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Materials Science & Engineering A: A. Fawzy, S.A. Fayek, M. Sobhy, E. Nassr, M.M. Mousa, G. Saad
Materials Science & Engineering A: A. Fawzy, S.A. Fayek, M. Sobhy, E. Nassr, M.M. Mousa, G. Saad
art ic l e i nf o
a b s t r a c t
Article history:
Received 21 January 2014
Received in revised form
17 February 2014
Accepted 18 February 2014
Available online 24 February 2014
Recently, nano-composite solders have been developed in the electronic packaging materials industry to
improve the mechanical response of solder joints to be used in service under different conditions. In this
study mechanical mixing has been used to disperse nano-metric ZnO particles in Sn3.5Ag0.5Cu
(SAC355) solder at 420 1C for 2 h. In comparison with SAC355 solder, addition of nano-metric ZnO
particles effectively suppressed the formation and restricted the volume fraction of the Ag3Sn and Cu6Sn5
intermetallic compound particles, lowering grain sizes and controlled the growth of -Sn grains in the
matrix. An improvement in tensile creep resistance of the reinforced SAC355 composite is noticed. This
improvement seems to be due to its effect in structural renement and makes the composite solder to
display a large creep life time. The addition of nano-metric ZnO particles keeps the melting temperature
nearly at the SAC355 level, indicating that the composite solder is t for the existing soldering process.
& 2014 Elsevier B.V. All rights reserved.
Keywords:
Nano-metric
Composite solder
Structural renement
Creep resistance
1. Introduction
Currently, concern over the toxicity of lead in eutectic SnPb
solders has prompted the development of new tin rich lead free
solder alloys for electronic packaging [14]. This has prompted
a search for lead-free solders and more attention in the research
activities in this eld. To date, several types of binary and
ternary Sn-based lead-free solders such as SnAg, SnCu, SnAu,
SnAgCu and SnZn have been developed and applied in the
electronic packaging industry [46]. Among the various types of
lead-free solders SnAgCu solder has been proposed as one of the
most promising substitutes for conventional SnPb solder [7,8].
However, many problems with the ternary SnAgCu lead-free
solders still exist such as an excessive reaction between SnAgCu
solder and substrates, the formation of large brittle intermetallic
compounds (IMCs) and the short creep-rupture life time in service.
In addition, the formation of large primary Sn dendrite reduces the
resistance to thermalmechanical fatigue [9]. In order to further
enhance the properties of SnAgCu solder alloys, alloying elements
such as rare earth, Bi, Sb, In, Co, Ga, Ni, Ge and nano-metric
particles were selected by many of researchers as alloys addition
into these alloys [1015].
http://dx.doi.org/10.1016/j.msea.2014.02.061
0921-5093 & 2014 Elsevier B.V. All rights reserved.
2. Experimental procedures
As developed in our previous work [15], two lead-free solders
have the composition Sn3.5 wt% Ag0.5 wt% Cu (SAC355 plain
solder) and Sn3.5 wt% Ag0.5 wt% Cu0.5 wt% ZnO nanoparticles
(SAC355 composite solder) are designed to understand the effect
of nano-metric ZnO particles on the thermal and microstructure of
the plain Sn3.5Ag0.5Cu solder. These samples were prepared by
the same method used in the previous work [15]. Rod-like samples
were obtained with a diameter of approximately12 mm. These
rod-like samples were mechanically machined (cold drowning)
into wires of 0.8 mm in diameter and working length of 50 mm for
tensile creep tests and sheets of 0.4 mm thickness for structure
investigations. The small sized solder tensile test specimens used
in this work were more advantageous than the test standards
since the tensile creep behavior follows a simple power law.
Besides, the metallization material changes not only the absolute
creep strength, but also the stress sensitivity (stress exponent) of
the creep behavior. Such effects could not be found in bulk
specimens. Details are described in [24,25]. The microstructure
was carried out by using scanning electron microscopy (SEM)
JSM-5410, Japan. A solution of 80% glycerin, 10% nitric and 10%
acetic acid was prepared and used to etch the surface of samples.
Phase identication was based on two complimentary techniques,
namely X-ray diffraction (XRD) and Energy Dispersive X-ray
Spectrometry (EDS). For XRD, we used a Philips diffractometer
with monochromatic Cu K radiation and individual phases and
their crystal structures were identied by matching the characteristic XRD peaks recorded from the bulk specimens against JCPDS
data. Differential scanning calorimetry (DSC) (shimadzu DSC-50)
was carried out to understand the melting process of the two,
plain and composite, solder alloys. Heating the specimens in DSC
was carried out at 10 K/min with heating rate.
