Materials Science & Engineering A 578 (2013) 6271

Contents lists available at SciVerse ScienceDirect

Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Novel SiC nanoparticles-containing Sn1.0Ag0.5Cu solder with good

drop impact performance
A.A. El-Daly a,n, A. Fawzy b, S.F. Mansour a, M.J. Younis c
a

Physics Department, Faculty of Science, Zagazig University, Zagazig, Egypt

Physics Department, Faculty of Education, Ain Shams University, Cairo, Egypt
c
Physics Department, Faculty of Science, Islamic University of Gaza, Gaza, Palestine
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 22 January 2013
Received in revised form
7 March 2013
Accepted 5 April 2013
Available online 25 April 2013

In this study, the SiC nanoparticles were successfully fabricated by high energy ball milling. Mechanical
mixing technique has been used to disperse nanometric SiC in Sn1.0Ag0.5Cu (SAC105) solder at 450 1C
for 2 h. In comparison with SAC(105) solder, the addition of SiC nanoparticles can effectively increase the
primary -Sn phase and decrease the percentage of Ag3Sn and Cu6Sn5 IMC particles, which produce a
weak interface with the -Sn matrix. The formation of few numbers of IMC particles, together with the
weak interface have resulted in slight decrease of ultimate tensile strength (UTS), 0.2% yield strength
(0.2%YS) and elastic modulus, whereas the ductility has improved. The improved plasticity is due to the
structural renement of the sub-grain sizes of primary -Sn phases, which makes the composite solder to
display large elongation. The addition of SiC nano-sized particles can also effectively reduce the
undercooling and pasty range, while the melting temperature is maintained at the SAC105 level,
indicating that the novel composite solder is t for existing soldering process. These effects could
increase the elastic compliance and plastic energy dissipation ability of the bulk solder, which play an
important role in drop impact performance enhancement.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Lead-free composite solders
SnAgCu alloys
Microstructure
Mechanical properties

1. Introduction
The development of lead-free solders has become impartment
for material researchers due to health and environmental concerns
regarding the high toxicity of lead [1]. The high Ag-content SnAg
Cu alloys are considered one of the most popular solders for
surface mount technology (SMT), chip scale package (CSP) solder
interconnects and ball grid array (BGA) applications [2]. Because of
the rigidity of high Ag-content SnAgCu alloys, compared with
the SnPb solder alloy, more drop and high impact failures have
been observed for these replacement alloys in mobile electronics
[3]. In addition, their high joint strength often yields a serious chip
joining problem such as chip-to-package interaction (CPI) or white
bump defects in a back-end-of-line (BEOL) structure. Consequently, the performance of SAC solder joints under high strain
rate and large temperature range typical of drop impact situations
is a major concern. To solve these problems, efforts have been
made to develop solders with low Ag or Cu content. Reducing the
Ag content of the SAC alloys, such as Sn1.0Ag0.5Cu (SAC105)
alloy gives rise to more primary -Sn phase (large -Sn grains) and

n
Corresponding author. Tel.: +20 552303252 (Univ.), +20 552362536 (Faculty),
+20 1271020082 (mobile); fax: +20 552308213.
E-mail addresses: dreldaly11@yahoo.com, dreldaly@zu.edu.eg (A.A. El-Daly).

0921-5093/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2013.04.022

decreases the number of Ag3Sn IMC particles. It is therefore

expected to result in lower elastic modulus and lower yield
strength than the high Ag content SAC alloys. This, in turn
increases the elastic compliance and plastic energy dissipation
ability of the bulk solder, which are the key factors to enhance the
drop resistance [4]. The other reason is ofcourse they are less
expensive due to their lower silver content.
However, most of the existing studies are focused on low
Ag-content SAC alloys doped with fourth alloying elements such
as Ni, Mn, Ce, Ti, In, Cr, and Al with specic applications [5,6].
Shnawah et al. [7] investigated the drop reliability of SAC(105)
alloys with small additions (0.1 and 0.3 wt%) of Fe and demonstrated that the addition of Fe leads to formation of large FeSn2
IMC particles, together with the presence of large primary -Sn
grains, which resulted in signicant reduction of the elastic
modulus and yield strength, with maintaining the total elongation
at the SAC105 level. This effect could increase the elastic compliance and plastic energy dissipation ability of the bulk solder,
which play an important role in drop impact performance
enhancement. Previous studies [8,9] demonstrated the signicantly enhanced fracture resistance of SAC105 compared
with the high-Ag alloy (SAC405) when suffering drop impact.
They found that the drop performance of SAC105 is 10 times
higher than that of SAC(405) if a 5% failure rate is operationally
dened as the onset of failure. Iyer et al. [10] investigated the drop

