materials

Article
Soldering Characteristics and Mechanical
Properties of Sn-1.0Ag-0.5Cu Solder with Minor
Aluminum Addition
Yee Mei Leong and A.S.M.A. Haseeb *
Centre for Advanced Materials, Department of Mechanical Engineering, Faculty of Engineering,
University of Malaya, Kuala Lumpur 50603, Malaysia; leongyeemei@siswa.um.edu.my
* Correspondence: haseeb@um.edu.my; Tel.: +60-3-79674492

Academic Editor: Geminiano Mancusi

Received: 26 May 2016; Accepted: 16 June 2016; Published: 28 June 2016

Abstract: Driven by the trends towards miniaturization in lead free electronic products, researchers
are putting immense efforts to improve the properties and reliabilities of Sn based solders. Recently,
much interest has been shown on low silver (Ag) content solder SAC105 (Sn-1.0Ag-0.5Cu) because of
economic reasons and improvement of impact resistance as compared to SAC305 (Sn-3.0Ag-0.5Cu.
The present work investigates the effect of minor aluminum (Al) addition (0.1–0.5 wt.%) to SAC105 on
the interfacial structure between solder and copper substrate during reflow. The addition of minor Al
promoted formation of small, equiaxed Cu-Al particle, which are identified as Cu3 Al2 . Cu3 Al2 resided
at the near surface/edges of the solder and exhibited higher hardness and modulus. Results show that
the minor addition of Al does not alter the morphology of the interfacial intermetallic compounds,
but they substantially suppress the growth of the interfacial Cu6 Sn5 intermetallic compound (IMC)
after reflow. During isothermal aging, minor alloying Al has reduced the thickness of interfacial
Cu6 Sn5 IMC but has no significant effect on the thickness of Cu3 Sn. It is suggested that of atoms of
Al exert their influence by hindering the flow of reacting species at the interface.

Keywords: intermetallic; mechanical properties; nanoindentation; interfacial reaction; microstructure;

differential scanning calorimetry; scanning electron microscopy; minor Al addition

1. Introduction
Restriction on the use of lead based solder in the electronic industry has led to extensive
developments in lead free solders. Driven by the necessity to improve the reliability of lead free
electronic products and by the trend towards miniaturization, researchers are putting intense efforts
into improving the properties of Sn based solders. Sn-Ag-Cu (SAC solder) alloys have been a favored
replacement for Sn-Pb solders. However, the currently used ternary eutectic (Tm = 217 ˝ C) or near
eutectic SAC solders have some drawbacks. These SAC solders were reported to have relatively
high amount of undercooling (10–30 ˝ C), as β-Sn requires large undercooling to nucleate and solidify.
This large undercooling promotes the formation of large, plate-like Ag3 Sn structures that have been
reported to cause joint embrittlement and reliability problem [1]. Research has been done on solders
with lower silver content of, e.g., Sn-1.0Ag-0.5Cu (SAC105), in an attempt to inhibit the formation
of Ag3 Sn and also to reduce the solder cost, as the price of Ag has increased dramatically in recent
years [2–5]. Although it has been reported that SAC105 performs better in drop tests, it has a higher
liquidus temperature, which requires a higher reflow profile than the eutectic Sn-3.8Ag-0.7Cu (SAC387)
alloy [5]. It also performs poorly in thermal cycling tests [6]. These drawbacks have prompted
researchers to modify the solder content by adding small amounts of other alloying elements to further
improve its reliability and lower its melting temperature.

Materials 2016, 9, 522; doi:10.3390/ma9070522 www.mdpi.com/journal/materials

Materials 2016, 9, 522 2 of 17

Fourth minor alloying elements (0.05–0.1 wt.%) that have been added into SAC solder include Ni,
Co, Fe, Mn, Zn, Ti, Ce, In and Al [7–10]. The effects of the fourth alloying element on the microstructure
and mechanical properties have been investigated. Improvements in mechanical properties such as
shear strength [10], tensile strength [7], impact resistance [5], and creep resistance [7] have been
reported. It has been observed that the addition of fourth alloying elements imparts their influence
on the mechanical properties by modifying the microstructure of the solder. It was observed that
the fourth alloying element modify the microstructure, by: (i) refining the microstructure of the
solder matrix; (ii) suppressing brittle intermetallic compound (IMC) formation; and (iii) changing the
morphology of the IMC in solder matrix/interface [11].
The addition of aluminum has attracted much interest in recent years. Research on Al addition
as nanoparticles or minor alloying element has been reported [12–18]. Amagai [12] observed that
the addition of 0.05% Al nanoparticles did not have any significant effect on the interfacial IMC.
As for the addition of aluminum as minor alloying element, a few works on the effect of Al on
the mechanical properties, microstructure and solder/Cu substrate interfacial reaction have been
reported [2,9,11,14–18]. Previous studies have shown that minor addition of Al gives promising results
in suppressing undercooling of β-Sn and reduced formation of brittle phase Ag3 Sn in SAC solder
matrix [14]. It was found that Al addition (0.05 wt.%) results in excellent shear strength retention after
thermal aging at 150 ˝ C for up to 1000 h. Faizul et al. have investigated the effect of Al (0.1–2 wt.%)
on the tensile strength of SAC105 [12,19]. They found that with 0.1 wt.% Al addition, Al reduced the
yield strength and ultimate tensile strength (UTS) and promoted ductile fracture. When Al addition
was more than 0.1 wt.%, the yield strength and ultimate tensile strength of the solder increased as a
function of Al content and brittle fracture modes were seen.
A couple of studies dealt with the effects of Al on the bulk microstructure and interfacial IMC
between solder and copper substrate [15,16,18]. With the addition of Al into Sn-Ag (SA) solder,
Al2 Cu IMC and ambiguous Al-Cu IMC were found in the bulk microstructure of SA solder on copper
substrate after reflow [16,18]. On the other hand, only ambiguous Al-Cu IMC (Anderson et al. reported
it as δ-Cu33 Al17 ) was found in the bulk microstructure of SAC [14,19]. Though the reported effect
of Al on the bulk microstructure seen by other researchers seems consistent, there are contradictory
reports on the effects of Al addition on the interfacial solder/Cu reaction. With addition of 0.5 wt.%
of Al into SA solder, Xia et al. observed a spalled layer of Al2 Cu compound layer near the interface
and the suppression of the growth of the Cu6 Sn5 layer. When Al was added up to 1 wt.%, a layer of
Al2 Cu compound was formed at the solder/Cu interface, which completely replaced Cu6 Sn5 layer [15].
On the other hand, Kotadia et al. reported that spherical Al-Cu IMC spalled away from the solder
matrix when Al was depleted in the solder and there was no suppression of the growth of interfacial
Cu6 Sn5 layer when 0.5 to 2.0 wt.% of Al was added in to SA solder [18]. Li et al. have reported that
with the addition of 1 wt.% Al into SAC387 solder, layered δ-Al2 Cu3 formed at the interface after
10 min reflow and the growth of the Cu6 Sn5 layer was reduced [16]. Dhaffer et al. have investigated
the effect of 0.1.wt.% Al addition on the interfacial reaction by dipping method, they reported that
0.1% Al addition have suppressed the growth of Cu6 Sn5 layer [20]. Until now, no detailed study has
been done for the effect of minor Al addition (<1 wt.%) on interfacial reaction of SAC/Cu.
Nanoindentation as a mechanical testing method has attracted a great deal of attraction in many
fields of research as it has the ability to measure the properties of sample in extremely small scales
such as thin films and coating in nanometer range [21]. This technique is well suited to investigate
the mechanical properties of IMCs, which have thicknesses of only several nanometers/micrometers.
Cu-Al IMC was reported to form in SAC even with addition of as low as 0.05 wt.% [22]. Besides, it has
been reported that Al is likely to substitute into Cu6 Sn5 as well [14] Previous studies with addition
such as Ni, and Mn have shown that solubility of minor alloying element in Cu6 Sn5 could alter the
nanomechanical properties of Cu6 Sn5 [14]. Thus, understanding the mechanical properties of Cu-Al
IMC and Cu6 Sn5 is essential in the understanding of deformation behavior and failure mechanisms in
lead-free solder joints.
The present work investigates the effect of Al on the interfacial IMC between SAC105 solder alloy
and copper substrate. This work concentrates on the effect of the lower percentage of Al (0.1–0.5 wt.%)
Materials 2016, 9, 522 3 of 17
Materials 2016, 9, 522 3 of 17

