Materials and Design 32 (2011) 47204727

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Materials and Design

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

Effect of addition of TiO2 nanoparticles on the microstructure, microhardness

and interfacial reactions of Sn3.5AgXCu solder
S.Y. Chang a, C.C. Jain b, T.H. Chuang b, L.P. Feng c, L.C. Tsao c,
a

Department of Mechanical Engineering, National Yunlin University of Science & Technology, Touliu, Yunlin 64002, Taiwan
Department of Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan
c
Department of Materials Engineering, National Pingtung University of Science & Technology, Neipu, Pingtung 91201, Taiwan
b

a r t i c l e

i n f o

Article history:
Received 16 February 2011
Accepted 21 June 2011
Available online 1 July 2011
Keywords:
A. Non-ferros metals and alloys
D. Brazing and soldering
F. Microstructure

a b s t r a c t
In this work, TiO2 nanoparticles were successfully incorporated into Sn3.5Ag and Sn3.5Ag0.7Cu solder, to
synthesize novel lead-free composite solders. Effects of the TiO2 nanoparticle addition on the microstructure, melting property, microhardness, and the interfacial reactions between Sn3.5AgXCu and Cu have
been investigated. Experimental results revealed that the addition of 0.5 wt.% TiO2 nanoparticles in
Sn3.5AgXCu composite solders resulted in a nely dispersed submicro Ag3Sn phase. This apparently provides classical dispersion strengthening and thereby enhances the shear strength of composite solder
joints. After soldering, the interfacial overall intermetallic compounds (IMC) layer of the Sn3.5AgXCu
lead-free solder joint was observed to have grown more signicantly than that of the Sn3.5AgXCu composite solder joints, indicating that the Sn3.5AgXCu composite solder joints had a lower diffusion coefcient. This signied that the presence of TiO2 nanoparticles was effective in retarding the growth of the
overall IMC layer.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Solder is extensively used in the electronics industry for packaging applications. In particular, leadtin solders are widely used
for chip-to-package connections. Such solders have excellent properties due to the unique combination of electrical, chemical, physical, thermal, and mechanical behaviors [1,2]. However, the use of
Pb in electronic products is being discontinued for environmental
and health reasons. Many lead free solders have been studied as
replacements for SnPb solders. SnAgCu alloys (SAC) are considered one of the most promising types of lead-free solder. However,
there are still some shortcomings to be overcome [3,4]. Numerous
studies have revealed that additions of nanoparticles to Pb-free
solders provide a marked improvement in microstructural modication and mechanical properties, and such intermixed solders
have attracted considerable attention. Lin et al. added nanoparticles of titanium dioxide to a conventional PbSn solder paste
[5,6]. Nai et al. [7] and Kumar et al. [8,9] successfully synthesized
SnAgCu-based solder materials with different weight proportions
of carbon nanotubes via the powder metallurgical technique. Tsao
and Chuag [10] reported that the addition of TiO2 nanoparticles
into a SAC solder reduced the average size and spacing of Ag3Sn
Corresponding author. Address: Department of Materials Engineering, National
Pingtung University of Science & Technology, 1, Hseuhfu Road, Neipu, Pingtung
91201, Taiwan. Tel.: +886 8 7703202x7560; fax: +886 8 7740552.
E-mail address: tlclung@mail.npust.edu.tw (L.C. Tsao).
0261-3069/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2011.06.044

particles signicantly. Similar descriptions can be found elsewhere

in the literature [11,12].
During the soldering process, metallurgical reaction between liquid solder and copper pads or pads with Ni/Au metallization
forms a layer of IMC at the solder/metallization interface, which
weakens the solder joints due to the brittle nature of the IMCs.
The strength of the solder joint decreases with increasing thickness
of the IMC layer formed at the interface, and the IMCs act as initiation sites for microcracks [13,14]. Thus, nickel is widely used in
between Cu and solder in order to sustain both the diffusion barrier
and a long period of service. However, no work has been performed
on the interaction and interdiffusion behavior of a lead-free SAC
composite solder mixed with TiO2 nanoparticles and Cu substrate.
Therefore, the present work studies the microstructural morphology and microhardness of such solder. IMC growth at the
Sn3.5AgXCu composite solder/Cu substrate interface during soldering was also investigated.

