Materials and Design 51 (2013) 789796

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Materials and Design

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Evolution of thermal property and creep resistance of Ni and Zn-doped

Sn2.0Ag0.5Cu lead-free solders
A.A. El-Daly, A.M. El-Taher
Physics Department, Faculty of Science, Zagazig Univ., Zagazig, Egypt

a r t i c l e

i n f o

Article history:
Received 4 March 2013
Accepted 21 April 2013
Available online 3 May 2013
Keywords:
Lead-free solder
Microstructure
Mechanical properties

a b s t r a c t
The effect of small amount of Ni and Zn additions on thermal behavior and creep properties of Sn2Ag
0.5Cu (SAC 205) lead free solder alloy was investigated. Additions of Ni and Zn, respectively, into SAC
(205) solder caused its undercooling temperature to decrease signicantly from 26.1 C to 18.0 and
1.4 C. The results show that the formation of new (Cu,Ni)6Sn5 and Cu5Zn8 hard particles in the b-Sn
matrix are drastically strengthen the SAC (205) solder. The lead-free SAC (205) 0.5Zn solder joints
showed superior creep resistance in terms of much lower creep rate and elongated creep fracture lifetime
over the traditional SAC (205) and SAC (205) 0.05Ni solders. However, the ductility of SAC (205) 0.5Zn
alloy is lower than that of the other two alloys. This difference was attributed to the lower precipitate
coarsening and higher precipitate density of Cu5Zn8 and Ag3Sn IMCs in Zn-doped SAC (205) cast alloy,
which could provide more obstacles for dislocation pile up in the adjacent b-Sn grains. Nevertheless,
the strengthening effect depends on the undercooling of the solder.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Currently, the concern over the toxicity of lead in eutectic Sn
Pb solders has prompted the development of new tin rich lead free
solder alloys for electronic packaging [1]. There are several promising candidate lead-free solders for consideration of different
applications, including SnAg, SnCu, SnAgBi, SnZn and Sn
AgCu systems. Among these candidates, the near-ternary eutectic
SnAgCu (SAC) system solders seem to be more promising as the
substitute for SnPb based solders because of its relatively low
melting temperature, better solderability and mechanical properties compared with SnAg binary eutectic alloy [2]. In view of that,
the SAC solders are commonly used in surface mount technology
(SMT) assembly for microelectronics into industrial production
[3]. Since the solder material normally has a relatively low melting
temperature, Tm, creep deformation is the dominant deformation
mode in metallic materials when the homologous temperature,
TH = T/Tm, exceeds 0.4. Therefore, creep failure and fatigue failure
related to creep are crucial factors in designing reliable electronic
packaging modules (EPMs), as their service temperatures are often
higher than 0.4Tm [4]. Hence, creep resistance is one of the properties required for use of lead-free solders in low and high temperature applications. Creep resistance of lead-free solder alloys can be
enhanced by dispersions of ne precipitates either in direct or indirect manner. The direct effect is a barrier to dislocation glide, by
Corresponding author. Tel.: +20 552327173/2303252; fax: +20 552308213.
E-mail
addresses:
(A.M. El-Taher).

ahmedeltaher80@yahoo.com,

a_eltaher@zu.edu.eg

0261-3069/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.04.081

which high-temperature creep rates are signicantly reduced.

The indirect effect is the inhibition of grain growth, recrystallization, and grain boundary sliding. Therefore, creep resistance is
strongly sensitive to the morphology of secondary phases, depending on the composition and processing parameters, which determines the alloys service life and credibility [5]. In view of that, it
is necessary to improve the mechanical properties of lead free solder alloys. One approach adopted for achieving this objective is the
addition of small quantities of Zn, Ni, Bi, Sb, In, Co, Ga or other
nanoparticles to near-ternary eutectic SnAgCu (SAC) system solders [610]. Most of the alloying elements in SAC alloys are known
to increase the creep resistance by causing precipitate hardening or
solid solution hardening of the mother alloy. Among the published
investigations about the creep behavior of SnAgCu solders, only a
few focused on the relevant aspects of material physics which
are closely connected to solder creep. For example, with the addition of Ni and Sb into SAC (105) solder, signicant improvement in
creep resistance of (210%) and (350%) is realized when compared
with the SAC (105) solder alloy [11]. Investigations by Zhang
et al. [12] have shown that the addition of element Bi with an
amount of 2.03.0% (wt) to Sn3.5Ag0.7Cu solder can reduce
the creep rate and thus improve processing performance of the solder. Zhang et al. [13] studied the effects of rare earth Ce doping on
the properties of SnAgCu solder alloys. They found that SACCe solders show higher creep resistance than SAC alloys. However, an
effective development of advanced SAC alloys for low temperature
applications should be based on knowledge of the mechanisms
that determine their resistance to creep. So, the aim of this study
is to investigate the effect of Ni and Zn additions on the thermal