A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

reliability of BGA packages with SAC(105) and SAC(305) alloys and

revealed that the number of drops to failure of SAC(105) was 45%
higher than that of SAC(405).
One of the new methods for microstructure enhancement and
correspondingly improvement of the mechanical properties of
metals and alloys is the modication with nano- and micronsized particles [11,12]. Most of the nano-modiers have low
wetability and hence they are difcultly moistened by the molten
solders. The introduced nano-modiers form the self-organized
dispersive systems, which contribute to the heterogeneous nucleation. As a result, it causes signicant changes in the microstructure
formation process. It is supposed that the self-organized dispersive
nano-modiers could control the melt crystallization [13] but
however, a limited number of studies are available about the exact
mechanisms responsible for the improvement of the mechanical
properties of the nano-modied alloys. For example, Nai et al. [14]
investigated the effects of nano-size alumina and tin oxide
particulates addition on the physical, microstructural, and
mechanical properties of Sn0.7Cu and Sn3.5Ag lead-free solders.
They found that the best tensile strength was realized for composite solders reinforced with 1.5 vol% alumina and 0.7 vol% tin oxide
particulates, which far exceeds the strength of eutectic SnPb
solder. The same study also revealed that morphology of pores was
observed to be one of the most dominating factors affecting the
strength of materials. To the best of our knowledge, there is still
lack of data about the inuence of the nano-sized SiC particles on
the microstructure, thermal behavior and mechanical properties of
SAC(105) for soldering application [15,16]. The effect of SiC is
expected to be signicant because the SiC has no solubility in the

63

-Sn matrix. Thus, the aim of this study is to investigate the

inuence of nano-sized SiC particles addition on the microstructure, thermal behavior, and mechanical properties of SAC(105)
solder alloy. The test conditions cover the temperature range and
strain rates, which are important for assessment of the solder joint
reliability. The key factors that affect the mechanical behavior of
the solder alloy are discussed.

2. Experimental procedures
2.1. Preparation of SiC nanoparticles
The SiC microparticles (99.99% purity) with an average particle
size of 10 m and density of 3.21 g/cm3 were used as raw material.
The morphology of powder is shown in Fig. 1(a). The -SiC
particles (hexagonal Bravais lattice) of the 6H type were polygonal
in shape. To produce nano-SiC powder with average particle size
less than70 nm, the milling process was carried out at room
temperature and argon atmosphere (with purity of 99.999%) using
hardened steel balls in high-energy attrition mill (Union Process,
model1-S).The ball-to-powder weight ratio and rotational speed
were 20:1and 320 rpm, respectively. The nal product (50 h of
milling) of the SiC powder was then examined by TEM and X-ray
diffraction patterns. Fig. 1(b and c) shows TEM micrograph and the
XRD of SiC nanoparticles. The TEM micrograph and the observed
peak broadening in XRD conrm the generation of nanometric
sized particles. The crystal size of milled SiC powders (70 nm) was
quantied by XRD peak broadening using WilliamHall method

Fig. 1. Microstructure of: (a) as-received SiC microparticles, (b) TEM of SiC nanoparticles and (c) XRD of SiC nanoparticles.

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A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

[11]. However, a detailed examination shows small-scale clustering of SiC particles in some local areas of the matrix, as seen in the
inset on the upper right of Fig. 1(b).
2.2. Preparation of SiC/Sn1.0Ag0.5Cu composite solders
The chemical compositions of both solder alloys are listed in
Table 1. The SAC(105) solder was prepared from bulk Sn, Ag and Cu
rods (all with 4 N purity). The process of melting was carried out
in a vacuum arc furnace under the protection of high purity argon
atmosphere at 450 1C for about 2 h. In order to get a homogeneous
composition within the ingots, the alloy was re-melted three times
to produce rod-like specimen with a diameter of about 1.5 cm.
The SAC(105)0.75SiC composite solder was prepared by
mechanically mixing SiC particles (with an average size of
70 nm) into the SAC(105) alloy melt. During preparation, the
pre-weighted ingot and SiC particles were rst put into an Al2O3
crucible and then was heated up to 450 1C. After that, an electromagnetic stirrer was activated to mechanically mix the SiC
particles into the melt for 40 min to ensure a homogeneous
distribution of the reinforcing particles. Finally it was casted with
an air-cooling condition of 8.5 1C s1, so as to create the ne
microstructure typically found in small solder joints in microelectronic packages.

