forced convection
oven (Heraeus Instruments UT6) for different periods of time up to
2500 h at 150 1C. The cross-sections of the samples were prepared
with the standard metallographic methods, and they were ana-
lyzed with a field emission scanning electron microscope (JEOL
6335 F FE-SEM) equipped with an energy dispersive spectrometer
(EDS, Oxford ISIS).
3. A brief review of previous work
3.1. The binary systems
The three binary systems have already been extensively inves-
tigated both experimentally and theoretically. The Au–Ni binary
system was studied by Wang et al. in 2005 utilizing the CALPHAD
approach [11]. In that work, the authors considered all the avai-
lable experimentally determined phase boundaries and thermo-
chemical values. By using that set of thermodynamic parameters,
most of those results can be reproduced. Thus, those parameters
were directly adopted at present assessment work. A variety of
thermodynamic description of Au–Sn binary system has been
published [12–15]. However, the description had to be redone
due to the new lattice stability data for Sn(hcp) reported recently
by SGTE (i.e., 3900  7.464  T þGSERSn ) instead of 3900  4.4 
T þGSER
Sn ) as well as newly measured enthalpies of formation of
several compounds [16]. Thus, it was modified in our recent work
[17], and those values were applied to this simulation. As for the
Ni–Sn binary system, the work from Zemanova et al. [18] was
directly adopted in this work except for that of Ni3Sn4. The
parameters of Ni3Sn4 phase was modified on the basis of the
model described in [18], in order to fit the reported homogeneity
ranges [19].
3.2. The Au–Ni–Sn ternary system
The first reported ternary information was an isothermal
section at 400 1C. It was examined by Neumann et al. [20] via
powder X-ray diffraction, metallography, electron-probe microa-
nalyzer (EPMA), and thermal analysis. They measured the struc-
ture of a ternary compound τ (i.e., Fe3S4-s-type, with a¼ 422.6
(1) and c¼2656.6(4) pm) and all the ternary solubility in binary
compounds at 400 1C. Especially, they found a continuous solid
solution from Ni3Sn2 to AuSn phase. Then, in 1998, Anhöck et al.
investigated the Au–Ni–Sn ternary system by using scanning
electron microscopy (SEM), and energy dispersive X-Ray spectro-
meter (EDX) [21]. They constructed the isothermal section of
solid solubility of Au in Ni3Sn4 was not found, and the maximum
solubility of Ni in AuSn was 11.9 at% which was achieved at high
temperature (at 400 1C). The above information implies that the
deduced room temperature tie-triangle could not represent the
true phase equilibria, and those proposed ternary solubility were
incorrect. Therefore, the results from [21] were not taken into
consideration. In the work of [22], the complete phase equilibria of
Au–Ni–Sn ternary system were experimentally determined and
thermodynamically calculated by means of differential scanning
calorimetry, X-ray diffraction, scanning electron microscopy,
EPMA, and CALPHAD approach [22]. In that work, they proved
that there was no such continuous solid solution from Ni3Sn2 to
AuSn phase, and AuSn dissolved a smaller amount of Ni (i.e., 5 at%
at 200 1C) than that reported in [21]. Besides, using their own
parameters, they could reproduce the experimental results. How-
ever, as discussed in Section 3.2, the thermodynamic description
for Au–Sn, and Ni–Sn systems were recently updated, which
require to reassess the ternary system. Therefore, at present work,
the thermodynamic descriptions of Au–Ni–Sn were reassessed
based on the new binary information as well as the combined
experimental information from [20,22].
4. Thermodynamic models
The lattice stability of the element i (i ¼Au, Ni and Sn)
is referred to as the constant enthalpy value of the standard
element reference H SER
i at 298.15 K and 1 bar as recommended
by Scientific Group Thermodata Europe (SGTE). Different models
were employed to describe the involved solution phases and
intermetallic compounds.
4.1. Solution phases
An ordinary substitutional solution model was applied to
describe the liquid, fcc, bcc, bct, hcp, and dhcp solutions. The
molar Gibbs energy of a solution phase ϕ (ϕ representing the afore
mentioned solution phases) can be represented as a sum of the
Gibbs energy for these pure components, the ideal entropy term
describing a random mixing of components, and the excess Gibbs
energy describing the deviation from ideal behavior, i.e.,
ϕ ϕ
Gϕ ¼ ∑ x0i Gi þ RT ∑ xi lnðxi Þ þ ex G ð1Þ
i ¼ Au;Ni;Sn i ¼ Au;Ni;Sn
where R is the gas constant, T is the temperature in K, xi is the molar
ϕ
fraction of component i (i¼Au, Ni and Sn), and 0 G i is the molar
Gibbs energy of pure element i, with the reference state of ϕ. Here
the excess term is formulated as
ðjÞ ϕ
N
ex ϕ
G ¼ xAu xNi ∑ L Au;Ni ðxAu  xNi Þj
j ¼ 0;1:::