2. Experimental procedure
Sn3.5Ag(SA), Sn3.5Ag0.7Cu(SAC), SA-0.5TiO2, and SAC-0.5TiO2
solder alloys were fabricated in nominal weight percent compositions. Pure tin (99.99%), silver (99.99%), and copper (99.99%) were
melted in a vacuum furnace at 650 C for 2.5 h to produce solder
alloys of SA and SAC solder (wt.%). The lead-free composite solders
were prepared by mechanically dispersing 0.5 (wt.%) of TiO2 nano-

S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

particles into the SA and SAC solder with subsequent remelting in

vacuum furnace at 650 C for 2.5 h and casting in a mold. The solder was melted in a crucible and chill cast in a water-cooled copper
mold to form square ingots of 8  10  20 mm. The average diameter of the nominally spherical TiO2 nanoparticles was 20 nm [10]
(Nanostructured & Amorphous materials, USA). Fig. 1a shows a
eld-emission gun scanning electron microscope (FEG-SEM) image
of the TiO2 nanoparticles taken by a LEO 1530. X-ray diffraction
(XRD, D/max 2500 V/PC) analysis was performed to determine
the phase composition of the TiO2 nanoparticles (Fig. 1b). Cu substrates with a dimension of 8 mm  12 mm were cut from a 1 mmthick Cu plate (3N5), ground with SiC paper, and polished with
1 lm and 0.3 lm Al2O3 powders. For the study of interfacial reactions, the SAC solder foil was placed on the Cu substrate and heated
in a furnace under a vacuum of 103 torr. Through a water cooling
system installed within the furnace, the specimens were quickly
cooled to room temperature. Soldering reactions were conducted
at temperatures 275 C for 10 min and 30 min.
The microstructures of both the lead-free composite solder alloys and Sn3.5AgXCu composite solder/Cu interfacial reactions
after soldering reactions were revealed using scanning electron
microscopy (SEM). The specimens were cross-sectioned, ground
with sandpaper, polished with 1 lm, 0.3 lm and 0.05 lm Al2O3
powders, and etched with 5% HCl and 95% H2O solution. Microhardness was determined using an automatic digital microhardness
tester with a 10 gf indenting load and a load dwell time of 15 s. The
Cu/solder/Cu joint specimens for tensile test were prepared a. Before soldering, the end surfaces of the Cu rods were cleaned with

Fig. 1. (a) FEG-SEM image of the TiO2 nanoparticles; (b) X-ray diffraction spectra of
the TiO2 nanoparticles.