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A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

behavior and creep performance of SAC (205) solder alloy. The test
conditions cover the temperatures and applied stresses, which are
important for the assessment of solder joint reliability. The key factors that affect the creep behavior of the solder alloy are discussed.
2. Experimental procedures
The alloys investigated had a composition of Sn2.0Ag0.5 wt.%
Cu, Sn2.0Ag0.5Cu0.05 wt.% Ni and Sn2.0Ag0.5Cu0.5 wt.% Zn
(which are hereafter called SAC (205), SAC (205) 0.05Ni and SAC
(205) 0.5Zn, respectively). Chemical analysis was conducted by
Thermo iCAP 6300 Radial View ICP Spectrometer from chilled samples obtained during casting. The chemical compositions of the
tested alloys are given in Table 1. They were prepared from high
purity (99.99%) tin, Cu, Ag, Ni and Zn as raw materials. The processing of these alloys was carried out by melting these ingots in a vacuum arc furnace under high purity argon atmosphere to produce
rod-like specimen with a diameter of approximately10 mm. The
melt was held at 600 C for 2 h to complete the dissolution of Sn,
Cu, Ag, Ni and Zn, and then poured in a steel mold to prepare the
chill cast ingot. A cooling rate of 68 C/s was achieved, so as to
create the ne microstructure typically found in small solder joints
in microelectronic packages. The microstructure was characterized
by scanning electron microscopy (SEM) JSM-5410, Japan. A solution of 3% HCl, 2% HNO3 and 95% (vol.%) Ethyl alcohol was prepared
and used to etch the samples. Phase identication was based on
Energy Dispersive X-ray Spectrometry (EDS). Because of different
approaches in the specimen design, test setups and experimental
methodology are necessary to investigate solder tensile behavior
at different volumes. The homogenized cast ingots were then
mechanically machined into a wire samples with a gauge length
marked 3  102 m for each samples and 2.0  103 m diameter,
as developed in our previous work [11]. The small sized solder
specimens used in this work had more advantageous than the test
standards since the creep behavior follows a simple power law. Besides, the metallization material changes not only the absolute
mechanical strength, but also the stress sensitivity (stress exponent) of the deformation behavior. Such effects could not be found
in bulk specimens. Before testing, the specimen was annealed at
120 C for 30 min to reduce the residual stress induced in the sample preparation. Tensile creep tests are conducted on a 3360 universal material testing system, and GWT 504 high temperature
testing system respectively. The tensile creep tests were conducted
at temperature range of 25120 C, and different constant loads
(with load cell capacity meet or exceed ASTM: E4-10). The stress
dependence of the creep rate e_ at a single temperature was usually
obtained from three tests. The temperature variation inside the
high temperature furnace is maintained within 1.5 C. The loading
process is controlled and the experimental data are recorded by
computer system. The axial strain is measured in accordance with
the ASTM: E83 10a.