Au–Ni–Sn system at the Sn–Au and Sn–Ni3Sn2 corner at room N

ðjÞ ϕ
temperature, which included the tie-triangles and the room þ xAu xSn ∑ L Au;Sn ðxAu  xSn Þj
j ¼ 0;1:::
temperature ternary solubility in the AuSn4, AuSn2, AuSn, Hcp,
ðjÞ ϕ
N
Au(Fcc), Ni3Sn4, and Ni3Sn2. However, the samples used in their þ xNi xSn ∑ L Ni;Sn ðxNi  xSn Þj
investigation were either untreated or annealed at high tempera- j ¼ 0;1:::

ture (i.e., 170 1C for 300 h). No equilibrium sample at room ϕ ϕ

þ xAu xNi xSn LAu;Ni;Sn þ mag G ð2Þ
temperature was prepared. Therefore, such isothermal section at
room temperature could not represent the equilibrium phase ϕ ϕ ϕ
where the values of ðjÞ L Au;Ni , ðjÞ L Au;Sn and ðjÞ L Ni;Sn are cited from
relation. Besides, some of their results are conflict with the others:
previous works (i.e., [11,17,18]), respectively, except for these of
(1) the AuSn4 phase should not be observed at room temperature
ðjÞ dhcp dhcp
which is unstable lower than 50 1C [17]; (2) the Au5Sn and Au10Sn and ðjÞ L Ni;Sn . In following text, dhcp was replaced by Au10Sn.
L Au;Ni ,
binary phases were missing in the proposed isothermal section, as The temperature dependent equation can be used to describe these
well as the ternary compound (τ); and (3) the extremely high interaction parameters
ternary solubility in Ni3Sn4 ( 20 at% Au) and AuSn (  20 at% Ni)
ðjÞ ϕ
were not testified in later investigation [22]. According to [22], the L ¼ a þ bT þ cT ln T þ dT 2 þeT 3 þ f T  1 ð3Þ
 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70 63

Parameters a and b were directly cited from former work [11,17,18]. þ 0:25nRTðY IINi LnY IINi þ Y IISn LnY IISn Þ
 
Only the ternary interaction parameter Lhcp
Au;Ni;Sn was optimized in ðNiÞ0:25 :ðNi;SnÞ0:25 :ðSnÞ0:5
þ Y IINi Y IISn Σ j j L Ni:ðNi;SnÞ:Sn ðY Ni  Y Sn Þj
ϕ
this work. The rest of them (LAu;Ni;Sn ) will not be optimized and were ð8Þ
set to be zero due to the lack of reliable experimental information.
here
ðNiÞ :ðNi;SnÞ0:25 :ðSnÞ0:5
GNi:Ni:Sn
0:25
¼ 0:5n0 G Fcc 0 Bct
Ni þ 0:5n G Sn þ E 3 þ F 3 nT ð9Þ
4.2. Intermetallic compounds
ðNiÞ :ðNi;SnÞ0:25 :ðSnÞ0:5
Out of the binary compounds, only the parameters of Ni3Sn4 GNi:Sn:Sn
0:25
¼ 0:25n0 G Fcc 0 Bct
Ni þ 0:75n G Sn þ E 4 þ F 4 nT ð10Þ
were modified in this work. This was done on the basis of the
j ðNiÞ0:25 :ðNi;SnÞ0:25 :ðSnÞ0:5
thermodynamic model in [18]. Extending to ternary system, the L Ni:ðNi;SnÞ:Sn ¼ E5 þF 5 nT ð11Þ
ternary solubility of 5 binary compounds was investigated, as well
where the values of En and Fn (n ¼1,2..,5) were assessed at
as a ternary compound was modeled [20,22]. In all the 5 binary
present work.
compounds, two of them are line compound, the rest have
The Ni3Sn2 compound, having a large solubility of Au, was
solution ranges. Thus, the two line compounds in binary system,
described by a three sublattice sites, i.e., (Au, Ni, Va)1:(Ni, Va)1:
i.e., Au5Sn and AuSn4, can be modeled as (Au, Ni)m:(Sn)n, and
(Ni, Sn)1. The Gibbs energy was formulated as
the followed equations can be adopted to describe their Gibbs
energy: GðAu;Ni;VaÞ1 :ðNi:V aÞ1 :ðNi;SnÞ1 ¼ ∑ ∑ ∑ Y Ii Y IIk Y III
l Gi:k:l
i k l
ðAu;NiÞ :ðSnÞ
GðAu;NiÞm :ðSnÞn ¼ Y IAu GðAu;NiÞ I
Au:Sn þ Y Ni GNi:Sn
m n
þ RTðY IAu LnY IAu þ Y INi LnY INi þ Y IV a LnY IVa Þ
m
þ RTðY IAu LnY IAu þY INi LnY INi Þ þ RTðY IINi LnY IINi þ Y IIVa LnY IIV a Þ
mþn
!
þ RTðY III III III III
Ni LnY Ni þ Y Sn LnY Sn Þ
þ Y IAu Y INi
ðAu;NiÞm :ðSnÞn
∑ j L ðAu;NiÞ:Sn ðY IAu  Y INi Þj ð4Þ !
ðAu;Ni;V aÞ :ðNi;VaÞ1 :ðNi;SnÞ1
j
þ Y IAu Y INi Y IIV a Y III
Sn ∑ j L ðAu;NiÞ:Va:Sn
1 I I
nðY Au Y Ni Þj
j ¼ 0;1
here
0 ðAu;Ni;V aÞ1 :ðNi;V aÞ1 :ðNi;SnÞ1
m 0 Fcc n 0 Bct þ Y IAu Y IINi Y IIV a Y III
Sn n L Au:ðNi;VaÞ:Sn
II II
nðY Ni  Y V a Þ0 ð12Þ
ðAu;NiÞm :ðSnÞn
GNi:Sn ¼ G þ G þ E1 þ F 1 nT ð5Þ
m þ n Ni m þn Sn where j refers to as Au, Ni and Va; k refers to as Ni and Va; and
ðAu;NiÞ :ðSnÞn
l refers to as Ni and Sn. As for the parameters relating to
LðAu;NiÞ:Sn
m
¼ E 2 þ F 2 nT ð6Þ 0 ðAu;Ni;V aÞ1 :ðNi;VaÞ1 :ðNi;SnÞ1 0 ðAu;Ni;VaÞ1 :ðNi;V aÞ1 :ðNi;SnÞ1
G Au:Ni:Sn ; G Au:V a:Sn ,
0 ðAu;Ni;VaÞ 1 :ðNi;V aÞ1 :ðNi;SnÞ1 1 ðAu;Ni;V aÞ1 :ðNi;VaÞ1 :ðNi;SnÞ1
L ðAu;NiÞ:Va:Sn ; L ðAu;NiÞ:V a:Sn ,
where Y IAu , and Y INi are the site fractions of Au and Sn in the first
0 ðAu;Ni;VaÞ1 :ðNi;V aÞ1 :ðNi;SnÞ1 ðAu;Ni;V aÞ1 :ðNi;VaÞ1 :ðNi;SnÞ1
ðAu;NiÞ :ðSnÞn
sublattice of (Au, Ni)m:(Sn)n; the value of GAu:Sn m are cited from L ðAu;NiÞ:Ni:Sn and 0 L Au:ðNi;V aÞ:Sn are optimized in
previous work [17]. this work, on the basis of the reported results. The parameters of other
The AuSn phase was described by a three sublattice site (i.e., items were directly cited from the work of [18].
(Sn)1:(Sn, Va)1:(Au, Ni)1), in order to reproduce the ternary Phase, Ni3Sn_LT, was determined to dissolve about 4.4 at% Au at
solution range. Its Gibbs energy was formed as 400 1C [20], such ternary solubility was ignored in the work of [22].
ðSnÞ :ðSn;V aÞ1 :ðAu;NiÞ1 In this work, it was taken into consideration during the opti-
GðSnÞ1 :ðSn;V aÞ1 :ðAu;NiÞ1 ¼ ∑ ∑ Y IIo Y III
p GSn:o:p
1