alcohol was prepared and used to etch the samples. Energy

Dispersive X-ray Spectrometry (EDS) was adopted to identify the
phase structure of the prepared composite solder. The solder
ingots were then mechanically machined into a wire samples with
a gauge length marked 4
102 m for each samples and
2.5
103 m in diameter, as developed in our previous work [1].
To obtain samples containing the fully precipitated phases and free
from any plastic strain accumulation during machining, the
samples were annealed at 120 1C for 30 min, then left to cool
slowly to room temperature. Thermal behaviors of two solder
alloys were examined by differential scanning calorimetry (DSC) in
argon atmosphere. The heating and cooling rates were 5 1C min1
and the testing temperature range was 50260 1C. The tensile tests
were conducted with (Instron 3360 Universal Testing Machine) at
temperature range of 25120 1C for both solders, under different
strain rates of 105 s1103 s1. Each datum represents an average
of three measurements. The environment chamber temperature
could be monitored by using a thermocouple contacting with
specimen.

3. Results and discussion

3.1. Microstructure of plain SAC(105) and SAC(105) composite
solders

2.3. Characterization
The microstructure was examined by scanning electron microscopy (SEM). A solution of 2%HCl, 3%HNO3 and 95%(vol%) Ethyl
Table 1
Chemical composition of the solders studied (wt%).
Alloy

Cu

Ag

Fe

As

SiC

Sb

In

Sn

SAC(105)
SAC(105)0.75SiC

0.505
0.506

1.002
1.001

0.003
0.003

0.001
0.001

0.000
0.760

0.014
0.014

0.003
0.005

Bal.
Bal.

Fig. 2 shows the low- and high-magnications backscattered

scanning electron micrographs of SAC105 solder and solder containing 0.75 wt% SiC nano-particles. In the microstructure of SAC
(105), a relatively coarse primary -Sn matrix with an average size
of 70 m and the ne IMC particles appeared sparsely within the
matrix, as shown in Fig. 2(a). To reveal the IMC morphology better,
the magnied micrograph of the eutectic region in SAC(105) bulk
solder is shown in Fig. 2(b). Using EDS analysis, the ne bright
ber-like particles are identied as Ag3Sn IMCs with the spacing
between them of about 2 70.7 m. The small gray dispersoids
particles are identied as Cu6Sn5 IMC with an average size of

sub-grain -Sn
-Sn
Ag3Sn

Cu6Sn5

Eutectic

-Sn

-Sn
Cu6Sn5

Ag3Sn
Eutectic

-Sn
sub-grain -Sn

Fig. 2. Low- and high-magnication backscattered scanning electron micrographs of: (a and b) SAC105 solder, (c and d) SAC(105)0.75SiC solder.

A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

7 70.5 m. It is interesting to note that the Cu6Sn5 particles are

dispersed within the eutectic area as well as the -Sn matrix, and
thus would improve the mechanical strength. Besides, the small
primary sub-grains of -Sn with an average size of 15 73 m
appeared sparsely within the -Sn matrix.
To study the inuence of SiC nanoparticles on the morphology
of SAC(105) solder, we will propose an optimized composition of
SAC(105) alloys, which will avoid the formation of large volume
fraction of IMCs, both at the same cooling rate. Fig. 2(c and d)
shows the morphology of SAC(105) composite solder. Worthy of
notice is that the -Sn-rich phases became larger, and the average
size of more Cu6Sn5IMCs is decreased with the addition of SiC
nanoparticles. Especially, the rened Cu6Sn5 particles are dispersed only within the eutectic area. The volume fraction of the
Ag3Sn IMC particles in the eutectic area also tends to decrease and
the interparticle distance tends to increase with the addition of SiC
nanoparticles. As mentioned at the beginning, it has been a fact
that reducing the IMC particles in the SAC solder could improve
the drop impact reliability. These trends are consistent with the
theory of heterogeneous nucleation [16] that the rapid increase in
adsorption elements decreases the surface energy and therefore
decreases the growth velocity of IMCs. The SiC nanoparticles have
been found to control the melt crystallization of SAC(105) solder.
In other words, the reinforcing SiC particles can generate smaller
sub-grain size (9 7 1 m) than the SAC(105) solder (15 72 m).
However, it is expected that these small sub-grains could be one of
the exact mechanisms responsible for improvement of the
mechanical properties of the nano-modied alloy.
The high-magnication SEM micrograph in Fig. 3(a) presents
the conguration of SAC(105)0.75SiC composite solder. In
Fig. 3(b), it was observed that there is a partial de-bonding
occurring at the interface between Ag3Sn and the -Sn solder
matrix. However, for SAC(105) based alloys, unlike the large solid
solubility of Cu and Ag in -Sn, the extremely non solid solubility
of SiC in -Sn limits its diffusion. Hence, the mass of defects
(e.g. dislocations and vacancies) at the interface boundary could