4721

a 5 vol.% HCl solution. Two copper rods of diameter D = 2 mm were

then xed in a holder and positioned such that the two end surfaces were separated by a distance of 0.5 mm (Fig. 2). The specimens were dipped in a solder bath (275 C for 60 s) and then
cooled in air. All the tensile experiments were carried out on an
MTS Tytron 250 testing machine under a constant strain rate of
about 1.0  102 s1.
3. Results and discussion
3.1. Differential scanning calorimetry
Fig. 3 illustrates the DSC curves of the lead-free Sn3.5AgXCu
composite solders used upon heating, summarized in Table 1.
DSC scans of lead-free Sn3.5Ag solder without any TiO2 nanoparticles added exhibits an endothermic heat process, which is indicated by a sharp endothermic eutectic peak, as shown in Fig. 3a.
The onset temperature (solidus, TS) of lead-free SA solder is
219.2 C. The peak temperature (liquidus, TL) is observed to be
225.5 C, rather than the equilibrium eutectic point at 221 C. Under a nearly thermodynamic equilibrium solidication condition,
Sn will solidify as nearly pure b phase, without any signicant solid
solution of either Ag or Ag3Sn in the SnAg system. However, under most industrial solidication conditions, the eutectic reactions
will not be at equilibrium; thus, the b-Sn may contain solid solute
atoms of Ag. Subsequent precipitations of stable or metastable
intermetallic phases are possible at room temperature and during
solidication [15]. Fig. 3c shows the DSC scans of lead-free SA solder reinforced with 0.5 wt.% of the TiO2 nanoparticles. It is evident
from the DSC scan of the lead-free SA composite solders that the
addition of TiO2 nanoparticles to the solder matrix resulted in discernible changes in the solidus temperature (TS) and liquidus temperature (TL) of lead-free SA solder. It can be seen that the solidus
temperature (TS) and liquidus temperature (TL) of the lead-free SA
solder both increased slightly, from 219.2 to 219.6 C and from
225.5 to 226.6 C, respectively, when 0.5 wt.% of TiO2 nanoparticles
was added to the solder. Fig. 3b exhibits the DSC curve of the leadfree SAC without any addition. Since the heating process was not at
equilibrium, the lead-free SAC solder showed a melting temperature range from 217.3 C to 221.2 C, rather than the equilibrium
eutectic point of the lead-free SnAgCu system at 217 C. In addition, the DSC curves of the SAC composite solder specimens doped
with 0.5 wt.% addition of TiO2 nanoparticles show only one eutectic peak, and the melting temperature of the SAC composites is
higher than that of the un-reinforced solder alloy (Fig. 3d), which
agrees well with previous results from other rigid nano-reinforcements [10,16]. These characteristics are similar to those of
lead-free SA composite solder, as shown Fig. 3a and c. Shen et al.
reported that the addition of ZrO2 nanoparticles increased the
solidication temperature of Sn-3.5Ag-ZrO2 solder [11].
For the lead-free Sn3.5AgXCu composite solders, the solidus
temperature was quite similar to that of the un-reinforced solder
alloy. However, the rise in the liquidus (TL) of the lead-free composite solder due to the addition of TiO2 nanoparticles can be
attributed to the high melting point of the TiO2. Since TiO2 has a
high melting point, the observed increase in melting point of the

Fig. 2. The schematic conguration of the tensile specimen.

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S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

Fig. 3. DSC scans for: (a) SA; (b) SAC; (c) SA-0.5TiO2; and (d) SAC-0.5TiO2.

Table 1
Solidus, liquidus, and melting range of the lead-free SAC composite solder in this
study.
Specimens

Nano-TiO2 (wt.%)

TS (C)

TL (C)

DT (C)

SA
SA-0.5TiO2
SAC
SAC-0.5TiO2

Nil
0.5
Nil
0.5

219.2
219.6
217.3
217.7

225.5
226.6
221.2
224.1

6.3
7.0
3.9
6.4

TS: solidus; TL: liquidus; DT: melting range.

TiO2-reinforced composite suggests local dissolution of the TiO2

nanoparticles in the molten solder. Lin et al. determined that nanoparticle materials have a profound effect on the thermal characteristics of solder solidication. The TiO2 nanoparticle-reinforced
composite solder showed an increase in the melting point, together
with melt undercooling before solidication [6]. Therefore, an increase in the melting point of reinforced solders is reported in
the present work.
3.2. Microstructure evaluations
The microstructures of Sn3.5AgXCu composite solders are
shown in Fig. 4. The compositions of various phases in the microstructure are shown in Table 2. According to microstructural observations and energy dispersive spectroscopy (EDS) analysis, the
dendritic phase of SA solder (Fig. 4a) contained nearly 100% Sn
(Mark a), while the irregularly dispersed phases (particle-like and

needle-like) in the Sn-rich matrix were composed of Sn and Ag.