o p mization procedure. It was described by a two-sublattice sites,

þ RTðY IISn LnY IISn þ Y IIVa LnY IIV a Þ
þ RTðY III III III III
Au LnY Au þY Ni LnY Ni Þ Ni
!
ðSnÞ :ðSn;VaÞ :ðAu;NiÞ1
þ Y IISn Y IIVa Y III
Au ∑ j L Sn:ðSn;VaÞ:Au
1 1
ðY Sn  Y V a Þj
j ¼ 0;1
!
j ðSnÞ1 :ðSn;VaÞ1 :ðAu;NiÞ1
þ Y IISn Y IIVa Y III
Ni ∑ L Sn:ðSn;VaÞ:Ni ðY Sn  Y V a Þj
j ¼ 0;1
!
ðSnÞ :ðSn;V aÞ :ðAu;NiÞ1
þ Y IISn Y III III
Au Y Ni ∑ j L Sn:Sn:ðAu;NiÞ
1 1
ðY Au  Y Ni Þj
j ¼ 0;1
!
þ Y IIVa Y III III ðSnÞ :ðSn;V aÞ :ðAu;NiÞ1
∑ j L Sn:Va:ðAu;NiÞ ðY Au  Y Ni Þj ð7Þ Au80Sn20 (wt-%)
Au Y Ni
1 1

j ¼ 0;1

In the above equation, o and p indicate to elements in second and

third sublattice site, respectively. The binary parameters relating to
Au–Sn were cited from [17], and the rest were optimized in the
present assessment.
The thermodynamic description of Ni3Sn4 phase was modified
in this work, in order to fit better with the determined binary
solution ranges [19]. In this work, the same model was employed
as that described in [18], i.e., (Ni)0.25:(Ni, Sn)0.25:(Sn)0.5, and its
Gibbs energy was expressed as Ni
ðNiÞ0:25 :ðNi;SnÞ0:25 :ðSnÞ0:5 ðNiÞ0:25 :ðNi;SnÞ0:25 :ðSnÞ0:5
G ¼ Y IINi 0 G Ni:Ni:Sn
ðNiÞ0:25 :ðNi;SnÞ0:25 :ðSnÞ0:5
þY IISn GNi:Sn:Sn Fig. 1. Ni|Au80Sn20 interfacial microstructure after soldering at 320 1C for 100 s.
64 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70

i.e., (Au, Ni%, Sn)0.75:(Ni, Sn%)0.25, and its Gibbs energy was 5. Results and discussion
described as
5.1. Experimental determination
GðAu;Ni;SnÞ0:75 :ðNi;SnÞ0:25 ¼ ∑ ∑ Y Iy Y IIz 0 G ðAu;Ni;SnÞ
y:z
0:75 :ðNi;SnÞ0:25

y z
þ RTðY IAu LnY IAu þY INi LnY INi þ Y ISn LnY ISn Þ
þ RTðY IINi LnY IINi þY IISn LnY IISn Þ þGex
Fig. 1 shows the general microstructure of the solid Ni|liquid
Au–20 wt% Sn sandwich joint after soldering at 320 1C for 100 s.
The fine grained eutectic solidification structure is seen in the
ð13Þ

where y is represented by Au, Ni and Sn, z refers to as Ni and Sn. The (Au5Sn+AuSn)eut
values of Gex are related to interaction parameters. The parameters,
required in Ni–Sn binary system, equal to the value reported in [18].