the peaks of Ag3Sn and g-Cu6Sn5 IMC particles with the b-Sn phase
were detected in all SAC (205)-based solder samples. The addition
of Ni leads to the formation of new (Cu,Ni)6Sn5 IMC due to alloying
of Cu and Ni. Ni is known to be one dominant and widely used doping material in SAC solders due to its excellent performance in
improving solder microstructure and increasing the drop lifetime
of electronic assembly [14]. However, the addition of Zn enhances
the formation of Cu5Zn8 phase in SAC (205) 0.5Zn alloy sample
owing to the solubility of Zn in Cu. The formations of such new
(Cu,Ni)6Sn5 and Cu6Zn5 IMCs have been recognized to reinforce
the solder matrix and enhance its mechanical properties.
3.2. Effect of Ni and Zn additions on the solidication microstructures
It was reported that the microstructure of near eutectic SnAg
Cu solder is formed by dendritic b-Sn, Ag3Sn and Cu6Sn5 ternary
eutectic phase [6,15]. In this study, the microstructure of SAC
(205) solder is consistent with the literature. Fig. 2a shows the dark
and bright phases being the primary b-Sn phases and eutectic SAC
(205) phases, respectively. According to XRD analysis, the eutectic
areas were found to contain Ag3Sn and g-Cu6Sn5 IMCs. The average size of b-Sn grains was 70.0 3.5 lm. The structure of the eutectic network is superne, and there are no big block-like Ag3Sn
and g-Cu6Sn5 IMC particles due to the formation of high nucleation density of the second phase in the Sn melt, which acts as
nucleating sites during solidication.
After Ni and Zn additions, the microstructure is drastically
changed. Addition of Ni enlarges the primary b-Sn dendrites and
changes g-Cu6Sn5 into (Cu,Ni)6Sn5 IMC particles, as shown in
Fig. 2b. The b-Sn matrix (dark) and small particles of (Cu,Ni)6Sn5
mixed with needle-like Ag3Sn IMC (gray) were dispersed in b-Sn
matrix. However, the additions of Zn into SAC (205) solder leads
to decrease the average size of b-Sn grains signicantly. The average size of b-Sn grains was reduced from 70.0 3.5 to
30.0 lm 2.5 lm, as seen in Fig. 2c. Besides, the eutectic areas
were found to contain Ag3Sn and g-Cu6Sn5 IMCs with large
amount of near-spherical morphology Cu5Zn8 IMC particles as conrmed with XRD analysis. Moreover, the uniform eutectic network
structure was observed in SAC (205) 0.5Zn without any large
massive Ag3Sn IMC.
Fig. 3 shows the high-magnication SEM microstructures of the
three alloys and corresponding EDS analysis in some locations. It
can be seen from Fig. 3a that, although the microstructure of SAC

3. Results and discussion

3.1. X-ray diffraction analysis
The XRD analysis was performed to examine the phase structure of IMCs in the three solders, as illustrated in Fig. 1. Actually,
Table 1
Chemical composition of the solders studied (wt.%).
Alloys

Cu

Ag

Ni

Zn

Sn

SAC (205)
SAC (205) 0.05Ni
SAC (205) 0.5Zn

0.5
0.5
0.5

2.0
2.0
2.0

0.05

0.5

Bal.
Bal.
Bal.

Fig. 1. XRD pattern of (a) SAC (205), (b) SAC (205) 0.05Ni and (c) SAC (205)
0.5Zn solder alloys.

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791

Fig. 2. Low-magnication SEM microstructures of (a) SAC (205), (b) SAC (205) 0.05Ni and (c) SAC (205) 0.5Zn solder alloys.

(205) solder is mainly composed of large b-Sn grains, the microstructure of IMCs in the eutectic regions has more ner dot-shaped
precipitates morphology (0.51.5 lm) and less needle-like morphology (5 lm). The dense IMCs precipitates in between b-Sn
grains were identied as Cu6Sn5 and Ag3Sn eutectic according to
EDS analysis shown in Fig. 3d.
The microstructure of the SAC (205) 0.05Ni solder was composed of the primary b-Sn phase (dark) and mixed plate-like
(Cu,Ni)6Sn5 with needle-like Ag3Sn IMC (gray), which was dispersed in b-Sn matrix, as seen in Fig. 3b and e. The formation of
plate-like (Cu,Ni)6Sn5 morphology may result from anisotropy of
surface energies and compositional supercooling related to the
presence of Ni, which inuences the growth behavior of Cu6Sn5.
It has been suggested that [16] the incorporation of Ni in the
(Cu,Ni)6Sn5 IMC makes this phase more thermodynamically stable
at room temperature, since Ni was found to retard the transformation of hexagonal structure to monoclinic structure at 186 C,
thereby stabilizing the hexagonal structure at room temperature.
As a result, the stabilization of hexagonal (Cu,Ni)6Sn5 will suppress
the volume change associated with phase transformation and will
eventually prevent IMC cracking. This is expected to improve solder performance. Conversely, alloying of Zn triggers the morphology change of large b-Sn dendrites into small dark-gray b-Sn
primary dendrite grains surrounded by light eutectic regions of rened Cu6Sn5 and Ag3Sn IMC phases with large amount of spherical
Cu5Zn8 IMC particles dispersed in b-Sn matrix, as shown in Fig. 3c
and identied by EDS analysis in Fig. 3f.
3.3. Melt properties of SAC (205) solders
DSC analysis was carried out in order to investigate the fundamental thermal reactions of SAC (205) solder alloys during heating
and cooling. The results are demonstrated in Fig. 4 and summarized in Tables 2 and 3. Fig. 4 shows that each scan contains one
endothermal peak corresponding to the melting of the SAC (205)
solder doped with Ni and Zn elements. It can be seen that additions
of Ni and Zn have a little effect on the melting property of SAC
(205) solder during the heating process. Evidently, all the solidus

