Thermochimica Acta 542 (2012) 4245

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Thermal diffusivity of SnAgCu-based, Pb-free, micro- and nano-sized solder

balls
Inkoo Kim a , Man Il Kang a , Sok Won Kim a, , Eun Jung b , Sang Hyun Lee c
a
b
c

Department of Physics, University of Ulsan, Ulsan 680-749, Republic of Korea

School of Materials Science and Engineering of Ulsan, Ulsan 680-749, Republic of Korea
Division of Physical Metrology, Korea Research Institute of Standards and Science, Daejon 305-600, Republic of Korea

a r t i c l e

i n f o

Article history:
Available online 12 November 2011
Keywords:
Solder ball
SnAgCu
Ball size effect
Laser ash method
Thermal diffusivity

a b s t r a c t
In order to determine the effects of ball size and porosity on the thermophysical properties of solder
materials, several Sn3.0Ag0.5Cu solder balls with average ball diameters of 170 nm, 10 m, 29 m,
and 140 m were prepared, and disk-type samples were formed under compaction pressures of 100,
200, and 300 psi. The thermal diffusivity of each sample was then measured using a laser ash apparatus
over a temperature range of room temperature to 150 C. The results showed that the thermal diffusivity
increased as both the diameter of the solder ball and the compaction pressure increased. On the other
hand, the thermal diffusivity decreased by as much as 28% for the same ball sizes and pressures at higher
temperatures. Overall, the sample with a ball diameter of 140 m prepared under a compaction pressure
of 300 psi exhibited the highest thermal diffusivity (about 30 106 m2 /s). Thus, it was found that the
thermal diffusivity of a sample composed of solder balls is strongly dependent on the ball size, porosity,
and preparation temperature.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Tinlead (SnPb)-based solders have long been the most popular materials for electronic packaging because of their low costs and
excellent properties for interconnecting electronic components.
In particular, of the many assembling technologies that utilize
these solders, ball grid array (BGA) technology has been used for
high-volume package productions during the last few years. BGA
joints provide both high mechanical strength and high electrical
conductivity, which play signicant roles in the establishment of
connections between electronic components and printed circuit
boards [1,2].
Yet, due to the toxicity of lead, conventional SnPb solders are
gradually being replaced with Sn-based soldering alloys containing additives of other metals such as Ag, Cu, Bi, Ga, In, Sb, and Zn.
This shift has forced the development of Pb-free solders, and the
SnAgCu ternary eutectic alloy is considered to be a promising
alternative [37]. In fact, several studies have already investigated
many of the properties of the SnAgCu alloy, but its thermal properties remain relatively unexplored. Our previous study found that,
among the numerous SnAgCu alloy series with varying Ag and

Corresponding author. Tel.: +82 52 259 2388; fax: +82 52 259 1693.
E-mail address: sokkim@ulsan.ac.kr (S.W. Kim).
0040-6031/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2011.10.022

Cu contents, the Sn3.0Ag0.5Cu solder ball had the most desirable

thermophysical properties [8].
In this study, in order to determine the effects of ball size and
porosity on these thermophysical properties, the thermal diffusivity of several disk-type samples composed of Sn3.0Ag0.5Cu
solder balls with different ball sizes and compaction pressures were
measured using a laser ash apparatus.

2. Experimental
Disk-type samples were prepared using solder ball powders
with ball diameters of 170 nm to 140 m under compaction pressures of 100, 200, and 300 psi without resin. The solder balls were
composed of Sn3.0Ag0.5Cu ternary alloys. The nano-sized solder
balls were fabricated using a ne solder wire-explosion process (the
diameter of the ne solder wire was 0.3 mm) [9] and micron-sized
solder balls were fabricated using a centrifugal atomization process (with a disc rpm of 60,000) [10]. All of the ball sizes were then
measured using a SEM and a TEM. The diameter and thickness of
each disk-type sample was about 10 mm and 2 mm, respectively. Xray diffraction patterns of the solder balls used in the samples were
obtained using an X-ray diffractometer (XRD; RAD-3C, Rigaku) with
and micromorphologies of
Cu K radiation of wavelength 1.54 A,
the samples were investigated using a scanning electron microscope (SEM; JSM-6500F, JEOL). The masses of the solder balls were
measured using a precise electronic balance (E04130, Ohaus).