4.3. Ternary compounds

In this ternary system, only one ternary compounds (i.e., τ) was Ni

determined. And it was regarded as a line compound. Thus its
Gibbs energy expression was written in the following way:

Gτ ¼ 0:143n0 G Fcc 0 Fcc 0 Bct

Au þ 0:286n G Ni þ 0:571n G Sn þH þ J nT ð14Þ AuSn

AuSn
The parameters H and J were obtained in this work.

Au5Sn

(Au 5Sn+AuSn) eut AuSn

(Ni,Au)3Sn2

Ni3Sn

Au5Sn
Ni

AuSn Fig. 3. The microstructure of Au–20 wt% Sn/Ni diffusion couple after annealing at
Ni 150 1C for 1200 h.

(Au 5Sn+AuSn) eut (Au5Sn+AuSn)eut

Au5Sn

AuSn
(Ni,Au)3Sn2

Ni
Ni

(Au 5Sn+AuSn) eut

Au5Sn
AuSn
AuSn

(Ni,Au)3Sn2
(Ni,Au)3Sn2
Ni3Sn
AuSn

Ni
Ni
Fig. 2. Ni|Au80Sn20 interfacial microstructure after soldering at 320 1C holding for
different periods: (a) keeping at 320 1C for 100 s; (b) keeping at 320 1C for 2500 s; Fig. 4. The microstructure of Au–20 wt% Sn/Ni diffusion couple after annealing at
and (c) keeping at 320 1C for 10,000 s. 150 1C for 2500 h.
 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70 65

Table 1
Thermodynamic parameters used in this work.

Phase Parameters Reference

L model: (Au, Ni, Sn) LLiq [11]

Au;Ni ¼ þ 9500  5:249nT
0

LLiq [11]
Au;Ni ¼ þ 1614
1

0 Liq
LAu;Sn ¼  48822:94 þ 19:6767nT [17]
1 Liq
LAu;Sn ¼  17990:36 þ 0:7892nT [17]
2 Liq
LAu;Sn ¼  5222:53 [17]
0 Liq
LNi;Sn ¼  104602:87 þ 197:8089nT  21:6959nT nLNðTÞ [18]
1 Liq
LNi;Sn ¼  30772:17 þ 52:5528nT  7:56094nT nLNðTÞ [18]
2 Liq
LNi;Sn ¼ þ 6582:31 [18]

Bcc model: (Au, Ni, Sn) 0

LBcc
Au;Ni ¼ þ 5000
[11]
0
LBcc
Ni;Sn ¼ þ 2369 þ 43:736nT
[18]
1
LBcc
Ni;Sn ¼  654762:56 þ 63:2724nT
[18]
2
LBcc
Ni;Sn ¼ þ 689895:17  94:7409nT
[18]
0
LBcc
Au;Ni;Sn ¼ þ 85000
This work

Bct model: (Ni, Sn) 0

LBct
Ni;Sn ¼  21500 [18]

fcc model: (Au, Ni, Sn) 0

T Fcc
cNi ¼ þ 633
[18]
0 Fcc [18]
BmagnNi ¼ :52
0 Fcc [11]
LAu;Ni ¼ þ 28696  11:274nT
1 Fcc [11]
LAu;Ni ¼  10945 þ 6:154nT
2 Fcc [11]
LAu;Ni ¼ þ 2519
0 Fcc [11]
T cAu;Ni ¼  500
0 Fcc [17]
LAu;Sn ¼  28802:84  5:5753nT
1 Fcc [17]
LAu;Sn ¼ þ 8815:07  9:7873nT
0 Fcc [18]
LNi;Sn ¼  69507:35 þ 74:5698nT  8:0319551nT nLNðTÞ
1 Fcc [18]
LNi;Sn ¼  12395:19
0 Fcc
T cNi;Sn ¼  6000 [18]
1 Fcc [18]
T cNi;Sn ¼ þ 3000
0 Fcc [18]
BmagnNi;Sn ¼  6:8002
1 Fcc [18]
BmagnNi;Sn ¼ 4:3689

Hcp model: (Au, Ni, Sn) 0

T Hcp
cNi ¼ þ 633
SGTE
0
BHcp
magnNi ¼ :52
SGTE
0
LHcp
Au;Ni ¼ þ 10000
[11]
0
LHcp
Au;Sn ¼  13163:98  4:4860nT
[17]

LHcp [17]
Au;Sn ¼  18954:81  23:2973nT
1

0
LHcp
Ni;Sn ¼ þ 10000
[18]
0
LHcp
Au;Ni;Sn ¼  274600 þ 210nT
This work

Au10Sn model: (Au, Ni, Sn) 0

GAu 10 Sn
¼ 125 þ 0:79nT þ GHSERAU [17]
Au
0 Au10 Sn
GSn ¼ 3804  3:46nT þ GHSERSN [17]
0
GAu 10 Sn
¼ þ 5000 þ GHSERNI This work
Ni
0
LAu 10 Sn
¼ þ 10000 [11]
Au;Ni

LAu 10 Sn [17]
Au;Sn ¼  13546:66  4:7107nT
0

LAu 10 Sn [17]
Au;Sn ¼  14193:13  22:3922nT
1

0 Au10 Sn
LNi;Sn ¼ þ 10000 This work

LAu 10 Sn This work

Au;Ni;Sn ¼  553355 þ 635nT
0

AuSn2 model: (Au)0.33333:(Sn)0.66667 GAuSn [17]