temperatures are shifted to temperatures slightly lower than the

equilibrium solidus temperature of SAC (205) solders, and the
melting temperature is further depressed as the Zn is added. The
same tendency of melting point depression has also been detected
in SAC systems [11]. Table 2 shows also that the pasty range of
three solders lies in the range of 7.08.9 C, which is lower than
11.5 C for SnPb eutectic [17]. This narrow pasty range of SAC
(205) solders may evade manufacturing problems, such as increasing the sensitivity to vibration during wave soldering. Also, it can
decrease the probability of llet lifting phenomena, the tendency
towards porosity and hot tearing due to the effect of alloy shrinkage. For that reasons, Ni- and Zn-containing SAC (205) solders have
displayed satisfactory reliability.
Undercooling is dened as the difference between the melting
point during heating and the solidication temperature during
cooling, and relates to the difculty of nucleating a solid phase in
a liquid state [18]. A non-uniform temperature distribution due
to undercooling of the b-Sn phase will supersaturate the alloying
elements, leading to an inhomogeneous distribution of unwanted
phases in the SAC (205) solder joint. By having a direct effect on
nucleation during solidication, Ni and Zn could alleviate these
problems, and this may cause signicant repercussions on the
microstructure of the solidied sample. In Fig. 4 and Table 3 it is
interesting to note that, the exothermal peaks upon cooling for
all alloy samples appeared at lower temperature compared with
their endothermic peaks due to the undercooling, but the reductions in temperature were not identical. The differences in the onset temperatures during cooling are caused by the solidication of
the primary phases. The primary phases may have provided suitable sites for heteronucleation of tin, so the undercooling value
of the solder decreases with Ni and Zn content. It is worthy of notice that the degree of undercooling of SAC (205) solder was
strongly decreased from 26.2 to 18.0 and 1.4 C after Ni and Zn
additions, respectively. This means that the solidication processes
of Ni- and Zn-containing SAC (205) alloys were initiated with the
nucleation of new (Cu,Ni)6Sn5 and Cu5Zn8 IMC particles. The literature showed also that a decrease in b-Sn undercooling resulted in
reducing Ag3Sn formation in the SAC alloys, and it can be achieved

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A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

Fig. 3. High-magnication SEM microstructures of (a) SAC (205), (b) SAC (205) 0.05Ni and (c) SAC (205) 0.5Zn solder alloys and the corresponding EDS analysis of some
locations.

by the addition of a fourth alloying elements such as Ni, Zn and Sb

[17,18]. In this case, addition Ni and Zn atoms not only substitute
at the Sn sites to form IMCs at the interfaces or in the solder, but
also precipitate together with Ag and Cu to form small particles
that were identied as the (Cu,Ni)6Sn5 and Cu5Zn8 IMC particles.
These particles may be the primary phase that forms upon cooling,
and could act as an additional nucleation sites, improving the rate
of nucleation, leading to a reduced undercooling effect. As a result,
one may expect that the microstructure of the Ni and Zn solidied
samples does not show any noticeable large Ag3Sn precipitates,
and the Ag3Sn growth is probably only limited to small phases in
the eutectic matrix due to the combined effects of streaming and
enhanced nucleation. These results are quite consistent with the
explanation proposed by Chen et al. [19] that primary IMCs might
act as heterogeneous nucleation sites for Sn dendrites upon solidication and are able to suppress the undercooling of SnAgCu
alloys.

3.4. Features of creep curves

Figs. 59 summarize the results of the creep experiments on the
three solders. The diagrams in Fig. 5 absolutely show the creep
kinetics of three alloys during a single creep test at room temperature and stress of 18.1 MPa. The creep strain vs. time data was
converted into a strain rate vs. time and strain rate vs. strain plots,
as this provides the best representation to compare the deformation kinetics of SAC (205), SAC (205) 0.05Ni and SAC (205)
0.5Zn solders with each other. The transitions between the three
distinct creep stages, primary, secondary and tertiary, are evident
for SAC (205) and Ni-containing alloys at the time interval investigated. The creep rate continuously decreases during primary stage
to reach a constant creep rate and is stabilized for longer time during secondary creep region before fracture, especially for SAC (205)
0.5Zn solder. Remarkably, SAC (205) alloy showed signicant primary creep: the accumulated creep strain was more than 5% in

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A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

Table 3
Comparison of solidus temperature (Tonset) during heating, liquidus temperature
(Tonset) during cooling and undercooling range for SAC (205), SAC (205) 0.05Ni and
SAC (205) 0.5Zn solder alloys.