I. Kim et al. / Thermochimica Acta 542 (2012) 4245

43

The thermal diffusivity of a solder ball was measured using a

laser ash apparatus (LFA 457, NETZSCH) [11,12] over a temperature range of room temperature to 150 C since the melting point
of the alloy is about 183 C. A Nd-YAG laser produced a maximum
pulse energy of 18.5 J for a pulse duration of 0.5 ms, which was used
to heat the front surface of the sample. Note that the apparatus used
in this experiment employed an improved CapeLehman model to
eliminate the possible errors caused by transient heat loss and the
nite laser pulse time effect [13].
3. Results and discussion
3.1. Structural properties
Fig. 1(a) shows an XRD pattern of the sample with a ball diameter
of 140 m under a compaction pressure of 100 psi. The pattern displays the diffraction peaks of Sn, Ag, and Cu and reveals a diffraction
peak for SnO2 in the (1 1 0) plane induced by oxidation. This result
indicates that the solder ball was, indeed, a ternary alloy composed
of Sn, Ag, and Cu. The samples with ball diameters of 10 m and
29 m had patterns similar to those of the 140-m ball under all
pressures. Fig. 1(b) shows an XRD pattern of the sample with a ball
diameter of 170 nm and a pressure of 100 psi. The pattern is again
similar to that of the 140-m ball. However, the SnO2 peak in the
(1 1 0) plane caused by oxidation was more intense than that from
the sample with a ball diameter of 140 m. These results imply that
oxidation was stronger when the diameter of the solder ball was
reduced to several hundred nanometers.
Fig. 2 shows surface morphologies of the samples with different
ball sizes under the same compaction pressure of 100 psi. Note that
the number of boundaries among the observed particles increased
with a decrease in ball size.
3.2. Density and porosity
The masses of the samples were measured using a precise electronic balance with an accuracy of 0.1 mg. The measured mass was
then used to calculate the density of the sample. The results in
Fig. 3 show that the density of the sample increased as the compaction pressure increased from 100 psi to 300 psi for every ball
size, indicating that the space between the particles in the sample

Fig. 1. XRD patterns of solder balls with ball diameters of (a) 140 m and (b) 170 nm
under a compaction pressure of 100 psi.

contracted as the pressure rose. As the ball diameter of the solder balls decreased from 140 m to 10 m, the densities of the
samples also decreased linearly; however, when the ball diameter
was reduced to 170 nm, the density abruptly dropped from about
6 g/cm3 to 4 g/cm3 for all compaction pressures. This drastic change
in density was likely a response to the surge in the number of
boundaries and pores in the samples with reduced ball diameters.
The number of solder balls included in a sample can be estimated
using the following equation:
N
=

Vsample
Vball

Fig. 2. SEM images of the samples with ball diameters of (a) 170 nm, (b) 10 m, (c) 29 m, and (d) 140 m and a compaction pressure of 100 psi.

(1)

44

I. Kim et al. / Thermochimica Acta 542 (2012) 4245

Fig. 3. Densities for various ball sizes and compaction pressures.

Fig. 5. Porosities for various ball sizes and compaction pressures.

where Vsample and Vball are the volumes of the sample and a solder ball, respectively. If the solder ball is a perfect sphere, then
Vball = (4/3)r3 and the volume of the ball is proportional to r3 .
Then, as the radius of the solder ball increases, the number of balls
in the sample should decrease in proportion to r3 . Fig. 4 shows
the results calculated using Eq. (1) namely, as the radius of the
solder ball decreased from 70 m to 5 m, the number of balls in
the sample increased from 9.56 104 to 2.64 108 . In particular,
when the radius of the ball was reduced to 170 nm, the number of
balls dramatically increased by about 2.10 105 (from 2.64 108
to 5.62 1013 ). Note that the line in Fig. 4 was obtained by plotting
the results via Eq. (2):

where sample is the total average density of the sample, and ball is
the density of the ball. The porosity results are illustrated in Fig. 5,
which shows that, as the pressure increased, the porosities of the
samples decreased. This result follows the theory that, in the packing of dry ne spheres, the dominant force between the spheres
is the van der Waals force and thus, the porosity increases with a
decrease in particle size [15]. Therefore, as the ball size of the solder
ball decreased from 140 m to 10 m, the porosities of the samples
increased linearly. Yet, as before, when the size of the ball decreased
to 170 nm, the porosities increased nonlinearly from 23.0, 17.4, and
13.3% to 42.1, 39.9, and 35.2% under pressures of 100, 200, and
300 psi, respectively.

N = ar b

(2)
3.3. Thermal properties

where N is the number of balls, and a and b are correlation coefcients. According to the curve, the coefcients were determined
to be a = 3.36 1010 1.50 106 and b = 3.01 1.80 105 . These
values imply that the change in the number of balls was approximately proportional to r3 when the radius of the solder ball was
decreased.
The porosities of the samples with various ball sizes were subsequently deduced from the obtained densities. The porosity () was
calculated using the formula for density, which can be expressed
as [14]:
=

sample
ball

100%

Fig. 4. The number of balls according to the radii of the solder balls.