Au;Sn ¼  14296:55þ 5:4538nT þ 0:33333nGHSERAU þ 0:66667nGHSERSN
0 2

AuSn4 model: (Au,Ni)0.2:(Sn)0.8 GAuSn [17]

Au;Sn ¼  7790:25þ 0:8355nT þ 0:2nGHSERAU þ 0:8nGHSERSN
0 4

GAuSn This work

Ni;Sn ¼  9569:66þ 5:0104nT þ 0:2nGHSERNI þ 0:8nGHSERSN
0 4

LAuSn This work

ðAu;NiÞ:Sn ¼  13747:5 þ 7:503nT
0 4

LAuSn This work

ðAu;NiÞ:Sn ¼ þ 4200
1 4

Au5Sn model: (Au,Ni)0.84:(Sn)0.16 GAu 5 Sn [17]

Au;Sn ¼  4036:78 3:3648nT þ 0:84nGHSERAU þ 0:16nGHSERSN
0

0 Au5 Sn
GNi;Sn ¼  11287:51þ 12:5013nT þ 0:84nGHSERNI þ 0:16nGHSERSN This work
0 Au5 Sn
LðAu;NiÞ:Sn ¼  18080:78 þ 12:0133nT This work
66 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70

Table 1 (continued )

Phase Parameters Reference

AuSn model: (Sn)1:(Sn, Va)1:(Au, Ni)1 GAuSn [17]

Sn:Va:Au ¼  31490 þ 4:3439nT þ GHSERAU þ GHSERSN
0

GAuSn [17]
Sn:Sn:Au ¼  1000 þ :5nT þ GHSERAU þ 2nGHSERSN
0

LAuSn [17]
Sn:ðSn;VaÞ:Au ¼  20000 þ T
0

GAuSn This wok

Sn:Va:Ni ¼  47800:92 0:3998nT þ GHSERNI þ GHSERSN
0

Ni3Sn_LT model: (Au, Ni%, Sn)0.75:(Ni, Sn%)0.25 0

GNi3 Sn_LT
¼ þ 6300 þ GHSERNI [18]
Ni:Ni
0
GNi3 Sn_LT
¼ þ 5000 þ 0:25nGHSERNI þ 0:75nGHSERSN [18]
Sn:Ni
0
GNi3 Sn_LT
¼  28408 þ 7:0009nT þ 0:75nGHSERNI þ 0:25nGHSERSN [18]
Ni:Sn
0
GNi3 Sn_LT
¼ þ 5000 þ GHSERSN [18]
Sn:Sn
0
GNi3 Sn_LT
¼  1574:54 þ 5:3114nT þ 0:725nGHSERAU þ 0:25nGHSERSN This work
Au:Sn

Ni3Sn4 model: (Ni)0.25:(Ni, Sn)0.25:(Sn)0.5 GNi3 Sn4 This work

Ni:Ni:Sn ¼  26678:56 þ 4:301nT þ 0:5nGHSERNI þ 0:5nGHSERSN
0

0 Ni3 Sn4
GNi:Sn:Sn ¼ þ 4613:24 þ 8:749nT þ 0:25nGHSERNI þ 0:75nGHSERSN This work
GNi3 Sn4 This work
Ni:ðNi;SnÞ:Sn ¼  41928:16
0

Ni3Sn2 model: (Au,Ni,Va)1 :(Ni,Va)1 :(Ni,Sn)1 GNi3 Sn2 2 [18]

Ni:Ni:Ni ¼ þ 31637:3þ 355:1761nT  66:288nT nLNðTÞ  0:0145221nT
0

GNi3 Sn2 2 [18]

Va:Ni:Ni ¼ þ 21091:53þ 236:784nT  44:192nT nLNðTÞ  0:0096814nT
0

GNi3 Sn2 2 [18]

Ni:Va:Ni ¼ þ 21091:53þ 236:784nT  44:192nT nLNðTÞ  0:0096814nT
0

GNi3 Sn2 2 [18]

Va:Va:Ni ¼ þ 10545:766 þ 118:58688nT  22:096nT nLNðTÞ  0:0048407nT
0

GNi 3 Sn2 [18]

Ni:Ni:Sn ¼  83734:818 þ 14:6888nT þ 2nGHSERNI þ GHSERSN
0

GNi 3 Sn2 [18]

Va:Ni:Sn ¼ þ 5000 þ GHSERNI þ GHSERSN
0

0 Ni3 Sn2
GNi:Va:Sn ¼  52177:98þ 10:774nT þ GHSERNI þ GHSERSN [18]
GNi 3 Sn2 [18]
Va:Va:Sn ¼ þ 20000 þ GHSERSN
0

GNi 3 Sn2 [18]

Ni:ðNi;V aÞ:Sn ¼  9784:4 12:385nT
0

GNi 3 Sn2 [18]

Ni:ðNi;V aÞ:Sn ¼ þ 12000
1

GNi 3 Sn2 This work

Au:Ni:Sn ¼  25039:16 þ 23:2401nT þ GHSERAU þ GHSERNI þ GHSERSN
0

GNi 3 Sn2 This work

Au:Va:Sn ¼  26604:42 þ 2:8011nT þ GHSERAU þ GHSERSN
0

0 Ni3 Sn2
LðAu;NiÞ:V a:Sn ¼  24022:03 þ 14:0021nT This work

LNi3 Sn2 This work

ðAu;NiÞ:V a:Sn ¼  1520:16
1

0 Ni3 Sn2
LðAu;NiÞ:Ni:Sn ¼ þ 18407:62  81:2035nT This work

LNi3 Sn2 This work

Au:ðNi;VaÞ:Sn ¼  29989:98
0

τ model: (Au)0.143:(Ni)10.286:(Sn)0.571 0
GτAu:Ni:Sn ¼  22224:16 þ 2:0665nT þ 0:143nGHSERAU þ This work
0:286nGHSERNI þ 0:571nGHSERSN