The present
on the Cu–Sn work
reaction investigates
during reflow and the isothermal
effect of Al aging.
on the As
interfacial
has been IMC between
noted SAC105
earlier [15,16],solder
absence
alloy
of Cu in and
the copper substrate.
solder led to theThis work concentrates
formation of Al2 Cu andon the effect
Al-Cu IMC of the lowerthe
near/at percentage
interfaceofduring
Al
(0.1–0.5 wt.%) on the Cu–Sn reaction during reflow and isothermal aging. As
reflow, and the IMCs tended to spall away from the solder matrix when Al was depleted in solder,has been noted earlier
thus[15,16], absence the
complicating of Cu in the solder
situation at theled to the formation
interface. ofpresence
With the Al2Cu andofAl-Cu
Cu inIMC
SACnear/at the
solder, it interface
is expected
during reflow, and the IMCs tended to spall away from the solder matrix when Al
that Al will react with Cu in the bulk and thus provide a more simplified scenario at the interface, was depleted in
solder, thus complicating the situation at the interface. With the presence of Cu in SAC solder, it is
which may lead to a better understanding of the effects of Al. This study concentrates on the lower
expected that Al will react with Cu in the bulk and thus provide a more simplified scenario at the
percentage of Al (0.1%–0.5%), as higher percentages may lead to formation of Al2 Cu and other IMCs
interface, which may lead to a better understanding of the effects of Al. This study concentrates on
at the interface. Furthermore, this study investigates the nanomechanical properties of Cu-Al IMC
the lower percentage of Al (0.1%–0.5%), as higher percentages may lead to formation of Al2Cu and
particles and also
other IMCs examines
at the interface.whether
Furthermore,addition of Alinvestigates
this study would affect the the nanomechanical
nanomechanical properties
properties of
of Cu 6
Cu-AlSn .
5 IMC particles and also examines whether addition of Al would affect the nanomechanical
properties of Cu6Sn5.
2. Results
2. Results
2.1. Differential Scanning Calorimetry
2.1. Differential
Figure 1 shows Scanning CalorimetryScanning Calorimetry (DSC) curves for SAC105, SAC105 + 0.1Al,
the Differential
SAC105Figure
+ 0.3Al
1 showsand theSAC105 + 0.5Al.
Differential Scanning During heating,
Calorimetry (DSC)SAC105
curves for and SAC105
SAC105, + 0.1Al
SAC105 solder
+ 0.1Al,
show an onset melting temperature ˝ ˝
SAC105 + 0.3Al and SAC105 + 0.5Al.(T m ) of 216.84
During heating, C ˘ 0.50and
SAC105 and 216.43+ 0.1Al
SAC105 C ˘ solder
0.38, respectively.
show an
Thisonset
onsetmelting
temperature corresponds
(Tm) of to the ternary eutectic reaction
°C ±(T0.38, ˝ C) of Sn-Ag-Cu
temperature 216.84 °C ± 0.50 and 216.43 m = 217
respectively. This onset alloy,
L Ñtemperature
Ag3 Sn + Cucorresponds
Sn + Sn to the
[23]. ternary
Two eutectic
prominent reaction
peaks (T
were m = 217
seen °C)
at of
~221 ˝ C and ~228
Sn-Ag-Cu alloy, ˝LC→ inAg Sn
SAC105
3
6 5
and+SAC105
Cu6Sn5 ++Sn [23].(Figure
0.1Al Two prominent peakstwo
1a,b). These were seen were
peaks at ~221 °C and ~228
associated with°Cthe
in SAC105
eutecticand SAC105 + for
temperature
0.1Al (Figure 1a,b). These two peaks were associated with the eutectic
Sn-Ag (L Ñ Ag3 Sn + Sn) and Sn-Cu (L Ñ Cu6 Sn5 + Sn), respectively. As the amount of Al was temperature for Sn-Ag
added
up to → Ag
(L 0.3 3Sn + Sn) and Sn-Cu (L → Cu6Sn5 + Sn), respectively. As the amount of Al was added up to
wt.%, there is a change in the DSC curve (Figure 1c). The onset temperature was shifted to
0.3 wt.%,
221.14 ˝ C ˘ there
0.36 and is a change
221.65 in
˝ Cthe
˘ DSC
1.02, curve (Figure 1c).
respectively for The
SAC105onset+temperature was shifted
0.3Al and SAC105 to 221.14
+ 0.5Al which
°C ± 0.36 and 221.65 °C ± 1.02, respectively for SAC105 ˝ + 0.3Al and SAC105 + 0.5Al which
corresponded to Sn-Ag eutectic temperature (Tm = 221 C). For SAC105 + 0.3Al, a first small peak of
corresponded to Sn-Ag eutectic temperature (Tm = 221 °C). For SAC105 + 0.3Al, a first small peak of
heat absorption appears at 224 ˝ C, followed by a second larger peak of heat absorption at ~231 ˝ C
heat absorption appears at 224 °C, followed by a second larger peak of heat absorption˝ at ~231 °C
(Figure 1c). For SAC105 + 0.5Al, only a large peak of heat absorption appears at ~231 C (Figure 1d).
(Figure 1c). For SAC105 + 0.5Al, only a large peak of heat absorption appears at ~231 °C (Figure 1d).
TheThe
peak at ~231 ˝ corresponds to the melting temperature of Sn (T = 231 ˝ C).
peak at ~231C°C corresponds to the melting temperature of Sn (Tmm= 231 °C).
During cooling, the
During cooling, the nucleation
nucleationtemperature
temperature was determinedby
was determined bythe
theonset
onset solidification
solidification of the
of the
exothermic peak (Figure 1b). SAC105 has an onset solidification at 200.12 ˘ 0.64 ˝ C. Addition
exothermic peak (Figure 1b). SAC105 has an onset solidification at 200.12 ± 0.64 °C. Addition of
of aluminum
aluminum to SAC105 shifted the
SAC105 shifted the exothermic
exothermicpeak peaktotothetheright,
right,where
where thethe onset
onset solidification
solidification
temperature
temperature is 215.84 ˝
is 215.84C°C˘ ±1.39, 1.39, 217.74
217.74 °C˝ C ˘ 0.83 and
± 0.83 and 219.17 ˝
219.17°CC± ˘0.21 0.21forfor SAC105
SAC105 + 0.1Al,
+ 0.1Al,
SAC105
SAC105 + 0.3Al
+ 0.3Al and and SAC105+ +0.5Al,
SAC105 0.5Al,respectively.
respectively.

(a)

Figure 1. Cont.
Materials 2016, 9, 522 4 of 17
Materials 2016, 9, 522 4 of 17

(b)
Figure 1. DSC curves for as cast SAC105, SAC105 + 0.1Al, SAC105 + 0.3Al and SAC105 + 0.5Al alloys:
Figure 1. DSC curves for as cast SAC105, SAC105 + 0.1Al, SAC105 + 0.3Al and SAC105 + 0.5Al alloys:
(a) heating; and (b) cooling.
(a) heating; and (b) cooling.
The degree of undercooling, ∆T, was defined by the difference of two onset temperatures in
The degree
cooling of undercooling,
and heating ∆T,1,was
curve. In Table defined
it can bythat
be seen theSAC105
difference
has of
thetwo onset
largest temperatures
undercooling of in
cooling
~17 °C. The addition of Al into SAC105 solder reduced the degree of undercooling significantly in all of
and heating curve. In Table 1, it can be seen that SAC105 has the largest undercooling
˝ C. The addition of Al into SAC105 solder reduced the degree of undercooling significantly in all
~17cases where Al was added.
cases where Al was added.
Table 1. Onset of melting, onset of solidification and undercooling of SAC105, SAC105 + 0.1Al,
Table 1. Onset
SAC105 + 0.3Alofand
melting,
SAC105onset of solidification and undercooling of SAC105, SAC105 + 0.1Al,
+ 0.5Al.
SAC105 + 0.3Al and SAC105 + 0.5Al.
Solder Onset of Melting (°C) Onset of Solidification (°C) Undercooling (°C)
SAC105
Solder 216.84 ± 0.50 ˝
Onset of Melting ( C) 200.12 ± 0.64 ˝ ~17 (˝ C)
Onset of Solidification ( C) Undercooling
SAC105 + 0.1Al 216.43 ± 0.38 215.84 ± 1.39 ~0.6
SAC105 216.84 ˘ 0.50 200.12 ˘ 0.64 ~17
SAC105 + 0.3Al 221.14 ± 0.36 217.74 ± 0.83 ~3.4
SAC105 + 0.1Al 216.43 ˘ 0.38 215.84 ˘ 1.39 ~0.6
SAC105 + 0.5Al
SAC105 + 0.3Al 221.65 ± 1.02
221.14 ˘ 0.36 219.17 ± 0.21
217.74 ˘ 0.83 ~2.48
~3.4
SAC105 + 0.5Al 221.65 ˘ 1.02 219.17 ˘ 0.21 ~2.48
2.2. Microstructure
Figure 2a–h shows the cross sectional Scanning Electron Microscopy (SEM) images of as-
2.2. Microstructure
received solder alloys and reflowed solder joints prepared on copper substrates. Cross sectional
Figureof2a–h
images shows the
as-received crosssamples
SAC105 sectionalshowScanning
primaryElectron
Sn phase Microscopy
having a (SEM)
lighter images
contrastofwhile
as-received
the
solder
darkeralloys and reflowed
contrast solder joints
phase represents Cu6Sn5prepared
. The Cu6Sn on5 formed
copper asubstrates.
continuousCross
networksectional images of
in the as-cast
as-received SAC105
SAC105 solder samples
and fine Ag show primary are
3Sn particles Sn phase having
also seen a lighter
in the as-castcontrast
solder. while
With the
the darker
additioncontrast
of
phase represents Cu
0.1 wt.% Al, Cu6Sn56phase Sn . The Cu
5 and particles
6 Sn formed a continuous network in the as-cast SAC105
5 of another new darker phase are seen distributed in the lighter solder
andcontrast
fine AgSn 3 Sn particles
phase. are also
The darker seen inare
particles theseen
as-cast solder. With
to agglomerate in the Sn
addition of 0.1 wt.%
phase (Figure Al, Cu
2b). With the6 Sn5
addition
phase of 0.3 wt.%
and particles of and
another0.5 wt.%
newAl, elongated
darker phaseshapes
are seenof new darker IMC
distributed phase
in the are seen
lighter distributed
contrast Sn phase.
Theindarker
the lighter contrast
particles are Sn
seenphase. It can be seen
to agglomerate inthat
the the Sn grain
Sn phase size decreases
(Figure 2b). With with
theAl additionofin0.3
addition thewt.%
as-received alloys. After reflow, the bulk microstructure of the reflowed solder
and 0.5 wt.% Al, elongated shapes of new darker IMC phase are seen distributed in the lighter contrast was different from
Sn that
phase.of the as-received
It can be seen solder.
that theFrom Figure
Sn grain 2e,fdecreases
size it can be seen
with that Cu6Sn5 and
Al addition Ag3Sn
in the particles are
as-received alloys.
larger after 1 × reflow as compared to Figure 2a,b. After 1 × reflow, with the addition of 0.3 wt.% and
After reflow, the bulk microstructure of the reflowed solder was different from that of the as-received
0.5 wt.% Al, equiaxed darker IMC was seen distributed in Sn phase instead of elongated shape of
solder. From Figure 2e,f it can be seen that Cu6 Sn5 and Ag3 Sn particles are larger after 1 ˆ reflow as
new darker IMC in the as-received sample. Sn grain size reduction as a function of Al content still
compared to Figure 2a,b. After 1 ˆ reflow, with the addition of 0.3 wt.% and 0.5 wt.% Al, equiaxed
persists in reflowed sample.
darker IMC was seen distributed in Sn phase instead of elongated shape of new darker IMC in the
as-received sample. Sn grain size reduction as a function of Al content still persists in reflowed sample.
Materials 2016, 9, 522 5 of 17
Materials 2016, 9, 522 5 of 17
Materials 2016, 9, 522 5 of 17