Undercooling

Cooling

(a)

Alloys

(Tonset) heating
(C)

Tonset cooling
(C)

Undercooling (Th  Tc)

(C)

SAC (205)
SAC (205) 0.05Ni
SAC (205) 0.5Zn

212.9
212.7
211.3

186.8
194.7
209.9

26.1
18.0
1.4

100

(a)

90

Heating

= 18.1 MPa

SAC (205)
SAC (205) - 0.05 Ni
SAC (205) - 0.5 Zn

T = 25 oC

80

( %)

70

Undercooling

60
50
40

(b)

Cooling

30
20
10

Heating

0
0

10000

20000

30000

40000

Time (sec)

(b)

Cooling

(c)

-3

10

-4

10

-5

T = 25 oC

. (s-1)

Undercooling

10

SAC (205)
SAC (205) - 0.05 Ni
SAC (205) - 0.5 Zn

= 18.1 MPa

Heating

10000

20000

30000

40000

Time (sec)
160

180

200

220

240
10

SAC (205)
SAC (205) - 0.05 Ni
SAC (205) - 0.5 Zn

= 18.1 MPa

(c)

T = 25 oC

-3

Table 2
Comparison of solidus temperature (Tonset) and liquidus temperature (Tend) for SAC
(205), SAC (205) 0.05Ni and SAC (205) 0.5Zn solder alloys from heating curve.
Alloys

Tonset
(C)

Tend
(C)

Pasty range (Tend

Tonset) (C)

Melting
temperature (C)

SAC (205)
SAC (205)
0.05Ni
SAC (205)
0.5Zn

212.9
212.7

220.0
221.6

7.1
8.9

213.5
214.1

211.5

218.5

7.0

212.5

. (s-1)

Fig. 4. DSC heating and cooling curves of (a) SAC (205), (b) SAC (205) 0.05Ni and
(c) SAC (205) 0.5Zn solder alloys.

10

10

-4

-5

10

20

30

40

50

60

70

Creep Strain
100 s, whereas, the beginning of primary creep at 100 s for the SAC
(205) 0.05Ni and SAC (205) 0.5Zn alloys appears at 3.4% and
1.7%, respectively. That means, the ductility of SAC (205) 0.5Zn

Fig. 5. (a) Comparison of creep curves at T = 25 C and r = 18.1 MPa (b) creep rate
time curves and (c) creep ratestrain curves for SAC (205), SAC (205) 0.05Ni, SAC
(205) 0.5Zn solder alloys.

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A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

T = 25 C
-4

T = 70 C

T = 25 C

T = 110 C
-4

SAC (205)

T = 70 C

T = 110 C

SAC (205)

-6
-6

n 1 = 8.6

-8

-8

ln ()

ln ()

= 0.65

= 0.6

-10

-10

n 1 = 9.0

-12
n 1 = 9.5

= 0.53

-12

-14
-16

-14

2.4
12

14

16

18
(MPa)

20

2.7

2.9

3.0

3.1

3.2

22

3.1

3.2

SAC (205) - 0.05 Ni

-8

0 .6

ln ()

0 .7

-10

n 1 = 9.0

-10
n 1 = 9.6

-12

-12

n 1 = 10.2

-14
=

-14

0 .5

9
-16
2.7

2.6

2.5

2.8

2.9

3.0

Ln (MPa)

-16
12

14

16

18
(MPa)

20

22
-4

SAC (205) - 0.5 Zn

-6

n1 = 10.0

SAC (205) - 0.5 Zn

-8

= 0.79

-6

ln ()

-4

2.8

SAC (205) - 0.05 Ni

-8

ln ()

2.6

Ln (MPa)
-6

-6

2.5

n 1 = 10.5

-10

ln ()

-8
-12
-10

= 0.74

n 1 = 11.0

-14

-12

-16
2.4

= 0.70

-14

14

2.6

2.7

2.8

2.9

3.0

3.1

3.2

Ln (MPa)

-16
12

2.5

16

18

20

22

Fig. 7. Relationship between ln (r) and ln (e_ ) for SAC (205), SAC (205) 0.05Ni and
SAC (205) 0.5Zn solder alloys at T = 25, 70 and 110 C.