However, large particles of Ag3Sn IMCs were not observed in the
rapidly-cooled SA solder. Fig. 5a shows the X-ray diffraction scan
of SA solder, indicating that both the b-Sn phase and Ag3Sn IMCs
were observed. After the addition of TiO2 nanoparticles to the solder, a different morphology was observed in the microstructure of
SA-0.5TiO2 solder (Fig. 4c). According to the EDS analysis results,
the matrix phase was b-Sn, and the rened second-phase particles
distributed uniformly in the eutectic area were Ag3Sn IMCs. The
eutectic areas (Mark d) were found to contain Sn, Ag, Ti and O, as
show in Table 2. Since the solders used were SA solders containing
TiO2 nanoparticles, and Ag3Sn was the only precipitate phase containing Ag in the solder, it can be concluded that these network eutectic areas comprise submicro Ag3Sn and TiO2 nanoparticles.
Fig. 5b presents a X-ray diffraction scan of the SA composite solder,
indicating that the TiO2 nanoparticles were successfully blended
with the SA solder. As illustrated in Figs. 4b and 5c, near-eutectic
SAC solders had a microstructure comprising Sn dendrites and the
interdendritic regions with eutectic phases, i.e. Sn, Ag3Sn and
Cu6Sn5 (Mark c). The addition of 0.5 wt.% TiO2 nanoparticles to
the SAC solder altered the as-solidied condition SEM microstructure, as shown in Fig. 4d, where at eutectic areas (Mark e in the gure), the Sn, Ag, Cu, Ti and O element had been found (Fig. 6). The
XRD pattern shows peaks of b-Sn, Ag3Sn, Cu6Sn5, and a low intensity of TiO2, as shown in Fig. 5d. Thus, the TiO2 nanoparticles were
successfully blended with the Sn3.5AgXCu solder. The b-Sn grain
size of SA and SAC solder alloy with/without TiO2 nanoparticles
are shown in Table 3. With the addition of 0.5% TiO2 nanoparticles,

S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

4723

Fig. 4. Microstructure of (a) SA; (b) SAC; (c) SA-0.5TiO2; and (d) SAC-0.5TiO2.

Table 2
EDS analysis results of indicated zone in Fig. 2.
Zone

a
b
c
d
e

Composition (at.%)

Phase identication

Sn

Ag

Cu

Ti

100
35.74
54.21
75.58
70.52

64.26

20.64
17.35

56.79

8.18

0.13
0.15

3.65
3.80

b-Sn
Ag3Sn
Cu6Sn5
Eutectic area
Eutectic area

the b-Sn grain size of SA and SAC solder alloy further decreased to
36.1% and 45.8%, respectively. In order to accurately determine the
inuence of TiO2 nanoparticles on the morphology of Ag3Sn IMCs,
the sizes of the Ag3Sn IMCs and the spacing between the IMCs in
the as-solidied solder alloys were investigated statistically. In this
procedure, 30 locations in the samples were chosen at random and
mean values calculated (Table 3). It was found that the addition of
TiO2 nanoparticles to the Sn3.5AgXCu solders reduced the average
size of Ag3Sn IMCs and the spacing between them signicantly
[10]. As shown in Table 3, the average size of the Ag3Sn IMCs in
the Sn3.5AgXCu composite solder decreased to 16.7% (X = 0) and
48.1% (X = 0.7) with 0.5 wt.% TiO2 nanoparticles, respectively. In
addition, the average spacing of the Ag3Sn IMCs in the Sn3.5AgXCu
composite solder decreased to 62.5% (X = 0) and 69.8% (X = 0.7).
The apparent strengthening effect can be attributed to the reduction of the spacing between IMCs [17].
3.3. Microhardness
The inuence of TiO2 nanoparticle reinforcement on the
microhardness of Sn3.5AgXCu composite solder is also summa-

rized in Table 4 and shown in Fig. 7. An increase in microhardness

resulted from the addition of TiO2 nanoparticles to the solder matrix. The microhardness of the Sn3.5AgXCu composite solders increased 15.5% (X = 0) and 16.6% (X = 0.7) above that of the SA
and SAC solders, respectively. As observed from the microstructural observation, both the reinforcing TiO2 nanoparticles and the
rened IMCs of submicro Ag3Sn can be considered the main reasons for the improved microhardness of the Sn3.5AgXCu composite
solders, due to the unique properties of TiO2 nanoparticles. As active nanoparticles, TiO2 nanoparticles will accumulate the interface
of Ag3Sn intermetallic particles. Since adsorption phenomenon
plays an important role during solidication process of alloy and
would greatly affect the microstructure, surface absorption theory
also can be used to explain the renement of Ag3Sn particles in the
SAC composite solder [18]. In our experiment, the uniform microstructure enhanced the mechanical properties, and the microhardness illustrates that.
3.4. Interfacial reactions between Sn3.5AgXCu and Cu substrate
The tensile strength of the Sn3.5AgXCu composite solder joints
is also summarized in Table 4 and shown in Fig. 8. Results show
that the tensile strength of Sn3.5AgXCu increases composite solders joints increased 9.1% (X = 0) and 12.6% (X = 0.7) above that
of the SA and SAC solders, respectively. The tensile strength of solder joints containing TiO2 nanoparticles is effect due to the homogeneous distribution of second phases (Ag3Sn and TiO2) as well as
the ne microstructure. Another, many study [19,20] reported that
the decrease in tensile strength is ascribed to the growth in IMC
thickness of the solder joints. This suggests that the addition of
TiO2 nanoparticles to the Sn3.5AgXCu composite solder effectively