Prior to the tensile creep testing, all specimens were heattreated at a temperature of 393 K for 2.5 h and then slowly cooled
to room temperature to stabilize the microstructure and to remove
the residual defects produced during the drawing process. In order
to understand the effect of adding nano-metric ZnO particles on
the tensile creep characteristics of SAC355 composite, tensile creep
SAC
0
-20
-40
221.18C (494.18 K)
-60
20
SAC+ZnO
0
-20
-40
222.26C (495.26 K)
-60
160
180
200
220
240
260
280
300
Temperature (C)
Fig. 1. DSC curves of (a) SAC355 and (b) SAC composite solder alloys.
(101)
(202)
(104)
(201)
(103)
(200)
(102)
(110)
(100)
(002)
nano-sized
ZnO
2 Theta
Fig. 2. (a) XRD proles and (b) bright eld TEM of ZnO nano-particles.
Cu6Sn5
Intensity (arb.units)
3000
2000
1000
0
30
40
50
30
40
50
60
70
80
60
70
80
3000
2000
1000
2 Theta
Fig. 3. XRD proles of (a) SAC355 solder and (b) SAC355 composite solder alloys.
Fig. 4. SEM micrographs showing the grains of (a) SAC355 solder and (b) SAC355 composite solder alloys.
This gure shows the representative creep curves for SAC355 and
SAC355 composite samples tested at 373 K under the effect of 7.2,
8.6, 10.1, 11.5 and 13.0 MPa. These isothermal creep curves of both
solders showed a monotonic shift towards higher strains and
lower fracture times on increasing the deformation temperature
and/or applied stress. Moreover, the level of creep strain for
SAC355 composite is generally lower than that of SAC355 plain
solder under the same testing conditions (Fig. 6a).
From this comparison, it is apparent that the SAC355 composite is
more creep resistant than that of SAC355 plain solder. Likewise, the
beginning of tertiary creep in SAC355 composite solder appears to
start at longer times than that of SAC355 plain solder which means
that the creep life time of SAC355 composite is longer than that of
SAC355 plain solder. Thus the composite solder has benet to enhance
its creep resistance in good agreement with the prediction of the
classical theory of dispersion strengthening created by the addition of
ZnO nanoparticles. This result is credible when the increased creep
resistance of SAC355 composite solder is mostly attributed to the
decrease of its grain sizes (Fig. 4) and renement of the IMC particles
Ag3Sn and Cu6Sn5 (Fig. 5). Similar trends are also found in SAC solders
in other studies [2630]. They suggested that adding nano-metric
particles increased the strength of Sn-rich composite solders and
Fig. 5. SEM micrographs showing the IMCs and the corresponding EDS curves in (a) SAC355 solder and (b) SAC355 composite solder alloys, and (c) over-etched SAC355
composite solder alloys.
0.45
= 11.5 MPa
Ttesting= 398 K
0.40
Strain
0.30
0.25
SA
C+
Zn
O
SA
C
0.35
0.20
0.15
0.10
0.05
0.00
0
1000
2000
3000
4000
5000
6000
Time (Sec)
(MPa) :
1 : 7.2
2 : 8.6
3 : 10.1
4 : 11.5
5 : 13
Strain
0.15
0.10
SAC+ZnO
0.20
(MPa) :
Ttesting = 373 K
0.15
Strain
Ttesting = 373 K
SAC
0.20
4
0.10
0.05
0.05
2
1
2
1
0.00
0.00
0
1000
2000
3000
4000
5000
6000
1000
2000
Time (Sec)
0.40
= 13 MPa
SAC
0.35
3000
4000
5000
6000
Time (Sec)
Tteasting (K):
0.30
0.25
0.20
1 : 323
2 : 348
3 : 373
4: 398
0.15
= 13 MPa
SAC+ZnO
Tteasting (K):
0.35
1 : 323
2 : 348
3 : 373
4: 398
0.30
0.25
Strain
0.40
Strain
1 : 7.2
2 : 8.6
3 : 10.1
4 : 11.5
5 : 13
0.20
0.15
0.10
0.10
2)
1
0.05
2
1
0.05
0.00
0.00
0
1000
2000
3000
4000
5000
6000
Time (Sec)
1000
2000
3000
4000
5000
6000
Time (Sec)
Fig. 6. Representative straintime curves showing the effect of: (a) nano-metric ZnO particles addition to the SAC355 plain solder, (b) stresses at a constant testing
temperature, as indicated, and (c) testing temperature at constant applied stress, as indicated, for both SAC355 and SAC355 composite solders.