65

Fig. 4. DSC results during heating (endothermal) and cooling (exothermal) of (a)
SAC(105) and (b) SAC(105)0.75SiC solders.

A g 3 Sn
Cu 6 Sn5
de-bonding
+

Spectrum 1

sub-grain -Sn

Fig. 3. High-magnication backscattered scanning electron micrographs of: (a) SAC(105)0.75SiC solder, (b) de-bonding occurring at the interface between Ag3Sn and -Sn
solder matrix, (c) formation of -Sn sub-grains and (d) EDS analysis of Cu6Sn5 IMCs.

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A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

enhance the diffusion of SiC along the interface boundaries. Most

notably, the small primary -Sn sub-grains are formed and small
particles of Ag3Sn and Cu6Sn5 IMCs are sparsely distributed within
the eutectic area as shown in Fig. 3(c), and conrmed with EDS
analysis shown in Fig. 3(d).
3.2. Thermal analysis
DSC analysis was carried out to investigate the fundamental
thermal reactions during heating and cooling of these alloys. Fig. 4
shows the typical DSC curves obtained for both alloys. The DSC
results are summarized in Tables 2 and 3. The melting temperature
of SAC(105) was 226.5 1C. During heating process, one may notice
that there was an elevated melting temperature less than 1.0 1C for
the SAC(105) solder reinforced with SiC nanoparticles. Wang et al.
[16] also reported that the addition of small amount of SiC
particles (with an average size of 1 m) did not signicantly affect
the melting point of Sn3.7Ag0.9Zn alloy. The slight increase in
the melting point of the composite solder could be possibly
attributed to the change in the surface instability and the variation
in physical properties of grain boundary/interfacial characteristics,
which could raise the melting point of SAC(105)0.75SiC solder.
The pasty range of SAC(105) and SAC(105)0.75SiC solders was
11.5 and 9.7 1C, respectively. That means, the pasty range was
improved with SiC nano-particles addition.
Undercooling is one of the critical factors that will inuence the
growth of IMCs. Thermodynamically, the larger the undercooling
is, the larger the driving force for the IMCs growth [17]. In the
onset-to onset method, undercooling is dened as the difference
between the Tonset during heating and Tonset associated with
cooling, and relates to the difculty of nucleating the solid phase
in a liquid state [1]. Due to undercooling, the exothermal peaks
upon cooling for both alloy samples appeared at lower temperature compared with their endothermal peaks, but the reductions
in temperature were not identical as seen in Fig. 4 and Table 3. It is
worthy of notice that the degree of undercooling for SAC(105)
solder was strongly decreased from 18.6 to 15.4 1C with SiC nanoparticles addition. In this case, the decrease in the -Sn undercooling could inhibit the IMCs formation in the SAC(105) alloys.
SiC nano-particles could act as additional nucleation sites. If higher
nucleation is induced, the rate of solidication of -Sn will be
faster and this will further reduce the time allowed for the Ag3Sn
formation to grow [17]. Alternatively, faster nucleation of the -Sn
phase evidently also promotes the growth of larger amount of -Sn