Figure 2. SEM images

SEMimages ofofcross
imagesof crosssectional
sectionalsamples of bulk
samples microstructure of of
as as
cast (a–d) and after 1×
Figure
Figure 2.2.SEM cross sectional samples of of bulk
bulk microstructure
microstructure of as castcast (a–d)
(a–d) andand
afterafter
1×
reflow (e–h)
1 ˆ reflow of SAC105, SAC105 + 0.1Al, SAC105 + 0.3Al and SAC105 + 0.5Al.
reflow (e–h)(e–h) of SAC105,
of SAC105, SAC105SAC105 + 0.1Al,
+ 0.1Al, SAC105
SAC105 + 0.3Al
+ 0.3Al and SAC105
and SAC105 + 0.5Al.
+ 0.5Al.
Figure 3a
Figure 3a showsthe the optical microscope cross-sectional images of SAC105 + 0.5Altopnear top
Figure 3a shows
shows theoptical microscope
optical microscope cross-sectional images
cross-sectional of SAC105
images + 0.5Al
of SAC105 + near
0.5Al nearsurface
top
surface
of solderof solder after 1 × reflow. It can be seenthethat thedarker
new darker phase equiaxed IMC agglomerated
surface of after
solder1 after
ˆ reflow. It can Itbe
1 × reflow. seen
can be that
seen thatnewthe new darkerphase equiaxed
phase IMCIMC
equiaxed agglomerated
agglomeratedand
and
was was mostly
mostly foundfound
near near
the the
toptop surface
surface of of
thethe solder
solder joint.
joint. Agglomeration
Agglomeration of
of the
the new
new darker phase
darker phase
and was mostly found near the top surface of the solder joint. Agglomeration of the new darker phase
near the
near the top
top surface
surface of
of solder
solder is
is also
also found
found SAC105
SAC105 + 0.3Al.
0.3Al. Figure 3b shows
shows the
the new
new darker
darker phase
phase
near the top surface of solder is also found SAC105 ++ 0.3Al. Figure3b
Figure 3b shows the new darker phase
equiaxed IMC
equiaxed IMC under
under high
high magnification.
magnification. It It can
can be
be seen
seen that the
thatthe new
thenew faceted
newfaceted IMC
facetedIMC particles
IMCparticles have
particleshave varied
havevaried
varied
equiaxed IMC under high magnification. It can be seen that
sizes,
sizes, ranging
ranging from
from 1
1 to
to 5
5 μm.
µm.
sizes, ranging from 1 to 5 μm.

(a) (b)
(a) (b)
Figure 3. (a) Optical microscope cross sectional images SAC105 + 0.5Al near top surface of the solder
Figure 3. (a)
(a)Optical
Opticalmicroscope cross sectional images SAC105 ++0.5Al near top
topsurface of
ofthe
thesolder
Figure
after 1 3.
× reflow andmicroscope
(b) FESEMcross sectional
images imagesbut
of equiaxed SAC105
faceted 0.5Al
IMCsnear
found surface
at solder
cross-sectioned of
after
after 1
1 ׈ reflow
reflow and
and (b)
(b)FESEM
FESEM images
images of
of equiaxed
equiaxed but
but faceted
faceted IMCs
IMCs found
found at
at cross-sectioned
cross-sectioned of
of
SAC105 + 0.5Al.
SAC105
SAC105++0.5Al.
0.5Al.
Energy-dispersive X-ray Spectroscopic (EDS) analysis was conducted on the new IMC phase
Energy-dispersive
Energy-dispersive X-ray
X-ray Spectroscopic
Spectroscopic (EDS)
(EDS) analysis
analysis was
was conducted
conducted on
on the new
new IMC
theindicated
IMC phase
phase
found in SAC105 + 0.1Al, SAC105 + 0.3Al and SAC105 + 0.5Al. Analysis results that the
found
found in SAC105
in SAC105 + 0.1Al,
+ 0.1Al, SAC105
SAC105 + 0.3Al and SAC105 + 0.5Al. Analysis results indicated that the
composition of the new phase was+ 60–65
0.3Al and
at.%SAC105
Cu, 35–40+ 0.5Al.
at.% Analysis
Al. EDS results
Line scanindicated that the
and elemental
composition
composition of the
of thenew
new phase was 60–65 at.% 35–40
Cu, 35–40 Al.at.% Al.Line
EDSscan
Line scan and elemental
mapping analysis werephase
also was 60–65
conducted at.%
on Cu,
the new at.%IMC phase EDS (Figures 4and
andelemental
5). Both mapping
analysis
mapping
analysis analysis
were were also conducted on thephase
new (Figures
IMC phase (Figures 4 and 5). confirmed
Both analysis
confirmed thatalso
thisconducted
darker IMCon phase
the new IMC
consists of only Al and4 Cu.
and 5). Both
Based onanalysis
the ratio of Al andthat Cu
confirmed
this darker that
IMCthis darker
phase IMC of
consists phase
only consists
Al andIMC of only
Cu. Based Al andtheCu. BasedAlonandthe ratio of Al possible
and Cu
content, possible identification this darker phase on is Cu ratio
3Al 2 (δ)ofor Cu9AlCu4 (γcontent,
1), both of which
content, possible this
identification identification ofphase
this darker IMC(δ)phase is Al
Cu3Al2 (δ) or Cu9Al4 (γ1), both of which
could exist in of darker IMC
the temperature range is Cu
below 3 Al°C
300 or Cu
2 [24]. 9 4 (γ1 ), both of which could exist in the
could exist in the temperature range
temperature range below 300 ˝ C [24]. below 300 °C [24].
Materials 2016, 9, 522 6 of 17
Materials 2016, 9, 522 6 of 17
Materials 2016, 9, 522 6 of 17

3 µm
3 µm

Figure 4.EDS
Figure EDSline
line scan
scan across
across equiaxed
equiaxed IMCs in SAC105 ++ 0.5Al.
0.5Al.
Figure 4.
4. EDS line scan across equiaxed IMCs in SAC105 + 0.5Al.

Figure 5. (a) Cross-sectioned image of SAC105 + 0.5Al after 1 × reflow. Elemental maps for the
Figure 5.5. (a)
(a) Cross-sectioned
Cross-sectioned image of SAC105 ++ 0.5Al
0.5Al after
after 11 ׈ reflow.
reflow. Elemental
Elementalmaps
mapsfor
forthe
Figure
constituent elements: (b) Al; (c)image ofSn;
Cu; (d) SAC105
and (e) Ag. the
constituent elements:
constituent elements: (b)
(b) Al;
Al; (c)
(c) Cu;
Cu; (d)
(d) Sn;
Sn; and
and (e)
(e) Ag.
Ag.
In the previous studies on minor addition of Al, many researchers attempted to identify Cu-Al
In the previous studies on minor addition of Al, many researchers attempted to identify Cu-Al
IMC bythe
In EDSprevious
analysis. studies
There on areminor
a few Cu-Aladdition of Al,
binary many
phases researchers
that attempted
have compositions to identify
close Cu-Al
to each other,
IMC by EDS analysis. There are a few Cu-Al binary phases that have compositions close to each other,
IMC
suchbyasEDS γ1-Cuanalysis.
9Al4, ζ2-Cu There4Al3,are and a fewδ-CuCu-Al binary
3Al2. This makesphases that have
it difficult forcompositions
researchers to close to each
accurately
such as γ1-Cu9Al4, ζ2-Cu4Al3, and δ-Cu3Al2. This makes it difficult for researchers to accurately
other, such
identify asexact
the γ1 -Cu Al
Cu-Al
9 4 2 , ζ
phase-Cu Al
form
4 3 , and δ-Cu
[2,17,20]. Al . This
Similarly,
3 2 makes
in this it difficult
study, EDX for researchers
analysis could to
not accurately
provide
identify the exact Cu-Al phase form [2,17,20]. Similarly, in this study, EDX analysis could not provide
identify the exact Cu-Al
clear identification phase
for the Cu-Al form [2,17,20]. Anderson
compound. Similarly, et in al.
thiswho
study, EDXthe
studied analysis
effect could not provide
of Al addition on
clear identification for the Cu-Al compound. Anderson et al. who studied the effect of Al addition on
clear identification for
the microstructure the Cu-Al
of solder havecompound.
identified the Anderson
Cu-Al IMC et al. who 33studied
as δ-Cu Al17. They thedid
effect
so byof Al addition
casting out
the microstructure of solder have identified the Cu-Al IMC as δ-Cu33Al17. They did so by casting out
ona Cu-Al block which has
the microstructure the similar
of solder havecomposition
identified the with the Cu-Al
Cu-Al IMC as IMCδ-Cu they
33 Alobtained
17 . Theyindid thesobulkby solder,
casting
a Cu-Al block which has the similar composition with the Cu-Al IMC they obtained in the bulk solder,
anda analyzed
out Cu-Al block it using
which X-rayhas diffraction
the similar(XRD) [14]. Though
composition with the Anderson
Cu-Al IMC et al. they
haveobtained
chosen toinrefer the to it
bulk
and analyzed it using X-ray diffraction (XRD) [14]. Though Anderson et al. have chosen to refer to it
as δ-Cu
solder, 33Alanalyzed
and 17, the generalit usingnomenclature
X-ray diffraction for these(XRD)
IMC is[14]. also known
ThoughasAnderson
δ-Cu3Al2 [24]. et al.Byhavecomparing
chosen
as δ-Cu33Al17, the general nomenclature for these IMC is also known as δ-Cu3Al2 [24]. By comparing
tothe morphology
refer to it as δ-Cu of Cu-Al
33 Al17IMC IMC (Figure
, the(Figure
general3a) 3a) in this studyfor
nomenclature to δ-Cu
these33AlIMC17 [14], it can
is also be seen
known as that
δ-Cuthey 2both
3 Alboth
[24].
the morphology of Cu-Al in this study to δ-Cu33Al17 [14], it can be seen that they
Byexhibit a
comparing similar morphology
themorphology
morphology(equiaxed (equiaxed
of Cu-Aland and
IMC faceted
(Figure dark color
3a) color
in this appearance
study to δ-Cu under33 AlField-emission
17 [14], it can
exhibit a similar faceted dark appearance under Field-emission
bescanning electron microscopy (FESEM) and size (size(equiaxed
varied from 1faceted
to 5 μm)). Thus, it would be
scanning electron microscopy (FESEM) and size (size varied from 1 to 5 μm)). Thus, itappearance
seen that they both exhibit a similar morphology and dark color would be
logical
under to assume
Field-emission both IMC
scanning are of the
electron same kind,
microscopy and it will
(FESEM) be referred
and size to
(size as Cu Al
varied
3 2 in
fromthe 1 following
to 5 µm)).
logical to assume both IMC are of the same kind, and it will be referred to as Cu3Al2 in the following
discussion.
Thus, it would be logical to assume both IMC are of the same kind, and it will be referred to as Cu3 Al2
discussion.
in the following discussion.
2.3. Interfacial Reaction after Reflow
2.3. Interfacial Reaction after Reflow
2.3. Interfacial Reaction after Reflow
Figure 6 shows cross-sectional FESEM micrographs at the solder/Cu interface after 1 × reflow. A
Figure 6 shows cross-sectional FESEM micrographs at the solder/Cu interface after 1 × reflow. A
typical
Figurescallop type Cu
6 shows 6Sn5 layer forms
cross-sectional FESEM at themicrographs
SAC105/Cu at interface after reflow
the solder/Cu (Figure
interface 6a).1Upon
after the
ˆ reflow.
typical scallop type Cu6Sn5 layer forms at the SAC105/Cu interface after reflow (Figure 6a). Upon the
addition
Aaddition of aluminum,
typical scallop type Cu the Sn scallop
layer
6 scallop
5 morphology
forms at the is still
SAC105/Cu seen, but the
interface IMCafter becomes
reflow more
(Figure flat as
6a). Al
Upon is
of aluminum, the morphology is still seen, but the IMC becomes more flat as Al is
added
the up
addition to 0.5 wt.% (Figure 6c). The IMC height is reduced with the addition of Al. The average
added up toof0.5 aluminum,
wt.% (Figure the scallop
6c). Themorphology
IMC heightisisstill seen, but
reduced withthe theIMC becomes
addition more
of Al. The flat as Al is
average
Materials 2016, 9, 522 7 of 17