Fig. 6 shows the averages of the measured thermal diffusivities at room temperature. The experiments were performed ve
times for each sample, and the uncertainties of all the obtained
values were found to be within 5.6%. The change in thermal diffusivity with ball size was similar to the variations in density,
and like density, the thermal diffusivity increased according to
the increased compaction pressure. As the ball size of the solder
ball decreased from 140 m to 10 m, the thermal diffusivities of

(3)

Fig. 6. Thermal diffusivities for various ball sizes and compaction pressures.

I. Kim et al. / Thermochimica Acta 542 (2012) 4245

Table 1
Thermal diffusivity at various temperatures.

30

-6

Thermal Diffusivity (10 m /s)

35

45

140 m

25

Temperature
( C)

29 m

20

50

75

100

125

150

Temperature (C)
Fig. 7. Thermal diffusivities for various temperatures and ball sizes under a compaction pressure of 100 psi.

10 m

29 m

140 m

0.92
1.28
1.38

16.78
17.43
18.15

22.88
23.24
27.32

28.58
29.65
30.01

100

100
200
300

0.89
1.25
1.33

15.65
16.22
17.01

21.05
21.58
25.21

25.99
27.16
27.39

150

100
200
300

0.73
1.02
1.13

14.96
15.41
16.17

20.09
20.67
24.12

24.57
25.63
25.96

0.6
25

170 nm
100
200
300

170 nm

0.9

Thermal diffusivity with ball

size (106 m2 /s)

RT

10 m

15

Compaction
pressure (psi)

Table 1 lists all of the thermal diffusivities measured across a

range of temperatures, showing that, as the temperature increased
from room temperature to 150 C, the thermal diffusivity decreased
slightly.
4. Conclusions

the samples decreased linearly; however, as the size of the ball

decreased to 170 nm, the thermal diffusivity dropped more rapidly
from 16.78 106 to 0.92 106 m2 /s under a pressure of 100 psi.
Similar results were obtained for the other pressures, as shown in
Figs. 3 and 5. Furthermore, as the radius of the solder ball decreased,
the porosity and number of balls in the sample changed in proportion to r3 . In general, thermal diffusivity is inversely proportional
to porosity and the number of boundaries among the balls [16].
Thus, as the number of balls in the sample increased due to a reduction in the solder ball size, the porosity and number of boundaries
of the sample also grew, and the thermal diffusivity of the sample
decreased rapidly. This decrease can further be explained by the
fact that solder balls with pores have a relatively low thermal diffusivity, especially when compared to metallic solder balls, and the
scattering of thermal carriers (e.g., electrons) increases boundary
resistance, thereby resulting in a lower overall thermal diffusivity
of the sample [17].
Additionally, the intense oxidation of the nano-sized particles,
as shown in Fig. 1(b), could be another reason for the rapid decrease
of thermal diffusivity. However, it is estimated to be within several
percents [18]; therefore it was not considered. Consequently, the
next study will investigate the effects of oxidation on the thermal
properties of nano-sized particles. Until then, the results of this
study indicate that larger ball sizes and lower porosities are the
most optimal for creating solder balls with high thermal conductivity for use as electronic packaging material.
Fig. 7 shows the thermal diffusivities for various temperatures and ball sizes under a compaction pressure of 100 psi. For
the ball sizes from 10 m to 140 m, the thermal diffusivities
decreased linearly by about 11, 12 and 13% (i.e., from 16.78 106 ,
22.88 106 , and 28.58 106 m2 /s to 14.96 106 , 20.09 106 ,
and 24.57 106 m2 /s), respectively, over temperatures ranging
from room temperature to 150 C. These results indicate that the
thermal diffusivity of the sample depends on its internal thermal
resistance, and that the temperature-dependent boundary scattering of thermal carriers, such as electrons in metal, increases
such resistance. Note that, in the case of the 170-nm ball size, the
thermal diffusivity decreased more drastically, from 0.92 106 to
0.73 106 m2 /s, than it did in the other cases with the same temperature variations. This phenomenon is thought to be caused by
the increased oxidation of nano-sized balls with the rising temperatures; however, further quantitative analysis is needed to fully
understand this effect.

The thermal diffusivities of Sn3.0Ag0.5Cu alloy samples made

of solder balls with various ball sizes and compaction pressures
were measured using the laser ash method over a temperature
range from room temperature to 150 C. As the solder ball size
decreased, the thermal diffusivity of the samples also decreased
since the thermal diffusivity depends strongly on the increased
porosity and the number of boundaries formed in the samples. In
addition, the thermal diffusivity was found to be proportional to
the compaction pressure of the sample. For a quantitative analysis
of the rapid decrease in the thermal conductivity of the samples
made from nano-sized particles, an investigation into the effects of
oxidation is needed.
Acknowledgment
This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF),
funded by the Ministry of Education, Science and Technology
(2009-0093818).
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