Values are in SI units. Parameters used in present calculation were listed in the table; the rest parameters which were not shown in table were given the value of zero. And
SGTE refers to as Scientific Group Thermodata Europe (http://www.sgte.org/).

middle of the joint. However the microstructure is coarsened close
to the Ni interface. This is clearly seen from the higher magnifica-
tion image shown in Fig. 2a. Fig. 2c illustrates the solid Ni|liquid
Au–20 wt% Sn interfacial microstructures soldered at 320 1C hold-
ing for 10,000 s. Dissolved Ni is not observed from either of the
IMCs in the eutectic structure, within the detection limits of EDS.
However, after 100 s annealing, small amounts of Ni (o2 at%) is
already detected from AuSn near the interface. As seen from
Fig. 2b and c, there is a layer of (Ni, Au)3Sn2 crystals formed at
the interface. Also some of (Ni, Au)3Sn2 precipitates are found
inside AuSn grains. Au5Sn did not contain any Ni even after
10,000 s annealing.
After making the sandwich joint at 320 1C for 100 s the solid
state Ni|Au–20 wt% Sn diffusion couples were annealed at 150 1C
for 1200 and 2500 h, respectively. Fig. 3 shows the microstructure
of the sample after annealing for 1200 h. As shown in Fig. 3,
the sample is composed of Ni/Ni3Sn/Ni3Sn2/AuSn/(Au5Sn þAuSn)
layers from the bottom to top. Here the Ni3Sn and Ni3Sn2 phase
formed a continuous layer. The AuSn layer is slightly irregular,
while still can be considered as an interlayer.
In this investigation, a large amount of ternary solubility in
Ni3Sn2 (  32 at% Au) and AuSn ( 3.5 at% Ni) compounds were
also found at the interfaces next to Ni. Besides, around 3 at%
Ni was measured in Au5Sn compound. As for the Ni3Sn compound,
it is too thin to be analyzed after 1200 h annealing. According to
[22], when temperature increases, the solubility of Ni at% to AuSn
phase also increases, and the solubility of Au at% in Ni3Sn2
compound decreases accordingly. As shown in [22], the Ni3Sn2
compound can dissolve up to 29.1 at% Au at 200 1C, and the AuSn
compound can dissolve up to 4.5 at% Ni at 200 1C. Therefore, the
ternary solubility of Ni3Sn2 and AuSn compounds at 150 1C,
determined in this work were in accordance with those reported
in [22].
Fig. 4 shows the microstructures of sample after annealing for
2500 h. The almost identical results were obtained as that of the
sample annealed for 1200 h. Only with the exceptions that the
Au5Sn areas next to AuSn layer was enlarged, and the thickness of
Ni3Sn2 and Ni3Sn layers were slightly increased. However, the
composition of Ni3Sn layer was still outside of the resolution limits
of SEM/EDS. The interfacial reaction layer structure of the diffusion
couple is proposed as Ni/Ni3Sn/Ni3Sn2/AuSn/(Au5Snþ AuSn).
5.2. Thermodynamic assessment
The thermodynamic descriptions of the Au–Ni–Sn binary sub-
systems have been taken from the literatures: Au–Ni according to
Wang et al. [11]; Au–Sn according to Dong et al. [17] and Ni–Sn
according to Li et al. [18] except for the parameters of Ni3Sn4.
The parameters of Ni3Sn4 phase was modified on the basis of the
model described in [18], in order to fit the reported homogeneity
 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70 67

ranges [19]. These binary systems have been combined and
phase models have been adopted in order to describe the ternary
solubility of the Bct, Hcp, Au10Sn, AuSn4, Au5Sn, Ni3Sn_LT, and
Ni3Sn2. Moreover, the terna1ry compound τ has been added.
New binary and ternary thermodynamic parameters have been
evaluated using the PARROT optimizer module in the Thermo-Calc
software package. Optimization has been performed by taking
into account the experimental information (i.e., phase equilibria in
different isothermal sections and relevant ternary solubility in
binary compounds) from literatures [20,22] and, in particular, from
the present experimental investigation. Table 1 lists the thermo-
dynamic parameters used in this work.
As shown in Table 1, the ternary interaction parameters of Hcp
and Au10Sn phases have strong temperature dependence. It can be
explained in this way: no ternary thermochemical quantities for
these phases have been determined before. There, the parameters
were adjusted according to phase equilibria involving them, and
then determined to locate within an optimal range (Table 2).
The experimental information are mainly on the basis of the
reported phase equilibria and ternary solubility in these phases

Table 2
Comparison of the ternary solubility of binary phase between previously reported data and the calculated results in this work.