(MPa)
Fig. 6. Relationship between r and ln (e_ ) for SAC (205), SAC (205) 0.05Ni and SAC
(205) 0.5Zn solder alloys at T = 25, 70 and 110 C.

alloy is lower than that of the other two alloys. Likewise, steady
creep rate, i.e., the minimum creep rate is a characteristic value
reecting the creep behavior of materials according to the creep
theory. The present study showed that steady-state creep rate is
characterized by the minimum creep rate of about 4.0  105 s1,
2.1  105 s1and 8.9  106 s1, in the entire alloys, respectively.
It can be seen that the steady state creep rate is drastically reduced
in case of SAC (205) 0.5Zn alloy when compared with the other
two solder alloys. From this comparison, it is evident that the

SAC (205) 0.5Zn solder showed much more creep resistant

(450%) than that of SAC (205) solder, while the SAC (205)
0.05Ni solder showed an increase of creep resistance of 190% only.
Assuming that the size, the type and morphology of precipitates affects the creep resistance, this result is credible when the microstructure is taken into account. It indicated that the increased
creep resistance of SAC (205) 0.05Ni or SAC (205) 0.5Zn alloys
is mostly attributed to the particle hardening of new (Cu,Ni)6Sn5
and Cu5Zn8 IMCs reinforced SAC (205) solder alloy. Similar trends
are also found for SAC solders by El-Daly and El-Taher [6], who
established that the creep resistance and creep life time of SAC
(105) alloys was remarkably enhanced (23 times) with minor

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A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

T = 25 C

T = 70 C

T = 110 C

= 18.1 MPa

-4

-4

SAC (205)
SAC (205) - 0.05 Ni
SAC (205) - 0.5 Zn

SAC (205)
-6

-6

Ln ( . )

n = 5.8

ln ()

-8
-10

-8

Q = 84.6 KJ/mol

-10

n = 6.9

Q = 88.3 KJ/mol

Q = 76.2KJ/mol

-12
-12

n = 7.8

-14

-14

-16
-0.3 -0.2 -0.1 0.0

0.2 0.3
Ln [ sinh ( ) ]

-6

0.4

0.5

2.6

0.6

2.8

n = 7.0

3.2

Table 4
Activation energy (Q) and stress exponent (n) values for SAC (205), SAC (205) 0.05Ni
and SAC (205) 0.5Zn solder alloys.

n = 7.9

Alloys

Q (kJ/mol)

Temperature (C)

a (MPa1)

SAC (205)

76.2

25
70
110

0.05578
0.06666
0.07558

7.8
6.9
5.8

SAC (205) 0.05Ni

84.6

25
70
110

0.05782
0.06771
0.07777

8.8
7.9
7.0

SAC (205) 0.5Zn

88.3

25
70
110

0.06363
0.07047
0.0790

9.7
8.0
8.3

n = 8.8

-14
-16
-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

Ln [ sinh ( ) ]
-4

SAC (205) - 0.5 Zn

-6

3.5. Constitutive creep equation and parameters

In order to understand the detailed creep mechanism of both alloys investigated, stress exponent (n) and activation energy (Q) of
deformation are calculated. It is generally accepted that the following sine hyperbolic equation, which combines the power law and
the exponential law in low- and high-stress ranges, respectively,
is suitable for constitutive analysis over wide ranges of deformation temperatures and strain rates [6]. The minimum creep rate
(e_ ) is related to the applied stress and temperature by means of
the conventional equation:

n = 8.3

-8

n = 8.0

-10
-12
-14

n = 9.7

e_ A sinharn expQ=RT

-16
-0.2

-0.1

0.0

3.4

1000/T (K) -1

-10
-12

ln ()

3.0

Fig. 9. Temperature dependence of steady state creep rate of the three solder alloys.

SAC (205) - 0.05 Ni

-8

ln ()

0.1

0.1

0.2

0.3

0.4

0.5

Ln [ sinh ( ) ]
Fig. 8. Relationship between ln [sinh (ar)] and ln (e_ ) for determination stress
exponent (n) values of SAC (205), SAC (205) 0.05Ni and SAC (205) 0.5Zn solder
alloys at T = 25, 70 and 110 C.

alloying additions of Ni and Sb. Besides, the present results also are
consistent with the testing results given by Che et al. [14] which
focused on two Ni doped solders of SAC (105) 0.02Ni and SAC
(105) 0.05Ni, and found that adding Ni particles to the SAC
(105) solder could improve the solder joint drop reliability, since
Ni additive could suppress the Cu3Sn IMC growth and improves
the solder microstructures and mechanical properties.