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S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

Table 3
Comparison of the Ag3Sn IMC average size and the spacing between Ag3Sn IMC in
composite solder matrices.
Ag3Sn (lm)

Samples

SA
SAC
SA-0.5TiO2
SAC-0.5TiO2

b-Sn (lm)

Grain size

Average spacing

0.30 0.14
0.54 0.32
0.25 0.11
0.28 0.18

0.56 0.24
0.63 0.31
0.21 0.07
0.19 0.08

15.5 7.35
14.72 6.85
9.91 3.51
7.98 2.89

Table 4
Comparison of the microhardness of solder and the tensile strength of the Cu/solder/
Cu joints.
Samples

Micro hardness (Hv)

Tensile strength (MPa)

SA
SAC
SA-0.5TiO2
SAC-0.5TiO2

14.8 0.51
15.1 0.74
17.1 0.56
17.6 0.63

43.2 1.89
46.1 1.56
47.1 1.34
51.9 2.15

Fig. 5. X-ray diffraction scans of the solders. (a) SA; (b) SA-0.5TiO2; (c) SAC; and (d)
SAC-0.5TiO2.

Fig. 7. Bar graph showing the inuence of TiO2 nanoparticles on microhardness of

the Sn3.5AgXCu solders.

Fig. 6. EDS analysis results of marked e zone in Fig. 4d.

Fig. 8. The tensile strength of various Cu/solder/Cu joints.

suppress the growth of CuSn IMC layer. Fig. 9 presents a cross section of the Cu plates reacted with SA and SA composite solders at
275 C for different times. It is clearly shown in Fig. 9a and b that
discontinuous and sharp scallop-shaped Cu6Sn5 IMC layers grew
at the interface. In addition, rough Cu6Sn5 IMCs are observed in
the solder matrix. With an increase in reowing time, the thickness
of the interfacial Cu6Sn5 IMC layer increases from 4.44 lm to

7.83 lm. In addition, at the SA composite/Cu interface, after

reowing at 275 C for 10 min, as shown in Fig. 9c, round, scallop-shaped Cu6Sn5 IMCs formed at the interfaces. The shape of
the Cu6Sn5 IMCs in the SA composite/Cu is different from that at

S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

4725

Fig. 9. Micrographs of cross-sectional view of interfacial IMC after soldering at 275 C and different times: (a) SA/Cu, 10 min; (b) SA/Cu, 30 min; (c) SA-0.5TiO2/Cu, 10 min;
and (d) SA-0.5TiO2, 30 min.