added up 2016,
Materials to 0.5 wt.% (Figure 6c). The IMC height is reduced with the addition of Al. The
9, 522 average
7 of 17
Materials 2016, 9, 522 7 of 17
thickness of the total IMC layer is plotted as a function of Al content in Figure 7. The influence of Al
thickness
addition of
on the the total IMC
interfacial layer
IMC is plotted
thickness as a function
is obvious. of
TheAl content in Figure
thickness ofFigure 7. The
the interfacialinfluence of
IMC does Al not
thickness
addition onofthetheinterfacial
total IMC IMClayerthickness
is plottedisasobvious.
a function The of thickness
Al contentofinthe 7. The IMC
interfacial influence
does ofnotAl
seemaddition
to varyon with the Al content
the interfacial of the
IMC thickness solder in the
is obvious. range 0.1–0.5
The thickness wt.%.
of the This may
interfacial indicate
IMC that that
doesthenot the
seem to vary with the Al content of the solder in the range 0.1–0.5 wt.%. This may indicate
addition of
seem to ofAl
varybeyond a certain
with theaAl percentage
content does
of the solder not bring additional benefit in terms of suppression
that the of
addition Al beyond certain percentage does innotthe range
bring 0.1–0.5 wt.%.
additional benefit This may indicate
in terms of suppression
IMC growth.
ofaddition ofCu
IMC growth. Al6 Sn wasathe
beyond
Cu56Sn5 was
onlypercentage
certain
the only
IMC found atat
does
IMC found
the
not interface,
thebring
and no trace
additional
interface, and nobenefit
of Al
inAl
trace of
in Cu
terms
in Cuof6SnSn 5 and Al-Cu
6suppression
5 and Al-
compound
of IMC could
growth. beCudetected
6Sn5 was at the
the onlyinterface
IMC of
found all
at aluminum-added
the interface,
Cu compound could be detected at the interface of all aluminum-added solder. and no solder.
trace of Al in Cu 6Sn5 and Al-

Cu compound could be detected at the interface of all aluminum-added solder.

(a) (b)
(a) (b)

(c) (d)
(c) (d)
Figure 6. Cross sectional FESEM micrographs of: (a) SAC105; (b) SAC105 + 0.1Al; (c) SAC105 + 0.3Al;
Figure 6.
Figure
Cross sectional FESEM
6. Cross+sectional FESEM
micrographs of: (a) SAC105; (b) SAC105 + 0.1Al; (c) SAC105 + 0.3Al;
micrographs of: (a) SAC105; (b) SAC105 + 0.1Al; (c) SAC105 + 0.3Al;
and (d) SAC105 0.5Al after 1 × reflow.
and and
(d) SAC105
(d) SAC105 + 0.5Al after
+ 0.5Al 1 1ˆ×reflow.
after reflow.

Figure 7. Variation of Cu6Sn5 thickness with Al content during 1 × reflow.

Figure 7. Variation of Cu6Sn5 thickness with Al content during 1 × reflow.
Figure 7. Variation of Cu6 Sn5 thickness with Al content during 1 ˆ reflow.
Materials 2016, 9, 522 8 of 17

2.4. Top View 2016,

Materials of Cu Sn5 Solder after 1 ˆ Reflow
9,6522 8 of 17

Figure
2.4. Top8a shows
View of Cu6top view after
Sn5 Solder image1 × of deeply etched SAC105 + 0.5Al after 1 ˆ reflow. Prior to
Reflow
FESEM imaging, both samples were deeply etched in a mixture of 93% CH3 OH, 5% HNO3 and 2%
Figure 8a shows top view image of deeply etched SAC105 + 0.5Al after 1 × reflow. Prior to FESEM
HCl to remove the solder matrix and thereby expose the interfacial IMC. The IMC grains found on the
imaging, both samples were deeply etched in a mixture of 93% CH3OH, 5% HNO3 and 2% HCl to
interface of SAC105 and SAC105 + 0.5Al were identified as Cu6 Sn5 .The
remove the solder matrix and thereby expose the interfacial IMC.
It can be seen from the images
IMC grains found on the
that SAC105 + 0.5Al shows somewhat faceted Cu
interface of SAC105 and SAC105 + 0.5Al were identified 6 Sn 5 grains.
as Cu6Sn5. It can be seen from the in
Under high magnification the high
images
Al concentration
that SAC105region,
+ 0.5Al small
shows and agglomerated
somewhat faceted Cu particles areUnder
6Sn5 grains. seen (encircled in yellow
high magnification in dotted
the highline).
EDS analysis was done
Al concentration on the
region, high
small Alagglomerated
and concentration particle.
particles are Figure 8b–d shows
seen (encircled the dotted
in yellow EDS elemental
line).
maps.EDS
Under highwas
analysis resolution
done onimaging
the high Aland elemental mapping,
concentration Al, Ag
particle. Figure and
8b–d Cu were
shows detected
the EDS elementalon the
maps. Under high resolution imaging and elemental mapping, Al, Ag and Cu were
surface of the exposed IMC. In Figure 8b, the presence of Al is indicated in green. The region of high detected on the
surface ofof
concentration theAlexposed IMC. In
is encircled inFigure
yellow.8b,Itthe presence
can be seen of that
Al is the
indicated
regioninwith
green.high
The Al
region of high
concentration
concentration of Al is encircled in yellow. It can be seen that the region with high Al concentration
corresponds to that of Cu (compare Figure 8b,c). The agglomerated particles are identical to the Cu-Al
corresponds to that of Cu (compare Figure 8b,c). The agglomerated particles are identical to the
IMC that was found in the bulk microstructure. The elongated and plate-like particles (right corner of
Cu-Al IMC that was found in the bulk microstructure. The elongated and plate-like particles (right
Figurecorner
8d) onofthe Cu Sn IMC grains are identified as Ag3 Sn.as Ag3Sn.
Figure 68d) 5on the Cu6Sn5 IMC grains are identified