Temperature (1C) Phase Ternary solubility (at%) Reference

150 Ni3Sn2 Au%:  32 Experimental result, this work

Au%: 31.5 Assessed, this work
Ni3Sn_LT Au%: 1.8 Assessed, this work
AuSn Ni%:  3.5 Experimental result, this work
Ni%: 2.8 Assessed, this work
Au5Sn Ni%:  3 Experimental result, this work
Ni%: 3.0 Assessed, this work
AuSn4 Ni%: 10.4 Assessed, this work

200 Ni3Sn2 Au%: 29.1 Experimental result [22]

Au%: 26.4 Assessed result [22]
Au%: 31.1 Assessed, this work
Ni3Sn_LT Au%: 1.9 Assessed, this work
AuSn Ni%: 4.5 Experimental result [22]
Ni%: 4.0 Assessed result [22]
Ni%: 4.1 Assessed, this work
Hcp Ni%: 0.2 Experimental result [22]
Ni%: 0.06 Assessed result [22]
Ni%: 0.16 Assessed, this work
AuSn4 Ni%: 10.5 Experimental result [22]
Ni%: 8.0 Assessed result [22]
Ni%: 10.1 Assessed, this work

300 Ni3Sn2 Au%: 29.2 Experimental result [22]

Au%: 28.7 Assessed result [22]
Au%: 30.4 Assessed, this work
Ni3Sn_LT Au%: 2.5 Assessed, this work
AuSn Ni%: 10.9 Experimental result [22]
Ni%: 8.1 Assessed result [22]
Ni%: 7.5 Assessed, this work
Hcp Ni%: 0.6 Experimental result [22]
Ni%: 0.6 Assessed result [22]
Ni%: 0.6 Assessed, this work
Au10Sn Ni%: 0.5 Assessed, this work

400 Ni3Sn2 Au%: a continuous solid solution with AuSn Experimental result [20]
Au%: 26.8 Experimental result [22]
Au%: 26.0 Assessed result [22]
Au%: 27.7 Assessed, this work
Ni3Sn_LT Au%: 4.4 Experimental result [20]
Au%: 3.1 Assessed, this work
AuSn Ni%: a continuous solid solution with Ni3Sn2 Experimental result [20]
Ni%: 11.9 Experimental result [22]
Ni%: 9.9 Assessed result [22]
Ni%: 10.8 Assessed, this work
Hcp Ni%: o1 Experimental result [20]
Ni%: 1.7 Experimental result [22]
Ni%: 1.7 Assessed result [22]
Ni%: 1.4 Assessed, this work
Au10Sn Ni%:o 1 Experimental result [20]
Ni%: 0.7 Assessed, this work

500 Ni3Sn2 Au%: 23.5 Experimental result [22]

Au%: 22.6 Assessed result [22]
Au%: 22.4 Assessed, this work

600 Ni3Sn2 Au%: 13.9 Experimental result [22]

Au%: 13.5 Assessed result [22]
Au%: 16.8 Assessed, this work
68 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70

by Neumann et al. [20] and Liu et al. [22], as listed in Table 2.
Neumann et al. studied the isothermal section at 400 1C and the
related ternary solubility in binary compounds [20]. Besides, they
found the phase equilibrium between Ni3Sn2 and Au10Sn com-
pounds which was not covered in the experimental determining
area of [22]. Liu et al. measured the composition ranges of Hcp and
compounds in Sn-rich side at different temperatures by analyzing
the equilibrated samples using EPMA, which implies that these
experimental data are reliable. Therefore, in order to fulfill the
phase equilibrium between Ni3Sn2 and ternary solubility of Hcp
determined at different temperatures, such strong temperature
dependence was required.
Fig. 5 illustrates the modified Ni–Sn phase diagram, with the
experimental invariant points superimposed [19]. Further, the
enthalpies of formation of Ni–Sn system were also calculated
and compared with the determined data [23,24] (i.e., Fig. 6).
According to these comparisons, it is evident that the present
modification of Ni3Sn4 can be considered acceptable. Thus,
they were used in the optimization of the ternary thermodynamic
database.
By using the present ternary database, the isothermal sections
at various temperatures were calculated, and are illustrated in
Fig. 7a–f. These isothermal sections are superimposed with some
of the critical experimental points from [20,22], as well as those
obtained in the present study with the help of diffusion couple
experiments. As shown in these isothermal sections, most of the
experimental information can be reproduced. Table 2 listed the
calculated ternary solubility in binary compounds by using the
present obtained parameters. Comparing with the thermodynamic
assessment work of [22], more experimental information was
included to the assessment in this work. It was found that a good
agreement was achieved between the calculated results in this
work and previous experimental data [20,22]. Further, the present
thermodynamic description can be considered better than that in
[22], not only because more experimental information was taken
into account, but due to the fact that it also includes the recently
updated binary information [16–19], and the ternary solubility in
Au5Sn and Ni3Sn_LT compounds as well as two ternary areas
which were determined in [20] while they were missing in [22].
Thus, this further confirms the fact that the present database can
be considered reasonable. In addition to the isothermal sections,
the liquidus projection was constructed, as shown in Fig. 8. Finally,
the relevant invariant reactions in this ternary system were
calculated, as listed in Table 3.
The diffusion path in the reaction couple, i.e., Ni/Au–20 wt% Sn
solder, at 150 1C is predicted based on the present experimental
and calculated results. This is shown by the dotted line in Fig. 9.
The path starts from Ni towards the Ni3Sn along the binary Ni–Sn
edge of the diagram as no Au was detected inside Ni3Sn. The
diffusion path then proceeds to (Ni, Au)3Sn2 by taking one of the
tie lines—again close to the binary edge, since Ni3Sn does not have
marked amounts of Au dissolved. The path travels inside the
(Ni, Au)3Sn2 one phase field towards AuSn. In Fig. 3 there one
can see that there is at least one location where three phases,
namely (Ni, Au)3Sn2, (Au, Ni)Sn and (Au, Ni)5Sn are in contact. This
corresponds to the corner of the tie-triangle for the given
equilibrium. Based on the Gibbs phase rule, when temperature
and pressure are fixed, only two-phase areas can be realized in the
diffusion couple if diffusion is to proceed, since concentration
(activity) differences are needed to drive the diffusion. In this case
there is naturally no three phase region, but a point, which
indicates that the diffusion path hits the corner of the (Ni, Au)3Sn2,
(Au, Ni)Sn and (Au, Ni)5Sn tie-triangle. Also at this point, as the
activity differences are no longer there, locally no diffusion should
occur. However, the global diffusion path then proceed to (Au, Ni)
Sn by taking one of the tie-lines in the corresponding two-phase
field implying a relatively straight interface between the phases.
After reaching (Au, Ni)Sn the path turns towards (Au, Ni)5Sn. There
are two options, which the diffusion path can utilize. It can
proceed along the two-phase field, most likely by crossing the
tie-lines, since the interface in Fig. 3 appears relatively wavy or it
can travel through the three phase triangle along a straight line to
Fig. 6. Calculated enthalpies of formation of Ni–Sn system at 298 K, comparing
with previously reported value [18,23,24]. Reference stages: Ni(Fcc), and Sn(Bct).