sub-grains in the bulk solder. This could be the reason why very
ne sub-grains were observed in the SAC(105)0.75SiC-solidied
samples (Fig. 2c). These results are quite consistent with the
explanation proposed by Song et al. [18] that the primary IMCs
might act as heterogeneous nucleation sites for Sn dendrites upon
solidication and are able to suppress the undercooling of SnAg
Cu alloys. This phenomenon also appeared in SAC(305) and SAC
(105) solders [19].
3.3. Tensile tests
Tensile testing analysis indicates the inuence of SiC nanoparticles on the room temperature tensile properties of SAC(105)
nano-composite solders at constant strain rate of 2
103 s1.
In each case, the average values of three different samples are
subjected to tensile testing. Fig. 5 shows the typical tensile stress
strain curves of the SAC(105) nanocomposite solder specimens.
The average values of UTS, 0.2YS, and percentage of elongation are
listed in Table 4. The UTS and 0.2YS values of SAC(105) solder were
31.2 MPa and 30.5 MPa, respectively. The addition of SiC nanoparticles had slight effect on the strength of SAC(105) nano-composite
solder, which decreased modestly. The SiC-containing solder
possess elastic modulus, UTS and 0.2% YS strength that are
approximately 18.3%, 12.5% and 18.0% respectively, lower than
those of the SAC(105) solder. At the same time, the total elongation
of SAC(105)0.75 SiC is approximately 30% higher than those of
SAC(105) solder. This means that, the SiC reinforcing SAC(105)
solder with higher elastic compliance are expected to exhibit
longer strain to failure (i.e., higher drop resistance) than the SAC
(105) with lower elastic compliance, under high strain loading
conditions. The higher ductility in the composite solder could be
attributed to the fact that the sub-grain sizes of primary -Sn
phases are ner in the composite solder than in the SAC(105)

Table 2
Comparison of solidus temperature (Tonset), liquidus temperature (Tend), pasty
range and melting temperature for SAC(105) and SAC(105)0.75SiC solder alloys
from heating curve.
Alloy

Tonset
(1C)

SAC(105)
215.1
SAC(105)0.75SiC 217.9

Tend
(1C)

Pasty range
(TendTonset) (1C)

Melting
temperature (1C)

226.6
227.6

11.5
9.7

226.5
227.3

Table 3
Comparison of undercooling range for SAC(105) and SAC(105)0.75SiC solder
alloys.

Alloy
SAC(105)
SAC(105)
0.75SiC

Fig. 5. Comparative tensile stressstrain curves obtained at T 25 1C and

2
103 s1 for SAC(105) and SAC(105) 0.75SiC solders.

Table 4
Tensile properties of SAC(105) and SAC(105)0.75SiC solder alloys.

(Tonset)
cooling (1C)

Undercooling
(ThTc) (1C)

Alloy

Elastic modulus
(GPa)

UTS
(MPa)

0.2%YS
(MPa)

Elongation
(%)

215.1

196.5

217.9

202.5

18.6
15.4

SAC(105)
SAC(105)
0.75SiC

30
24.5

31.2
27.3

30.5
24.6

14.9
19.6

(Tonset)
heating (1C)

A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

solder. It is well known that, the microstructural characteristics of

an alloy determine its mechanical performance. According to
Figs. 2 and 3, the SiC additions to the SAC(105) solder lead to the
formation of large primary -Sn phase and few numbers of Ag3Sn
and Cu6Sn5 IMC particles in the bulk solder. The high fraction of
the primary -Sn phase reduces the elastic modulus and yield
strength, which produce a soft and highly compliant bulk solder.
On the other hand, the effect of low numbers of Ag3Sn and Cu6Sn5
IMC on the mechanical properties of SAC(105)0.75 SiC is smaller
than that of the SAC(105) solder [3,7]. Moreover, the SiCreinforcing solder has also been shown to cause de-bonding at
the interface between Ag3Sn and the -Sn solder matrix due to the
agglomerated SiC particles around Ag3Sn IMC. Sequentially, these
properties can further increase the bulk compliance and the plastic
energy dissipation ability of the solder joints, which play an
important role in drop impact performance enhancement.

67

3.4. Fracture surface analysis

The fracture surfaces of the tensile specimens of SAC(105) and
SAC(105)0.75SiC solders tested at room temperature and strain rates
of 103 s1 are shown in Fig. 6(a and b). Obviously, the characteristic
of dimples is observed on the fracture surfaces of specimens with
and without SiC nanoparticles addition, indicating that these alloys
worked in a highly ductile manner. It is well known that the dimples
are a result of micro-voids coalescence. For the typical cup and cone
fracture mode that normally happens in ductile materials, the
dimples are normally equiaxed in shape as can be seen in both alloy
samples. In general, the larger and deeper dimple is, the better plastic
property is [20,21]. Accordingly, the fracture surfaces of SAC(105)
solder containing SiC nano-particles appeared to be more ductile
with very rough dimpled surfaces than SAC(105) solder due to the
uniform distribution of SiC nano-particles. That means, the plastic

Fig. 6. SEM fractrograph for (a) SAC(105) and (b) SAC(105)0.75SiC solders.