FigureFigure 8. (a)view
8. (a) Top Top view
imageimage of deeply
of deeply etched
etched SAC105
SAC105 + 0.5Al
+ 0.5Al after
after 1ˆ 1 ×reflow.
reflow.Elemental
Elemental maps
maps for
for the
the constituent elements: (b) Al; (c) Cu; and (d) Ag.
constituent elements: (b) Al; (c) Cu; and (d) Ag.
2.5. Interfacial Reaction After Isothermal Aging
2.5. Interfacial Reaction After Isothermal Aging
After 1 × reflow, some of the solder samples were also subjected to isothermal aging at 150 °C
After
for up1 to reflow,
ˆ 720 someto
h in order ofstudy
the solder samples
the effects of Al were also
addition onsubjected to isothermal
the solid state at 150 ˝ C
aging solder
reaction between
for upandto copper
720 h in order to
substrate. study9 shows
Figure the effects of Alsectional
the cross addition on the
images solid state reaction
of isothermally between
aged SAC105,
solderSAC105
and copper
+ 0.1Al,substrate.
SAC105 + Figure
0.3Al and9 shows
SAC105the cross After
+ 0.5Al. sectional
thermalimages
aging of
forisothermally
720 h, anotheraged
SAC105, SAC105 +layer
intermetallic 0.1Al, SAC105
(darker + 0.3Al
layer) formedand SAC105the
in between + 0.5Al. After thermal
first intermetallic layeraging
and Cuforsubstrate
720 h, another
in
both SAC and SAC + Al solders. EDS was used to determine the composition
intermetallic layer (darker layer) formed in between the first intermetallic layer and Cu substrate of each layer. It is in
confirmed by elemental ratio by EDS analysis that the outer layer is Cu 6Sn5 and the inner layer is
both SAC and SAC + Al solders. EDS was used to determine the composition of each layer. It is
Cu3Sn.by
confirmed Within the resolution
elemental ratio byofEDS
EDS,analysis
there wasthat
no aluminum
the outerdetected
layer isinCubothSn
Cu6and
Sn5 and
theCu 3Sn after
inner layer is
6 5
thermal aging. The morphology of Cu6Sn5 and Cu3Sn are seen to be similar in SAC105 and
Cu3 Sn. Within the resolution of EDS, there was no aluminum detected in both Cu6 Sn5 and Cu3 Sn
SAC105 + Al solders.
after thermal aging. The morphology of Cu6 Sn5 and Cu3 Sn are seen to be similar in SAC105 and
SAC105 + Al solders.
Materials 2016, 9, 522 9 of 17
Materials 2016, 9, 522 9 of 17
Materials 2016, 9, 522 9 of 17

(a)
(a) (b)
(b)

(c)
(c) (d)
(d)
Figure 9.Cross
Cross sectional images
images of:
of: (a) SAC105; (b) SAC105
(a) SAC105; + 0.1Al; (c) SAC105 + +
0.3Al; and
Figure 9.
9. Cross sectional (a) (b) SAC105 + 0.1Al; (c) SAC105
SAC105 + 0.3Al;
0.3Al; and
(d) SAC105 + 0.5Al after aging at 150 ˝°C for 720 h.
(d) SAC105
SAC105 ++ 0.5Al after aging at 150 °C C for 720 h.

From Figure 9, it is seen that the addition of Al up to 0.5 wt.% has slowed down the growth of
From
From Figure
Figure9,9,ititisisseen
seenthat
thatthetheaddition
additionofof
AlAl
upup to to
0.50.5
wt.% hashas
wt.% slowed down
slowed the the
down growth of the
growth of
the total interfacial IMCs. Figure 10 shows the thickness of Cu6Sn5 and Cu3Sn plotted as a function of
total interfacial
theAltotal IMCs. Figure 10 shows the thickness of Cu Sn56Sn
and Cu3CuSn3Sn
plotted as aasfunction of Al
interfacial IMCs. Figure 10 shows the thickness of
content. It can be seen that Cu6Sn5 is reduced as Al is added, up to 0.5 wt.%. However, the thickness of
6 Cu 5 and plotted a function
content.
Alof It can
content.
Cu3Sn be be
seen
It almost
is can thethat
seen Cufor
that
same 6 Sn
Cu 5 is
6Sn
all reduced
5 is reducedasasAl
samples. Alisisadded,
added,up uptoto0.5
0.5wt.%.
wt.%. However,
However, thethe thickness
of Cu33Sn is almost the same for all samples.

Figure 10. Variation of thickness of IMC with Al content after aging at 150 °C for 720 h.

10. Variation of thickness ˝

FigureProperties
2.6. Mechanical thickness of
of IMC
IMC with
with Al
Al content
content after
after aging
aging at
at 150 C for 720 h.
150 °C

Indentation
2.6. Mechanical testing was carried out on bulk solder and the intermetallic phase in the solders,
Properties
e.g., Cu6Sn5 and Cu3Al2. The hardness of the bulk solder was determined by Vickers hardness test
Indentation
while the hardnesstesting was carried
of individual out on bulk
intermetallic solder
phase and the intermetallic
was determined phase in Figure
by nanoindentation. the solders,
11
e.g.,
shows6 the5 hardness3 of 2solder with varying Al content. It can be seen that the hardness of the soldertest
Cu 6 Sn5 and
and Cu 3 Al
Al 2 . . The
The hardness
hardness of
of the
the bulk
bulk solder
solder was
was determined
determined by Vickers hardness
while the
the hardness
increases hardness of
of individual
as a function individual intermetallic
SAC105 phase
intermetallic
of Al content. washardness
exhibited determined by HV
of 9.78 nanoindentation.
while SAC105 +Figure
0.5Al 11
shows the hardness
exhibited the highest of solder
hardness with varying
value Al HV.
of 14.12 content. It can of
The result beSAC105
seen thatis the hardness
in good of thewith
agreement solder
increases as a function
other studiesfunction of Al content. SAC105
[25,26]. of Al content. SAC105 exhibited exhibited hardness of 9.78
9.78 HV while SAC105 + 0.5Al
HV while SAC105 +
exhibited the highest hardness value of 14.12 HV. The The result
result of
of SAC105
SAC105 is in in good
good agreement
agreement with
other studies [25,26].
[25,26].
Materials 2016, 9, 522 10 of 17
Materials 2016, 9, 522 10 of 17
Materials 2016, 9, 522 10 of 17

Figure 11.Variation
Figure11. VariationofofVickers
Vickershardness
hardness with Al content
with Al contentfor
foras
asreceived
receivedsamples.
samples.
Figure 11. Variation of Vickers hardness with Al content for as received samples.
Figure
Figure 1212 shows
shows typical
typical loadload displacement
displacementdata dataobtained
obtainedthrough
throughindentations
indentationsperformed
performedon onSn,
CuSn, Figure 12 shows typical load displacement data obtained through indentations performed on
6 SnCu
5 and6SnCu 5 and
3 AlCu
2 of 3Al of a maximum
a 2maximum load ofload 500 of µN.500ForμN. Forofathe
a test testsame
of the same maximum
maximum load, theload, the
maximum
Sn, Cu
penetration 6Sn5 and Cu3Al2 of a maximum load of 500 μN. For a test of the same maximum load, the
maximumofpenetration
the indenterofforthe indentersolder
Sn-Ag-Cu for Sn-Ag-Cu solder is
is approximately 4.5approximately
times of that measured4.5 timesfor ofCuthat
6 Sn5
maximumfor
measured penetration
Cu Sn and of Althe Cu indenter
. The for Sn-Ag-Cu
solder matrix, as solder is approximately
expected, is very soft, 4.5 atimes
with of that
hardness of
and Al3 Cu2 . The solder matrix, as expected, is very soft, with a hardness of 0.23–0.3 GPa. The matrix
6 5 3 2
measured
0.23–0.3 GPa. for The
Cu6Sn 5 and Al3Cu2. The solder matrix, as expected, is very soft, with a hardness of
matrix exhibited significant plasticity. Upon unloading, the solder recovers only
exhibited significant plasticity. Upon unloading, the solder recovers only approximately 10 nm of the
0.23–0.3 GPa. The matrix exhibited
230 nmsignificant plasticity.penetrated.
Upon unloading, the solder recovers both
only
230approximately
nm that the indenter 10 nm ofpenetrated.
the that
In the indenter
contrast to the solder, bothInintermetallics
contrast to the aresolder,
significantly
approximately
intermetallics 10 nm of the 230 nm that the indenter penetrated. In contrast to the solder, both
harder: Cu6 Sn5 are (~6.2significantly
GPa) andharder: Al3 Cu2Cu 6Sn5 (~6.2 GPa) and Al3Cu2 (~10.50 GPa). The intermetallics
(~10.50 GPa). The intermetallics typically recover around
intermetallics are around
significantly harder: Cu6Sn5 (~6.2 GPa) andof Althe
3Cu2 (~10.50 GPa). The intermetallics
40% of the maximum penetration of the indenterpenetration
typically recover 40% of the maximum upon unloading. indenter
From this, upon unloading. From
the deformation of the
typically recover around 40% of the maximum
this, the deformation of the intermetallic phases was found to be penetration of theboth
indenter
elasticupon unloading.
and plastic, whileFrom
the
intermetallic phases
this, the deformation was found
of the to be
intermetallic both elastic
phases was and plastic,
found while the deformation of the solder
the is
deformation of the solder is found to be primarily plastic [26].to be bothprobe
Scanning elasticmicroscopy
and plastic,(SPM) whilewas
found to be primarily
deformation plasticis [26].
of the solder found Scanning probe plastic
to be primarily microscopy (SPM) was used to accurately perform
used to accurately perform indentation on specific IMC[26]. Scanning
phases. It was probealsomicroscopy
used to observe(SPM) was
the
indentation
used to on specific
accurately IMC
perform phases.
indentation It was on also used
specific to
IMC observe
phases. the
It residual
was also indents,
used to as shown
observe the in
residual indents, as shown in Figure 13. As expected from the nanoindentation data in Figure 12, the
Figure 13. As
residual expected
indents, from the nanoindentation data in Figure 12, the residualdata indents in the 12,solder
residual indents inasthe
shownsolderin were
Figure 13. As
much expected
larger than from the nanoindentation
in intermetallics (Figure 13). AllinofFigure the residualthe
were
indents observed for the intermetallics exhibited a smooth profile with no detected pile-up or sink-inthe
much
residual larger
indents than
in the in intermetallics
solder were much (Figure
larger 13).
than inAll of the
intermetallicsresidual
(Figureindents
13). All observed
of the for
residual
intermetallics
indents
of material, exhibited
observed
while for a materials
the
softer smooth profile
intermetallics like Sn with
exhibited
exhibitno aadetected pile-up
smooth behavior.
pile-up or sink-in
profile with of material,
no detected pile-upwhile softer
or sink-in
materials like Sn
of material, whileexhibit
softer a materials
pile-up behavior. like Sn exhibit a pile-up behavior.