Fig. 5. Phase diagram of Ni–Sn with experimental data superimposed: (a) the partial phase diagram from 10 at% Ni to 45 at% Ni at temperature range 1000–1600 K; and
(b) the entire phase diagram of Ni–Sn binary system.
 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70 69

Fig. 7. Calculated isothermal section of Au–Ni–Sn ternary system, at various temperatures, superimposed experimentally determined both form this work and previous
works [20,22]. a) 1501C, b) 2001C, c) 3001C, d) 4001c, e) 5001C and f) 6001C.

Fig. 8. Calculated liquidus projection of Au–Ni–Sn, the figure in the right hand side is the enlarged part at the Au–Sn boundary.

the end composition. It is common knowledge that the so called
“virtual diffusion path”, as defined by Kirkaldy et al. [25], if made
to go through a tie-triangle, represents an apparent three-phase
equilibrium with three phases interwoven at the interphase area
(e.g., finger-like structure). However, as there are no such mor-
phological features in any of the micrographs, this feature of the
diffusion path is not likely. In addition, if the path would go
through the three phase equilibrium, mass-balance would not be
fulfilled. Hence, the path must first go to the Ni free Au5Sn and
then turn back to the original gross composition along the binary
Au–Sn edge in order to fulfill the mass-balance. It is to be noted
that there is a significant increase in the amount of Au5Sn in
contact with (Ni, Au)3Sn2 after 2500 h in comparison to 1200 h.
This implies that the local equilibria may not have been achieved
completely and further microstructural changes may occur after
longer annealing times. This will also naturally change the course
of the corresponding diffusion path. The details about the diffusing
species in Au–Ni–Sn system will be discussed in following
publications.
6. Conclusions
The microstructure characteristics of diffusion couple Au–20 wt%
Sn/Ni bulk was studied via SEM/EDX, for samples after annealing at
150 1C for 1200 h and 2500 h, respectively. The phase relations in Au–
Ni–Sn ternary system have been thermodynamically reassessed by
utilizing the CALPHAD method based on the available experimental
results as well as by utilizing the new updated thermodynamic
descriptions of the three binary systems. A set of self-consistent
70 H.Q. Dong et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 61–70

Table 3 Acknowledgments
Calculated ternary invariant reactions in Au–Ni–Sn ternary system.

Type Temperature (K) Reaction Liquid composition (at%)

The authors would like to thank Finnish Funding Agency for
Technology and Innovation, Okmetic and Murata Electronics Oy
Au Ni for their financial support. One of the authors, H.Q. Dong, thanks
the Graduate School in Electronics Telecommunications and Auto-
U1 1229.62 Lþ Bcc-Ni3Sn_LT þ Ni3Sn2 32.05 49.36
mation, Finland for the financial support.
U2 1220.95 Lþ Bcc-Ni3Sn_LT þ Fcc 24.41 62.00
U3 844.34 Lþ Ni3Sn_LT-Ni3Sn2 þFcc 78.73 1.98
U4 802.15 Lþ Fcc-Au10Sn þ Hcp 79.21 0.10
U5 577.88 Lþ AuSn-Ni3Sn2 þ AuSn2 24.16 0.036 Appendix A. Supplementary material
U6 577.57 Lþ Ni3Sn2-AuSn2 þτ 24.04 0.037
U7 563.33 Lþ τ-AuSn4 þAuSn2 19.99 0.04
Supplementary data associated with this article can be found in
U8 561.05 Lþ Ni3Sn2-AuSnþ Hcp 69.83 0.0061
U9 489.9 Lþ Ni3Sn4-AuSn4 þBct 0.95 0.08 the online version at http://dx.doi.org/10.1016/j.calphad.2013.10.001.
P1 835.91 Lþ Ni3Sn2 þ Fcc-Hcp 78.67 1.76
P2 693.39 Lþ Ni3Sn4 þ Ni3Sn2-τ 23.79 0.27
References
P3 572.82 Lþ τþ Ni3Sn4-AuSn4 12.55 0.10

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