where A (s1), a (MPa1), are material constants independent of

temperature, a is stress level parameter, R is the universal gas constant, n is the stress exponent constant related to strain rate, T (K) is
thermodynamic deformation temperature; r (MPa) is the steady
state ow stress and Q (kJ/mol) is the activation energy of
deformation.
The logarithm was taken and Eq. (1) was rearranged:

ln e_ ln A n ln sinhar  Q =RT

where a is the stress reciprocal at which the material deformation

changes from power to exponential stress dependence. The value
of a was calculated by a = b/n1, where b and n1 are the average
slopes of ln (e_ )r lines and ln (e_ )ln (r) lines at constant T, respectively. The plots of ln (e_ )r and ln (e_ )ln (r) lines at temperature of
25, 70 and 110 C for three alloys are given in Figs. 6 and 7. The

796

A.A. El-Daly, A.M. El-Taher / Materials and Design 51 (2013) 789796

slope of the ln e_ against ln [sinh(ar)] plot then gave the value of n

(Fig. 8). The value of ln (A) could then be obtained from the intercept of the ln e_ against ln [sinh(ar)] plot and the activation energy
Q can be expressed as the slope of ln (e_ ) against 1/T (Fig. 9 and
Table 4).
For all lead-free solders, the calculated stress exponents decrease, respectively, from 9.7 to 5.8 as the temperature increases
from 25 to 110 C, and these were attributed to the instability of
the microstructure, which occurs during high temperature deformation [11]. Generally, three creep mechanisms can occur during
creep deformation, either independently of one another to some
approximation, or be accommodated by each other. These are grain
boundary sliding accommodated by grain shape changing, dislocation slip, and diffusional creep. The stress exponent n  2 is usually
reported for grain boundary sliding, while n = 49 is generally reported for dislocation climb controlled creep [6]. However, the observed difference in n values suggests that creep deformation in
the solder alloy is inuenced by the precipitate hardening effects
of IMCs that could restrict the dislocation climbing during creep.
Nevertheless, dislocation climbing is controlled by the dislocation
pipe diffusion or lattice self-diffusion depending on the activation
energy of SAC (205) solders. In the present study, the activation energy of SAC (205) for corresponding strain rate, temperature and
strain level was found to be 76.2 kJ/mol, which is slightly increased
to 84.6 and 88.3 kJ/mol with Ni and Zn additions, respectively.
These Q values of creep deformation are close to the activation energy reported for dislocation pipe diffusion of b-Sn, and are almost
less than the value of lattice diffusion (approximately 100 kJ/mol)
[20]. Accordingly, dislocation-climb process around particles is
proposed as the dominant creep mechanism. The variations in Q
and n values with the other reported values can be explained by
differences in testing methods, microstructure, specimen preparation, measuring errors, and data processing method. The anisotropy of Sn unit cell and the differences in microstructural
features suggest that wide range of values for both n and Q is expected. Deformation mechanisms in the particle-strengthened or
multiphase eutectic structures of the Pb-free alloys may thus be
similar to those observed in pure tin, but operate at higher stress
than in pure Sn. However, the creep strain rate of SAC (205), SAC
(205) 0.05Ni and SAC (105) 0.5Zn alloys, respectively, can be
estimated from the constitutive equations represented by:

e_ 3:7  104 sinh0:0659r6:8 exp

e_ 2:8  104 sinh0:0677r7:9 exp
e_ 5:5  104 sinh0:0710r8:6 exp




76:2
RT
84:6
RT


3




88:3
RT

The steady-state creep strain rate and some temperatures can

be accurately predicted for the three solders by Eqs. (3)(5), since
the three equations give a good t for the temperature normalized
creep strain rate vs. the stress data.

4. Conclusions
Following conclusions can be made based on the results:
(1) The microstructure of SAC (205) solder is drastically changed
after Ni and Zn additions. Addition of Ni enlarges the primary b-Sn dendrites and changes g-Cu6Sn5 into (Cu,Ni)6Sn5
IMC particles. However, the addition of Zn into SAC (205)
solder leads to reduce the average size of b-Sn grains and
enhanced the formation of Cu5Zn8 IMC particles.

(2) The addition of small amounts of Ni and Zn tends to be associated with small undercooling, since such elements may
serve as extra heterogeneous nucleation sites and promote
solidication process.
(3) Signicant improvement in creep resistance of 190% and
450% is realized for Ni and Zn-containing SAC (205) alloy,
respectively, when compared with the SAC (205) solder
alloy. The improvement in creep properties obtained was
due to alloying element addition owing to the formation of
new (Cu,Ni)6Sn5 and Cu5Zn8 IMCs reinforced SAC (205) solder alloy. The Cu5Zn8 IMC in SAC (205) 0.5Zn is found to
be effective in retarding the dislocation motion during creep
and then enhances the creep resistance property.
(4) According to the obtained stress exponents and activation
energies, it is proposed that the dominant deformation
mechanism in SAC (205) solders is dislocation climb over
the whole temperature range investigated.