Figure 12. Load displacement data obtained for 500 μN maximum load indentations performed on
Figure
Sn,
Figure Cu 12.
6Sn
12. LoadCudisplacement
3Sn.
5 anddisplacement
Load data
data obtained
obtained forfor 500
500 µNμN maximum
maximum load
load indentationsperformed
indentations performedon
onSn,
Sn, Cu 6Sn5 and Cu3Sn.
Cu6 Sn5 and Cu3 Sn.
Materials 2016, 9, 522 11 of 17
Materials
Materials2016,
2016,9,9,522
522 11
11of
of17
17

(a)
(a) (b)
(b)

(c)
(c) (d)
(d)
Figure
Figure 13. 13. Scanning
Scanningprobe
Scanning probemicroscopy
probe microscopyimage
microscopy image
imageof: (a)
of:of: Sn
(a)(a)
SnSnand
and Cu 3Al
Cu3Cu
and before
Al232Al
before indentation;
indentation; (b)
(b) Sn
(b)and
Sn and
2 before indentation; Sn
Cu
Cu3AlAl after
2 after indentation; (c) Cu Sn before indentation; and (d) Cu Sn after indentation of SAC105 ++
3 Al2 indentation; (c) Cu6(c)
Sn5Cubefore
6 Sn5 indentation; and (d) and
Cu6Sn 5 after indentation of SAC105of
3 2 6 5 6 5
and Cu after indentation; before indentation; (d) Cu6 Sn 5 after indentation
0.1Al.
0.1Al. + 0.1Al.
SAC105

Hysitron
Hysitron nanoDMA
Hysitron nanoDMA with
nanoDMA with CMX
with CMX correction
CMX correction and
correction and maximum
and maximum load
maximum load of
load of 1000
of 1000 μN
1000 μN was
µN was used
was used to
used to perform
to perform
perform
continuous nanoscale
continuous nanoscale
continuous dynamic
nanoscale dynamic mechanical
dynamic mechanical measurement
mechanicalmeasurement
measurementofof Cu
ofCu Al
Cu3Al
3 22. Hardness and elastic modulusof
. Hardness and elastic modulus of
3 Al2 . Hardness and elastic modulus
Cu
CuCu
of 3 Al
3Al2Al
2 could
could be
be
could obtained
obtained
be as
obtainedas a
a function
function
as a of
of
functionindentation
indentation
of depth.
depth.
indentation Figure
Figure
depth. 14
14
Figureshows
shows14 the
the
shows hardness
hardness
the and
and
hardness elastic
elastic
and
3 2
modulus
modulus
elastic of
ofCu
modulus Cu33Al
Al plotted
plotted
of22Cu against
againstindent
indentdisplacement.
displacement. The
The hardness
hardnessand andelastic
elastic modulus
modulus of ofCu
Cu33Al
Al22
3 Al2 plotted against indent displacement. The hardness and elastic modulus of
was
was
Cu lower near the surface but was fairly constant at depths greater than ~15
lower near the surface but was fairly constant at depths greater than ~15 nm. The results are nm. The results are
3 Al2 was lower near the surface but was fairly constant at depths greater than ~15 nm. The results
similar
similar to
are similarto that
that obtained
obtained
to that from
obtainedfrom quasi-static
fromquasi-static measurement
measurement
quasi-static with
measurementwith maximum
maximum
with maximum load
load of
of 500
load 500 μN.
μN.µN.
of 500

Figure
Figure14.
14.Hardness
Hardnessand
andElastic
ElasticModulus
Modulusof
ofCu
Cu33Al
Al22plotted
plottedagainst
againstindent
indentdisplacement.
displacement.
Figure 14. Hardness and Elastic Modulus of Cu3 Al2 plotted against indent displacement.

As seen
seeninin
As seen in Table
Table 2, Sn
2,has has
has hardness
Sn hardness
hardness and elastic
elastic modulus
and modulus modulus of
of 0.22–0.36
0.22–0.36 GPa
GPa and
and ~50
~50 GPa,
GPa,
As Table 2, Sn and elastic of 0.22–0.36 GPa and ~50 GPa, respectively,
respectively,
respectively, while
while Cu
Cu 66Sn
Sn55 has
has hardness
hardness and
and elastic
elastic modulus
modulus of
of ~6.2
~6.2 GPa
GPa and
and ~92–110
~92–110 GPa,
GPa,
while Cu6 Sn5 has hardness and elastic modulus of ~6.2 GPa and ~92–110 GPa, respectively. The results
respectively.
respectively.The
Theresults
resultsare
areiningood
goodagreement
agreementwithwithother
otherstudies
studies[27–29].
[27–29].OnOnthe
theother
otherhand,
hand,CuCu33Al
Al22
exhibits a much higher hardness and elastic modulus as compared to Sn and Cu Sn
exhibits a much higher hardness and elastic modulus as compared to Sn and Cu6Sn5, with a hardness
6 5 , with a hardness
of
of ~10.50
~10.50 GPa
GPa and
and an
an elastic
elastic modulus
modulus ofof ~170.08
~170.08 GPa.
GPa.
Materials 2016, 9, 522 12 of 17

are in good agreement with other studies [27–29]. On the other hand, Cu3 Al2 exhibits a much higher
hardness and elastic modulus as compared to Sn and Cu6 Sn5 , with a hardness of ~10.50 GPa and an
elastic modulus of ~170.08 GPa.

Table 2. Hardness and modulus of Pure Sn, Cu6 Sn5 , and Cu3 Al2 .

SAC105 SAC + 0.1Al

Element/Compound
E (GPa) H (GPa) E (GPa) H (GPa)
Sn 49.43 ˘ 7.93 0.29 ˘ 0.07 50.43 ˘ 4.86 0.23 ˘ 0.04
Cu6 Sn5 92.25 ˘ 16.24 6.20 ˘ 0.59 100.99 ˘ 10.09 6.26 ˘ 1.07
Cu3 Al2 – – 170.08 ˘ 12.92 10.52 ˘ 1.71

3. Discussion
From the DSC curves (Figure 1), it is found that when 0.1 wt.% of Al was added to the solder,
the endothermic curve remains similar to that of SAC105. Both SAC105 and SAC105 + 0.1Al exhibit
twin peaks endothermic curve. The onset melting temperature of SAC105 + 0.1Al is the same as that
of SAC105, which is ~217 ˝ C. This corresponds to Sn-Ag-Cu ternary eutectic temperature. When the
percentage of Al is increased to 0.3 wt.% and 0.5 wt.%, the onset of melting temperature shifts to
~221 ˝ C (Sn-Ag eutectic temperature) [30]. The DSC curves of SAC105 + 0.3Al and SAC + 0.5Al solders
are similar to the DSC curve of non-eutectic Sn-Ag solder [31]. This shows that free Cu atoms are
not available in SAC105 + 0.3Al and SAC + 0.5Al solders as Sn-Ag-Cu solder alloy always shows the
onset melting at ~217 ˝ C [32]. One possible explanation for this is the formation of Cu3 Al2 compound,
which has reduced the available Cu in the bulk solder to react with Sn and Ag. The Cu3 Al2 compound
already formed in the as-received samples, which were supplied in the as-cast condition. As seen
in Figure 2b–d, Cu3 Al2 is formed in the as-cast solder. Cu3 Al2 has a higher melting temperature of
960 ˝ C [33]. Thus, during the melting of solders for up to 300 ˝ C, the stable Cu3 Al2 IMC did not
react and this lowers the activity of Cu in solder melts. The lack of free Cu atom in the solder is
further indicated by the shift of a prominent peak in the DSC curves of SAC105 and SAC105 + 0.1Al.
The ~228 ˝ C (Sn-Cu eutectic temperature) peak in SAC105 and SAC105 + 0.5Al has shifted to ~231 ˝ C
(Tm of Sn = 232 ˝ C) in SAC105 + 0.3Al and SAC105 + 0.5Al. This shift indicates that the deficiency of
Cu atom in SAC105 + 0.3Al and SAC105 + 0.5Al has reduced the strong eutectic reaction of Sn-Cu,
L Ñ Cu6 Sn5 + Sn. With Al addition, the peak indicating Sn melting is seen, as fractions of un-melted
Sn remaining in the solder melted when temperature increased to 232 ˝ C [30].
Table 1 shows that SAC105 has the largest undercooling of ~17 ˝ C. This is well within range of
undercooling values, 10–30 ˝ C reported for Sn-Ag-Cu solder [1]. This is because β-Sn requires large
undercooling to induce nucleation and solidification [1]. The presence of Al in SAC105 has reduced
the undercooling significantly. It is seen that with addition of Al up to 0.5%, undercooling has reduced
to 1–5 ˝ C. Kotadia et al. and Anderson et al. have observed the effect of Al in reducing undercooling
of Sn-3.5Ag and Sn-3.5Ag-0.95Cu solder to 7 ˝ C and 4 ˝ C respectively [14,34]. The addition of minor
alloying element into solder has been one of the effective ways of reducing undercooling by promoting
nucleation of β-Sn. Minor alloying atoms which have a much higher melting temperature can exist
in molten Sn and provide heterogeneous site for β-Sn nucleation. In the case of Al as minor alloying,
Cu3 Al2 compound is formed even when the addition of Al is as low as 0.1%. During exothermic
reaction in DSC, the existing Al-Cu intermetallic compounds act as a preferential site to promote
heterogeneous nucleation of β-Sn, and thus lowering the undercooling of SAC105.
Segregated Cu3 Al2 IMC was found near the top surface of the sample with addition of Al after
1 ˆ reflow. One of the possible reasons could be that, during reflow, solders are melted on the Cu
substrates at 250 ˝ C, the Cu3 Al2 particles are not wet by the molten solder, thus they are not drawn
into the melt as the molten solder particles solidify. This causes rejection of the Cu3 Al2 , which remain
near the surface/edges of the solder after reflow. Another possible reason for the segregation of
Materials 2016, 9, 522 13 of 17