Fig. 7. Effect of strain rate on: ultimate tensile strength (UTS), yield stress (YS) and total elongation for SAC(105) and SAC(105)0.75SiC solders at 70 1C.

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A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

property of the investigated specimens becomes privileged with

adding SiC nanoparticles.
3.5. Effect of strain rate on the mechanical properties
Fig. 7 shows the effect of strain rate on UTS, YS and percentage
of elongation of both solder alloys at 70 1C. The entire alloys
displayed an increase in both UTS and 0.2YS with increasing strain
rate, indicating that the tensile behavior of the two solder alloys is
strain rate dependant. It can be observed that the SiC-containing
solder possess lower strength and higher ductility levels than the
SAC(105) solder alloy. From this aspect, the mechanism study
indicated that the SAC(105)0.75SiC solder would generate better
bulk compliance and higher plastic energy dissipation ability
compared to SAC(105) solder, which enhanced fracture resistance
under different strain rate conditions.
3.6. Effect of temperature on the mechanical properties
It is well known that the mechanical behavior at different
temperatures was also dened as a very crucial thermomechanical property. Fig. 8 shows the effect of temperature on
the tensile properties of each solder at strain rate of 6
104 s1. It
can be seen that the UTS and 0.2YS of the two solders decrease
constantly with increasing temperature. The UTS and 0.2YS of SAC
(105)0.75SiC solder are approximately 15.6 and 16.7% smaller
than that of SAC(105) alloy. Although the difference in the UTS and
0.2YS values is nearly constant at all the temperature range, the
ductility as measured by percent elongation has increased with
the addition of SiC nanoparticles. Similar trends in the variation of
strength and ductility with test temperature have been observed
in other soft solder materials [12,13]. Since the Ag3Sn and Cu6Sn5

IMC particles possess much higher strength in the bulk material of

SAC(105) alloy, while primary -Sn has the lowest elastic modulus
and lowest yield strength among the constituent phases of SAC
(105) solder [7], it is suggested that the low strength properties of
SAC(105)0.75SiC can be attributed to more primary -Sn in the
bulk solder and few number of IMC particles in the bulk alloy
matrix, resulting in good drop impact performance ( see Fig. 2).
However, the reduced ductility in the composite solder at 120 1C
suggests that the interface between the SiC and the matrix is
slightly affected at higher temperatures, which then enhanced the
load transfer to the SiC particles in the composite solder. Under
this circumstance, the SiC particles can act as barriers that slow
down the diffusion process required for proper recovery.
3.7. Kinetic analysis of SAC(105)-based solders during hot
deformation
In the present investigation, Arhenius constituent model relating strain rate, temperature and activation energy with ow stress
during hot deformation is expressed as described elsewhere [1].
Asinhsn expQ =RT
1

where A (s ), (MPa ), are material constants independent of

temperature, 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, s (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 ln A nlnsinhsQ =RT

The value of represents the stress reciprocal at which the

material deformation changes from power to exponential stress
dependence. An approximate value of was calculated by /n1,

Fig. 8. Effect of temperature on; ultimate tensile strength (UTS), yield stress (YS) and total elongation for Sn SAC(105) and SAC(105)0.75SiC solders at strain rate of
6
104 s1.

A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

Fig. 9. Relationship between s and ln() at (a) T 25, (b) T 70 and (c) T 120 1C for SAC(105) and SAC(105)0.75SiC solders.

Fig. 10. Relationship between ln(s) and ln() at (a) T 25, (b) T 70 and (c) T 120 1C for SAC(105) and SAC(105)0.75SiC solders.