References
[1] El-Daly AA, Mohamad AZ, Fawzy A, El-Taher AM. Creep behavior of nearperitectic Sn5Sb solders containing small amount of Ag and Cu. Mater Sci Eng
A 2011;528:105562.
[2] Luo ZB, Zhao J, Gao YJ, Wang L. Revisiting mechanisms to inhibit Ag3Sn
plates in SnAgCu solders with 1 wt.% Zn addition. J Alloys Compd
2010;500:3945.
[3] Choi H, Lee TK, Kim Y, Kwon H, Tseng CF, Duh JG, et al. Improved strength of
boron-doped Sn1.0Ag0.5Cu solder joints under aging conditions.
Intermetallics 2012;20:1559.
[4] Zhang Y, Zhu H, Fujiwar M, Xua J, Dao M. Low-temperature creep of SnPb and
SnAgCu solder alloys and reliability prediction in electronic packaging
modules. Scripta Mater 2013;68:60710.
[5] El-Daly AA, Swilem Y, Hammad AE. Creep properties of SnSb-based lead-free
solder alloys. J Alloys Compd 2009;471:948.
[6] El-Daly AA, El-Taher AM. Improved strength of Ni and Zn-doped Sn2.0Ag
0.5Cu lead-free solder alloys under controlled processing parameters. Mater
Des 2013;47:60714.
[7] Gain AK, Chan YC, Yung WKC. Microstructure, thermal analysis and hardness
of a SnAgCu-1 wt% nano-TiO2 composite solder on exible ball grid array
substrates. Microelectron Reliab 2011;51:97584.
[8] Ventura T, Terzi S, Rappaz M, Dahle AK. Effects of solidication kinetics on
microstructure formation in binary SnCu solder alloys. Acta Mater
2011;59(4):164851.
[9] Gao L, Xue S, Zhang L, Sheng Z, Ji F, Dai W. Effect of alloying elements on
properties and microstructures of SnAgCu solders. Microelectron Eng
2010;87:202534.
[10] Zhu F, Zhang H, Guan R, Liu S. Effects of temperature and strain rate on
mechanical property of Sn96.5Ag3Cu0.5. J Alloys Compd 2007;438:
10095.
[11] El-Daly AA, Hammad AE, Fawzy A, Nasrallh DA. Microstructure, mechanical
properties, and deformation behavior of Sn1.0Ag0.5Cu solder after Ni and Sb
additions. Mater Des 2013;43:409.
[12] Zhang XP, Yu CB, Zhang YP, Shrestha S, Dorn L. Processing treatment of a
lead-free SnAgCuBi solder by rapid laser-beam reowing and the creep
property of its soldered connection. J Mater Process Technol 2007;192
193:53942.
[13] Zhang L, Xue SB, Gao LL, Zeng G, Chen Y, Yu Sl, et al. Creep behavior of SnAgCu
solders with rare earth Ce doping. Trans Nonferr Met Soc China
2010;20:4127.
[14] Che FX, Zhu WH, Poh Edith SW, Zhang XW, Zhang XR. The study of mechanical
properties of SnAgCu lead-free solders with different Ag contents and Ni
doping under different strain rates and temperatures. J Alloys Compd
2010;507:21524.
[15] Wang M, Wang J, Feng H, Ke W. In-situ observation of fracture behavior of Sn
3.0Ag0.5Cu lead-free solder during three-point bending tests in ESEM. Mater
Sci Eng A 2012;558:64955.
[16] Nogita K, Nishimura T. Nickel-stabilized hexagonal (Cu,Ni)6Sn5 in SnCuNi
lead-free solder alloys. Scripta Mater 2008;59:1914.
[17] El-Daly AA, Hammad AE. Enhancement of creep resistance and thermal
behavior of eutectic SnCu lead-free solder alloy by Ag and In-additions. Mater
Des 2012;40:2928.
[18] Chinnam RK, Fauteux C, Neuenschwander J, Janczak-Rusch J. Evolution of the
microstructure of SnAgCu solder joints exposed to ultrasonic waves during
solidication. Acta Mater 2011;59:147481.
[19] Chen WM, Kang SK, Kao CR. Effects of Ti addition to SnAg and SnCu solders. J
Alloys Compd 2012;520:2449.
[20] Geranmayeh AR, Nayyeri G, Mahmudi R. Microstructure and impression creep
behavior of lead-free Sn5Sb solder alloy containing Bi and Ag. Mater Sci Eng A
2012;547:1109.