Cu3 Al2 particles at the edge/surface could be attributed to the buoyancy effects. The density of Cu3 Al2
particles is 6.278 g/cm3 , which is lower than the density of liquid Sn, 6.99 g/cm3 [35]. Thus, during
reflow, the less dense Cu3 Al2 particles migrate to the surface/edges. Kotadia et al. have reported the
segregation of Al2 Cu in SA solder. They suggested that the segregation of Al rich phase and Al-Cu
compound is caused by Stokes and Marangoi motion, which is due to large stable liquid miscibility
gap in binary Sn-Al and ternary Sn-Ag-Al [18].
Minor alloying elements which could affect the growth of Cu-Sn compound are divided into two
categories: (i) elements that show marked solubility in either one or both of the Cu-Sn IMCs; and (ii)
elements that do not significantly dissolve in either of the Cu–Sn IMCs [11]. The effect of elements in
category 1 on IMC growth could be explained by using thermodynamic argument. These elements
stabilize Cu6 Sn5 and decrease the growth of Cu3 Sn. The elements in category 2 do not have a prominent
effect on IMC as they only affect the growth of IMC layers indirectly. It can be seen from Figures 4 and 5
that the addition of Al has reduced the growth of Cu6 Sn5 . Though Anderson et al. have suggested
Al has some solubility in Cu6 Sn5 , no trace of Al could be found in Cu6 Sn5 in this study. In this study,
the addition of up to 0.5 wt.% Al did not alter the scallop morphology of Cu6 Sn5 [14]. Scallop type
IMC formation is promoted by higher value of the IMC/liquid solder interfacial energy.
There is very limited amount of information available on the influence of Al on the Cu–Sn reaction.
Li et al. have reported the suppression of Cu6 Sn5 IMC growth with addition of 1% Al. They suggested
that the suppression is due to the formation of an Al-Cu IMC layer at the interface, which acts as a
barrier for Cu and Sn diffusion [16]. However, Al-Cu IMC layer is not found at the interface in this
study as the amount of Al added is less (ď5%). Dhaffer et al. have also reported suppression of Cu6 Sn5
IMC growth with addition of 0.1% Al during dip soldering and solid state reaction [20]. The Cu3 Al2
IMC found at the Cu6 Sn5 /Sn interface (Figure 8) could account for the suppression of Cu6 Sn5 . This is
seen in previous work where Zn found at the Cu6 Sn5 /Sn interface, hindered the flow of copper atoms
to the solder thereby slowing down the IMC growth [36]. Thus, the segregation of Al atoms at the
IMC/Sn interface may have similar effect on the growth of IMC, by hindering the flow of Cu or Sn
atom. With minor Al addition, most of the Al reacts with Cu in the bulk solder to form Cu3 Al2 . Hence,
Al does not form a layer of compound at the interface. Reduction of free Cu atom in the bulk solder
could also be attributed to the retardation of Cu6 Sn5 growth. When the amount of Al in the solder
increased (ě0.5 wt.% Al in SA, ě1 wt.% Al in SAC), it formed a layer of Cu-Al compound at the
solder/Cu interface [15,16]. By their presence at the interface, Cu3 Al2 IMC hinders the flow of Cu or
Sn atom to the solder thereby retarding IMC growth during reflow.
During isothermal aging, the Cu6 Sn5 IMC layer grows by interdiffusion of Cu and Sn and reaction
with each other, while the Cu3 Sn IMC forms and grows by reactions between the Cu substrate and
Cu6 Sn5 IMC layer, as given in the equation below [11]:

Cu6 Sn5 ` 9Cu Ñ 5Cu3 Sn (1)

The presence of Cu3 Al2 IMC at the Cu6 Sn5 /Sn interface hinders the flow of Cu or Sn atom to the
solder, however it does not affect the reaction in Equation (1). Cu3 Sn grows by consuming Cu6 Sn5 that
is formed during reflow. Thus, the thickness of Cu3 Sn was not significantly affected by the addition
of Al in solder. On the other hand, with slower interdiffusion of Cu and Sn at the interface (due to
presence of Cu3 Al2 ) and Cu3 Sn formation by consumption of Cu6 Sn5 , the thickness of Cu6 Sn5 was
reduced in SAC105 + Al solder.
The addition of Al has increased the hardness of bulk solder. This could be due to the grain
refinement of Sn, which can be seen in Figure 3. Kim et al. has also reported that addition of Al as
low as 0.01 wt.% could refine the Sn grain of Sn-Cu solder [8]. From nanoindentation, Cu3 Al2 that are
found in all SAC + Al solder exhibits higher hardness than other elements in SAC105 + Al. This seems
promising in strengthening the solder joints. However, its high elastic modulus should be considered
as well, as high elastic modulus could be detrimental for impact testing. Thus, further testing need to
be done to further verify the effects of strengthening effects of Cu3 Al2 .
Materials 2016, 9, 522 14 of 17

In spite of the incorporation by only a small fraction, Al is clearly seen to have influenced
decisively on the hardness, undercooling of solder and the interfacial characteristics during reflow.
However, the amount of Al must be kept below 0.3 wt.% in order to avoid large Cu3 Al2 agglomeration,
which could affect the performance of solder.

4. Materials and Methods

SAC105-xAl (where x = 0, 0.1, 0.3, 0.5 wt.%) were fabricated by Beijing Compo Advanced
Technology Co. Ltd. (Beijing, China). All the solder alloys were prepared in rod shape (0.7 cm
diameter, 15 cm length). The solder alloy was then cut into thin disks with 1 mm thickness by using
electric discharge machining (EDM, A500W, Sodick, Schaumburg, IL, USA).
As-received solder was prepared for micro-examination by standard metallographic technique
which included, cutting, mounting, grinding (up to 3000 grit paper) and polishing (diamond paste
with size 9 µm, 6 µm, 3 µm, 1 µm and colloidal silica with size 0.2 µm). The microstructure of the
as-received SAC105-Al solders was characterized by Field emission scanning electron microscope
(FESEM, FEI-FEG450, FEI, Houston, TX, USA) and intermetallic compound (IMC) composition was
investigated by energy dispersive X-ray spectroscope (EDS, EDAX-Genesis Utilities, EDAX, Mahwah,
NJ, USA). Differential scanning calorimeter, DSC (DSC Q20, TA Instruments, New Castle, DE, USA)
was used to evaluate the effect of the addition of Al on the onset melting and onset solidification
temperature of the SAC105 solder. Each of the samples was weighed to approximately 10 mg and
placed on an aluminum pan and covered with a lid. It was then heated from 25 ˝ C to 300 ˝ C and
then cooled down to room temperature at a rate of 10 ˝ C/min. For each composition, DSC test was
repeated 3 times to ensure the reproducibility of the DSC results.
For reflow, commercial grade polycrystalline copper (Cu) sheets (30 mm ˆ 30 mm ˆ 0.3 mm)
were used as substrates. Before soldering, Cu sheets were polished with 2000 Grit silica carbide paper,
washed with detergent and soaked in 10 vol.% H2 SO4 solution for 15–30 min to remove any oxide film
present. These were then rinsed with distilled water followed by drying with acetone. Sparkle Flux
WF-6317 (Senju Metal Industry, Tokyo, Japan) was then evenly placed on the Cu substrate. SAC-xAl
thin disc (diameter = 6.5 mm, thickness = 1.24 mm) were placed in the middle of copper substrates
which had been covered with Flux WF-6317. Reflow was carried out in an oven at 250 ˝ C for 60 s.
After the reflow process, the residual flux was cleaned and removed by rinsing the sample under
running distilled water. After that, the reflowed samples were prepared by standard metallographic
specimen preparation for microstructural investigation. The microstructure of the bulk solder and the
morphology of the IMCs formed at the solder/substrate interface were investigated by FESEM and the
composition of the IMCs was investigated by EDS. IMC thickness was calculated by dividing the IMC
area by the length of the IMC using a built-in image analyzer software in an Olympus SZX10 (Olympus,
Tokyo, Japan) stereoscope. For each experimental condition, thickness values were measured on 5
micrographs and the average IMC thickness is reported. For the top view observation of the interfacial
IMCs, the solders were etched in a mixture of 93% CH3 OH, 5% HNO3 , and 2% HCl to remove the
solder matrix and expose the interfacial intermetallic compound.
Vickers hardness measurement was performed to investigate the relationship between
microstructure and microhardness. The Vickers hardness values were obtained as [36]:
HV “ 2Psinϕ{2d (2)

where ϕ is the indenter apex angle, P is the applied load and d is the average length of diagonals.
The applied load and loading period are 1 kgf and 5 s, respectively. For each specimen, five points
were tested and the mean values were obtained.
Nanoindentation testing was done using Hysitron Ubi-750 (Hysitron, Minneapolis, MI, USA).
Two modes of indentation were conducted on the samples: Quasi-static and Continuous Dynamic
Measurement. Quasi-static indentation was conducted with a maximum load of 500 µN, holding
time of 2 s, loading rate and unloading rate of 16.67 µN/s and continuous dynamic measurement test
Materials 2016, 9, 522 15 of 17

was conducted with a maximum of 1000 µN, holding time of 2 s and a loading rate and unloading
rate of 16.67 µN/s. For each element, 5 points were tested and the mean values were obtained.
The load–displacement data obtained were analyzed using the method proposed by Oliver and
Pharr [37] to determine the hardness and elastic modulus as functions of the displacement of the
indenter. For quasi static nanoindentation testing, hardness (H) and reduced modulus (E) can be
obtained. The elastic modulus E of the material being indented is related to the reduced modulus
using the following equation [38]:

1 ´ v2
E“ (3)
1 1´v2i
Er ´ Ei

where v is the Poisson’s ratio of the indented material (usually assumed to be 0.3 if unknown), and vi
and Ei are the Poisson’s ratio and elastic modulus of the indenter tip material, respectively. The elastic
modulus Ei and Poisson’s ratio vi of the Berkovich indenter used in this study are 1141 GPa and 0.07
respectively. For continuous dynamic measurement, results for the hardness and complex modulus as
a function of indentation depth can be obtained.
Complex modulus, which is also known as dynamic modulus, is a ratio of stress strain under
vibratory conditions. It could be defined by the equation below [39]:

E˚ “ E1 ` iE2 (4)

where E* is the reduced complex modulus, E1 is the reduced storage modulus (or elastic modulus), E”
is the loss modulus and i is the imaginary unit.