the SA/Cu joint. In addition, it is interesting that a large number of

dot-shaped submicro Ag3Sn precipitates can be observed around
the eutectic network structure. However, the interfacial morphology of the Cu6Sn5 IMC layers and solder matrix after reowing
for 30 min, shown in Fig. 9d, resembles that of the sample reowed
for 10 min. The round, scallop-shaped Cu6Sn5 IMCs grew from
2.79 lm to 5.57 lm. For the SA solder/Cu and SA composite solder/Cu interfaces, the morphologies of both the Cu6Sn5 IMC layer
and solder matrix changed obviously.
Fig. 10 shows the cross-section SEM images of SAC/Cu and SAC
composite solder/Cu interfaces reowed at 275 C for different
times. It can be seen in Fig. 10a that a continuous scallop-shaped
Cu6Sn5 IMC layer formed at the solder/Cu interface and a large
number of Cu6Sn5 IMCs precipitated in the solder matrix after
the reowing process. With an increase in reowing time to
30 min, the morphology of the Cu6Sn5 IMC layer changed from a
continuous scallop shape to an elongated scallop-shape, as shown
in Fig. 10b. These phenomena differ markedly from those observed
in the SA/Cu samples. A comparison of the cross-section SEM
images of SA composite solder/Cu (Fig. 9c and d) and SAC composite solder/Cu (Fig. 10c and d) reveals the same morphology. Furthermore, the thickness of the Cu6Sn5 IMC layer of the SAC
composite solder was found to be thinner than that of SAC solder.
This indicates that the TiO2 nanoparticles had a signicant effect on
the observed phenomenon.
Based on the measured results using a powerful image processing
system together with scanning electron microscopy, the linear relationship between the thickness of the IMC layer and the square root
of soldering time are summarized and plotted in Fig. 11. It is obvious

that the order of CuSn IMC thicknesses for different samples is as

follows: SAC-0.5TiO2 composite solder < SA-0.5TiO2 composite solder < SA solder < SAC solder. The order of diffusion coefcients, kp
(kp = Dx2/t) at the composite solder joints is as follows: 1.40 
1014 lm/s1/2 for SAC-0.5TiO2 composite solder < 1.94  1014
lm/s1/2 for SA-0.5TiO2 composite solder < 3.47  1014 lm/s1/2 for
SA solder < 3.48  1014 lm/s1/2 for SAC solder. The composite solder joints in general exhibit lower diffusion coefcients as compared
to Sn3.5AgXCu solder joints. This indicates that the presence of TiO2
nanoparticles as reinforcements in the solder joints is effective in
retarding growth and restraining drifting of the IMC layer. Nai
et al. [7,21] studied the suppression of CNTs on the growth of IMC
layers between SnAgCu composite lead-free solders and Cu pads
after aging. Kao et al. [22] added nano-sized Cu6Sn5 IMC particles
into a SnAgCu solder to control the growth of (Cu, Ni)6Sn5 IMC particles in SnAgCu/Ni-P solder joints. It has been suggested that TiO2
nanoparticles in the solder matrix of Sn3.5AgXCu composite solders
may be present in the forms of (i) the dispersed single TiO2 nanoparticles and (ii) randomly distributed TiO2 nanopowder clusters. Furthermore, the addition of TiO2 nanoparticles in Sn3.5AgXCu solder
results in a nely dispersed submicro Ag3Sn phase (Fig. 4c and d).
Hence, it is proposed in this study that the presence of these TiO2
nanoparticles and submicro Ag3Sn phase retards the diffusion of
Sn and Cu atoms through the solder system by effectively providing
a barrier to Sn diffusion toward the Cu substrate, thus hindering the
growth of the interfacial IMC layer. A previous study showed that
nano-Ag3Sn precipitates are captured by the IMCs, which decreases the surface energy of the scallop-type Cu6Sn5 grains and retards the growth of the whole IMC layer [23].

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S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

Fig. 10. Micrographs of cross-sectional view of interfacial IMC after soldering at 275 C and different times: (a) SAC/Cu, 10 min; (b) SAC/Cu, 30 min; (c) SAC-0.5TiO2/Cu,
10 min; and (d) SAC-0.5TiO2/Cu, 30 min.

K
c AK

c  RT

cKo AK  RT

CK

AK

CK
c

!
dc AK

dc ! min

K
o

CK is the amount of adsorption of TiO2 nanoparticles at Ag3Sn particle K, c is the concentration of the TiO2 nanoparticles, R is the
Plank constant, T is the absolute temperature, cK is the surface tension of Ag3Sn particle K, cKc is the surface tension of Ag3Sn particles K
with adsorption of TiO2 nanoparticles, cKo is the surface tension of
Ag3Sn particles K without adsorption of TiO2 nanoparticles, AK is
the area of Ag3Sn particles K.
Given that the volume is constant, the surface energy of the
planes must be kept to a minimum in the equilibrium state. Here,
P K
K co AK is assumed to be constant because it is independent of the
concentration of TiO2 nanoparticles. That is,
Fig. 11. The growth thickness (X) of the IMCs formed during the Sn3.5AgXCu
composite solder(l)/Cu(s) interfacial reactions at 275 C as a function of the square
root of reaction time (t1/2).