69

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where and n1 are the average slopes of ln()s and ln()ln(s)

lines at constant T, respectively. The plots of ln()s and ln()ln(s)
lines at temperature of 25, 70 and 120 1C for the two alloys are
given in Figs. 9 and 10. As seen in Table 5, stress exponent values
n calculated from the slope of the ln against ln[sinh(s)] plot for
varying temperature are in the range of 5.58.0 for both alloys
(Fig. 11). The n values are consistent with dislocation core
diffusion-controlled climb [21]. A signicant decrease in n value
with increasing temperature has been related to the instability of
the microstructure, which occurs during high temperature deformation [22]. The difference in elastic moduli and thermal mismatch between matrix and hard ceramic nanoparticles may cause
local static stress in the form of interfacial crack, prior-particle
boundary cracks and particle de-bonding. At higher temperatures,
the amount of heat generated due to hot deformation is very high.
The heat generated during deformation could not be dissipated
throughout the material due to the higher strain rate, and which
causes the local static stress in the matrix [16].
The activation energy Q can be expressed as the slope of ln()
against 1/T (Fig. 12). The activation energy of both alloys for

corresponding strain rate, temperature and strain level was found

to be 4044 kJ/mole, in consistent with Q4065 kJ/mole for Sn
self-diffusion through dislocation cores [21], and is almost half the
value of that for lattice diffusion (approximately 100 kJ/mol) [22].
Therefore, the tensile deformation mechanism is dislocation core
diffusion-controlled climb. Accordingly, the addition of SiC nanoparticles apparently increased the barrier to Ag3Sn and Cu6Sn5
IMCs formation, and may have enhanced the solubility of Cu and
Ag in SAC(105)0.7SiC solder. Hence, it can suppress the growth of
Ag3Sn and Cu6Sn5 IMCs, yielding low volume fraction of these
IMCs particles.

Table 5
Activation energy (Q) and stress exponent (n) values for SAC(105) and SAC(105)
0.75SiC solder alloys.
Alloy

Q (kJ/mol)

Temperature (1C)

(MPa1)

SAC(105)

44.0

SAC(105)0.75SiC

40.0

25
70
120
25
70
120

0.04100
0.05556
0.07778
0.03415
0.06000
0.07500

8.0
7.4
6.0
7.5
6.4
5.5
Fig. 12. The activation energy (Q), values of SAC(105) and SAC(105)0.75SiC solders.

Fig. 11. Relationship between ln[sin h (s)] and ln() for determination stress exponent (n) values at (a) T 25, (b) T 70 and (c) T 120 1C for SAC(105) and
SAC(105)0.75SiC solders.

A.A. El-Daly et al. / Materials Science & Engineering A 578 (2013) 6271

By determining A, Q, n and values for SAC(105) and SAC(105)

0.7SiC alloys, the creep strain rate, respectively, can be estimated
from the constitutive equations represented by:


44:0
3
2:8
105 sinh0:05811s7:1 exp
RT


44:0
2:8
104 sinh0:05638s6:5 exp
RT

71

(7) According to the obtained stress exponents and activation

energies, it is proposed that the dominant deformation
mechanism in both solders is the dislocation core diffusioncontrolled climb over the whole temperature range
investigated.

Eqs. (3) and (4) give a good t for the temperature normalized
tensile strain rate versus the stress data. Hence, the steady-state
strain rate and some temperatures can be accurately predicted for
both solders by Eqs. (3) and (4).
4. Conclusion
Following conclusions can be made based on the results:
(1) The addition of SiC nanoparticles apparently increased the
barrier to Ag3Sn and Cu6Sn5 IMCs formation and leads to the
formation of large primary -Sn grains.
(2) The SiC nanoparticles have been found to control the melt
crystallization of SAC(105) solder. For that reason, the SiCcontaining solder displayed smaller sub-grain size (107 5 m)
than the SAC(105) solder (15 75 m).
(3) The pasty range and the undercooling are decreased with
addition of the SiC nano-sized particles into SAC(105) alloy,
although the melting temperature is maintained at the
same level.
(4) The improved plasticity of SAC(105)0.7SiC composite solder is
due to the structural renement of sub-grain sizes of primary
-Sn, which makes the composite solder to display large total
elongation. In addition, the fracture surfaces of SAC(105)
solder containing SiC nano-particles appeared to be more
ductile with very rough dimpled surfaces than SAC(105) solder
due to the uniform distribution of SiC nano-particles.
(5) The drop impact performance improvement of SAC(105)
0.7SiC over SAC(105) is attributed to the formation of few
numbers of IMC particles, together with the weak interface
formed with the large -Sn matrix, which resulted in a slight
decrease of UTS, 0.2%YS and elastic modulus of the composite
solder.
(6) Both the temperatures and strain rates were found to have a
signicant effect on the strengths of SAC(105) and SAC(105)
0.7SiC composite solders.

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