-2.5
-2.5
Ttesting= 373 K
SAC
-3.0
(Mp):
13
11.5
10.1
8.6
7.2
-3.5
-4.0
-5.5
-6.0
(Mp):
13
11.5
10.1
8.6
7.2
-4.0
-4.5
-5.0
-5.5
-6.0
-6.5
-6.5
-7.0
-7.0
-7.5
-7.5
-8.0
-8.0
-8.5
Ttesting= 373 K
-3.5
tr
-5.0
SAC+ZnO
-3.0
Ln
Ln
tr
-4.5
-8.5
3.5
4.0
4.5
5.0
5.5
6.0
6.5
3.0
Ln t
3.5
4.0
4.5
5.0
5.5
6.0
6.5
Ln t
Fig. 7. Relation between the ln tr and ln t for both SAC355 and SAC355 composite solder alloys at different applied stresses.
SAC
SAC-0.5 ZnO
0.9
0.00007
(MPa) :
1 : 7.2
0.00006
0.00005
(4)
st
0.00004
0.7
3 : 10.1
4 : 11.5
5 : 13
n average
0.8
(5) 2 : 8.6
0.00003
0.00002
(3)
0.00001
(2)
0.6
(1)
0.00000
0.5
320
320
340
360
380
400
T (K)
330
340
350
360
370
380
390
400
T (K)
Fig. 9. Temperature dependence of steady state creep rate st for both SAC355
(solid lines) and SAC355 composite solder alloys (dashed lines).
-9
-9
SAC
323
348
373
398
-10
Ttesting (K):
323
348
373
398
-10
-11
.
Ln st
-11
.
Ln st
SAC+ZnO
Ttesting (K):
-12
-12
-13
-13
-14
-14
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
Ln
Ln
Fig. 10. Relation between the ln st and ln s at different testing temperatures for both SAC355 and SAC355 composite solder alloys.
5.5
-9
SAC
SAC+ZnO
5.0
Ttesting (K):
323
348
373
398
-10
4.5
Ln st
4.0
SAC
3.5
-11
-12
3.0
2.5
-13
2.0
-14
6
1.5
320
330
340
350
360
370
380
390
10
12
14
(MPa)
400
T (K)
Fig. 11. The dependence of the stress sensitivity parameter, m, on the testing
temperature, T, for both SAC355 and SAC355 composite solder alloys.
0.45
0.35
o st
+Z
n
0.30
SA
SA
0.25
V x106
0.40
0.20
0.15
320
330
340
350
360
370
380
390
400
T (K)
Fig. 12. (a) Relation between the ln st and s at different testing temperature, T, for
SAC355 solder alloy. (b) The dependence of the activation volume, V, on the testing
temperature for both SAC355 and SAC355 composite solder alloys.
component, must be predictable. In short, the renement mechanism of grains and suppression of the growth of IMCs in lead-free
solders during solidication and aging can be achieved by additions
of nano-metric, non-reacting, non-coarsening oxide particles [27,37].
In order to precisely evaluate the inuence of nano-metric ZnO
particles on the microstructure and tensile creep properties of the
solidied SAC355 solder we will refer to the SEM micrographs
shown in Figs. 4 and 5. It has been found that addition of a small
percentage of nano-metric ZnO resulted in renement of the
microstructure of the near eutectic SAC355 composite solder.
It appeared as dot-shaped rened Ag3Sn and polygons of Cu6Sn5
precipitates around the eutectic as has been detected by EDS
investigations. This renement may be attributed to the adsorption of the nano-metric ZnO particles on these solidied grain
surfaces through the matrix during the solidication process.
-5.0
= 0.8
-5.5
= 0.85
Ln K
-6.0
C
SA
C
SA
-6.5
nO
+Z
-7.0
-7.5
-8.0
-13.5
-13.0
-12.5
-12.0
-11.5
-11.0
Ln st
Fig. 13. Relation between ln K and the ln st for both SAC355 and SAC355 composite
solder alloys.
Fig. 14. Dot-shaped rened Ag3Sn and Cu6Sn5 precipitates around the eutectic
areas (magnied part from Fig. 5b).
10
-9.0
SAC
Q= 0.3 eV
-9.5
(Mp):
13
11.5
10.1
8.6
7.2
-10.0
-10.5
Ln st
-11.0
-11.5
-12.0
-12.5
-13.0
-13.5
-14.0
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
1000/T
-9.0
SAC+ZnO
-9.5
References
Q= 0.35 eV
(Mp):
13
11.5
10.1
8.6
7.2
-10.0
-10.5
Ln st
-11.0
[1]
[2]
[3]
[4]
[5]
[6]
[7]
-11.5
[8]
[9]
[10]
[11]
[12]
[13]
[14]
-12.0
-12.5
-13.0
-13.5
-14.0
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
1000/T
Fig. 15. Relation between the ln st and 1000/T for: (a) SAC355 and (b) SAC355
composite solder alloys.
[15]
[16]
[17]
[18]
[19]
[20]
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