In short, in addition to the renement mechanism of grains in

lead-free solders by the addition of rare earth (RE) elements [18]
and the suppression of the growth of IMC layers in solder joints
during reow and aging by the additions of nano-sized, non-reacting, non-coarsening oxide particles [17,21], the renement of the
Ag3Sn IMCs in Sn3.5AgXCu composite solders also can be explained
by the adsorption of TiO2 nanoparticles. According to the adsorption theory of TiO2 nanoparticles [23], the surface free energy of
Ag3Sn submicro particles is:

X
K

AK

Z
o

CK
c

dc ! max;

which implies that the effect of the grain boundaries of the Ag3Sn
phase with the maximum CK value is most active.
In the Sn3.5AgXCu composite solders, the Ag3Sn particles are
larger than in solder with the TiO2 nanoparticles. Thus, the TiO2
nanoparticles, which were adsorbed on the surfaces of the Ag3Sn
particles, can be regarded as effective surface-active agents. It is
well known that adsorption phenomena play an important role
during the solidication process of solder alloys and will greatly affect the microstructure. First, when Ag3Sn grains had a relatively
large surface tension and grew rapidly during solidication, their

S.Y. Chang et al. / Materials and Design 32 (2011) 47204727

surfaces had a maximum adsorption of TiO2 nanoparticles, and

thus the surface energy of Ag3Sn grains decreased. Therefore, the
growth rate of Ag3Sn grains was suppressed, resulting in a rened
Ag3Sn phase. Second, this theory explains that the surface energy
of the Cu6Sn5 grains decreased and suppressed the growth of the
whole of the scallop-type Cu6Sn5 layer. This entire interface would
capture both the Ag3Sn submicro particles and TiO2 nanoparticles
preferentially. Gibbs tells us that the surface energy is reduced,
and this reduction will decrease the growth velocity of this Cu6Sn5
grain [23]. Until now, it has been quite difcult to calculate the surface energy in order to minimize the free energy of the entire in
SAC-0.5TiO2 composite solder. This is consistent with the experimental results that the size of both the Ag3Sn particles and the
thickness of Cu6Sn5 IMC layer decreased in the Sn3.5AgXCu composite solder. The morphology of Cu6Sn5 grains affects the absorbed nano-Ag3Sn particles. Especially, the scallop-type Cu6Sn5
grains that are formed by the ripening reaction are likely to be
captured by the large amount of nano-Ag3Sn particles. These
nanoparticles decrease the surface energy and hinder the growth
of the Cu6Sn5 IMCs.

4. Conclusions
This study investigated the effect of an addition of 0.5 wt.% TiO2
nanoparticles on the microstructure, melting property, interfacial
reactions, the morphology of IMC and the tensile strength of the
Sn3.5AgXCu (X = 0 and 0.7 wt.%) composite solder joints. Experimental results revealed that the addition of TiO2 nanoparticles in
Sn3.5AgXCu composite solders results in a nely dispersed submicro Ag3Sn phase. The Sn3.5AgXCu composite solder joints consistently displayed higher tensile strengths than that of the plain
Sn3.5AgxCu solder joints. In addition, the order of diffusion coefcients at the composite solder joints is as follows: 1.40  1014
lm/s1/2 for SAC-0.5TiO2 composite solder < 1.94  1014 lm/s1/2
for SA-0.5TiO2 composite solder < 3.47  1014 lm/s1/2 for SA solder < 3.48  1014 lm/s1/2 for SAC solder. It is reasonable to suggest that the TiO2 nanoparticles are effective in retarding the
growth of the overall IMC layer in Sn3.5AgXCu composite solder
joints. Moreover, adsorption theory is used to explain the formation of submicro Ag3Sn phase and interfacial Cu6Sn5 IMC layer
and their effect on the surface energy of the IMCs.

Acknowledgment
The authors acknowledge the nancial support of this work
from the National Science Council of Taiwan R.O.C. under Project
No. NSC97-2218-E-020-004.

4727

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