5. Conclusions
The following conclusions can be drawn from this study:
‚ Minor addition of Al has reduced the undercooling of SAC105 solder significantly.
‚ With addition of 0.1–0.5 wt.% Al to SAC105, Cu3 Al2 IMC was found.
‚ Cu3 Al2 IMC segregated near the edge of solder upon reflow as Al was added up to 0.3 wt.%.
‚ Minor alloying Al has reduced the thickness of interfacial Cu6 Sn5 IMC significantly but do not
alter the morphology of Cu6 Sn5 IMC.
‚ Minor alloying Al has reduced the thickness of interfacial Cu6 Sn5 IMC but has no significant
effect on the thickness of Cu3 Sn during isothermal aging.
‚ It is suggested that the influence of Al exert its influence on the interfacial reaction by hindering
the flow of reacting species at the interface during reflow.
‚ Cu3 Al2 IMC has higher hardness and elastic modulus than other microstructure in
SAC105 + Al microstructures.

Acknowledgments: The authors would like to acknowledge the financial support from High Impact Research
(HIR) Grant, University of Malaya (Project No. UM.C/625/1/HIR/MOHE/ENG/26).
Author Contributions: Y.M.L. and A.S.M.A.H. conceived and designed the experiments; Y.M.L. performed the
experiments; Y.M.L. and A.S.M.A.H. analyzed the data; A.S.M.A.H. contributed reagents/materials/analysis
tools; and Y.M.L. and A.S.M.A.H. wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Kang, S.K.; Shih, D.-Y.; Leonard, D.; Donald, N.Y.; Henderson, D.W.; Gosselin, T.; Sarkhel, A.;
Goldsmith, N.Y.C. Ag3 Sn plate formation in the solidification of near-ternary eutectic Sn-Ag-Cu. JOM
2004, 56, 34–38. [CrossRef]
2. Shnawah, D.A.A.; Sabri, M.F.M.; Badruddin, L.A.; Said, S.B.M.; Che, F.X. The bulk alloy microstructure and
mechanical properties of Sn-1Ag-0.5Cu-xAl solders (x = 0, 0.1 and 0.2 wt%). J. Mater. Sci. Mater. Electron.
2012, 23, 1988–1997. [CrossRef]
Materials 2016, 9, 522 16 of 17

3. Burke, C.; Punch, J.A. Comparison of the Creep Behavior of Joint-Scale SAC105 and SAC305 Solder Alloys.
In Proceedings of the IEEE Transactions on Components, Packaging and Manufacturing Technology, Kyoto,
Japan, 12 February 2014; pp. 516–527.
4. Cheng, F.; Gao, F.; Zhang, J.; Jin, W.; Xiao, X. Tensile properties and wettability of SAC0307 and SAC105 low
Ag lead-free solder alloys. J. Mater. Sci. 2011, 46, 3424–3429. [CrossRef]
5. Liu, W.; Lee, N.C. The effects of additives to SnAgCu alloys on microstructure and drop impact reliability of
solder joints. JOM 2007, 56, 26–31. [CrossRef]
6. Lee, T.; Bieler, T.R.; Kim, C.; Ma, H. Fundamentals of Lead-Free Solder Interconnect Technology; Springer:
New York, NY, USA, 2015.
7. Ahmad, A.E. Evolution of microstructure, thermal and creep properties of Ni-doped Sn-0.5Ag-0.7Cu low-Ag
solder alloys for electronic applications. Mater. Des. 2013, 52, 663–670.
8. Kim, K.S.; Huh, S.H.; Suganuma, K. Effects of fourth alloying additive on microstructures and tensile
properties of Sn-Ag-Cu alloy and joints with Cu. Microelectron. Reliab. 2003, 43, 259–267. [CrossRef]
9. Anderson, I.E.; Walleser, J.W.; Harringa, J.L.; Laabs, F.; Kracher, A. Nucleation control and thermal aging
resistance of near-eutectic Sn-Ag-Cu-X solder joints by alloy design. J. Electron. Mater. 2009, 38, 2770–2779.
[CrossRef]
10. Shi, Y.W.; Tian, J.; Hao, H.; Xia, Z.; Lei, Y.; Guo, F. Effects of small amount addition of rare earth Er on
microstructure and property of SnAgCu solder. J. Alloys Compd. 2008, 453, 180–184. [CrossRef]
11. Laurila, T.; Vuorinen, V.; Paulasto-Kröckel, M. Impurity and alloying effects on interfacial reaction layers in
Pb-free soldering. Mat. Sci. Eng. R 2010, 68, 1–38. [CrossRef]
12. Amagai, M.A. study of nanoparticles in Sn–Ag based lead free solders. Microelectron. Reliab. 2008, 48, 1–16.
[CrossRef]
13. Gain, A.K.; Chan, Y.C. The influence of a small amount of Al and Ni nano-particles on the microstructure,
kinetics and hardness of Sn-Ag-Cu solder on OSP-Cu pads. Intermetallics 2012, 29, 48–55. [CrossRef]
14. Boesenberg, A.J.; Anderson, I.E.; Harringa, J.L. Development of Sn-Ag-Cu-X Solders for Electronic Assembly
by Micro-Alloying with Al. J. Electron. Mater. 2012, 41, 1868–1881. [CrossRef]
15. Xia, Y.H.; Jee, J.K.; Yu, J.; Lee, T.Y. Effect of aluminum concentration on the interfacial reactions of
Sn-3.0Ag-xAl solders with copper and ENIG metallizations. J. Electron. Mater. 2008, 37, 1858–1862. [CrossRef]
16. Li, J.F.; Agyakwa, P.A.; Johnson, C.M. Effect of trace Al on growth rates of intermetallic compound layers
between Sn-based solders and Cu substrate. J. Alloys Compd. 2012, 545, 70–79. [CrossRef]
17. Kantarcıoğlu, A.; Kalay, Y.E. Effects of Al and Fe additions on microstructure and mechanical properties of
SnAgCu eutectic lead-free solders. Mat. Sci. Eng. A 2014, 593, 79–84. [CrossRef]
18. Kotadia, H.R.; Panneerselvam, A.; Mokhtari, O.; Green, M.A.; Mannan, S.H. Massive spalling of Cu-Zn
and Cu-Al intermetallic compounds at the interface between solders and Cu substrate during liquid state
reaction. J. Appl. Phys. 2012, 111, 074902–074906. [CrossRef]
19. Mohd, F.M.S.; Dhafer, A.S.; Irfan, A.B.; Suhana, B.M.S. Effects of aging on Sn-1Ag-0.5Cu solder alloys
containing 0.1 wt % and 0.5 wt % Al. J. Alloys Compd. 2014, 582, 437–446.
20. Dhafer, A.S.; Mohd, F.M.S.; Suhana, B.M.S.; Iswadi, J.; Mohammad, H.M.; Mohamed, B.A.B.; Mohamed, H.E.
Interfacial reactions between Cu substrate and Sn–1Ag–0.5 Cu solder containing 0.1 wt.% Al by dipping
method. J. Mater. Sci. Mater. Electron. 2015, 26, 8229–8239.
21. Whitehead, A.J.; Page, T.F. Nanoindentation studies of thin film coated systems. Thin Solid Films 1992, 220,
277–283. [CrossRef]
22. Song, J.-M.; Huang, B.-R.; Liu, C.-Y.; Lai, Y.-S.; Chiu, Y.-T.; Huang, T.-W. Nanomechanical responses of
intermetallic phase at the solder joint interface—Crystal orientation and metallurgical effects. Mater. Sci.
Eng. A 2012, 534, 53–59. [CrossRef]
23. Saunders, N.; Miodownik, A.P. The Cu-Sn (Copper-Tin) system. Alloy Phase Diagram Evaluations. Bull. Alloy
Phase Diagr. 1990, 11, 278–287. [CrossRef]
24. Funamizu, Y.; Watanabe, K. Interdiffusion in the Al–Cu system. Trans. Jpn. Inst. Met. 1971, 12, 147. [CrossRef]
25. Molnár, A.; Kardos, I.; Molnár, I.; Gácsi, Z. Effect of silver content on the properties of lead-free solders.
Mater. Sci. Eng. 2014, 39, 51–58.
26. Chen, H.-T.; Ya, B.-B.; Yang, M.; Ma, X.; Mingyu, L. Effect of grain orientation on mechanical properties and
thermomechanical response of Sn-based solder interconnects. Mater. Charact. 2013, 85, 64–72. [CrossRef]
Materials 2016, 9, 522 17 of 17

27. Maleki, M.; Cugnoni, J.; Botsis, J. Microstructure-based modeling of the ageing effect on the deformation
behavior of the eutectic micro-constituent in SnAgCu lead-free solder. Acta Mater. 2013, 61, 103–114.
[CrossRef]
28. Marquesa, V.M.F.; Wunderleb, B.; Johnstona, C.; Granta, P.S. Nanomechanical characterization of
Sn–Ag–Cu/Cu joints—Part 2: Nanoindentation creep and its relationship with uniaxial creep as a function
of temperature. Acta Mater. 2013, 61, 2460–2470. [CrossRef]
29. Lotfian, S.; Molina-Aldareguia, J.M.; Yazzie, K.E.; Llorca, J.; Chawla, N. Mechanical characterization of
lead-free Sn-Ag-Cu solder joints by high-temperature nanoindentation. J. Electron. Mater. 2013, 42, 1085–1091.
[CrossRef]
30. Karakaya, I.; Thompson, W.T. The Ag-Sn (Silver-Tin) system. Bull. Alloy Phase. Diagr. 1987, 8, 340–347.
[CrossRef]
31. Katoh, R.; Munekata, O.; Toyoda, Y. Tombstoning Prevented by the Use of a Twin-Peak Solder Alloy.
U.S. Patent 6554180 B1, 29 April 2003.
32. Kubaschewski, O.; Hari Kumar, K.C. Materials Science International Team MSIT® , Ag-Cu-Sn
(Silver-Copper-Tin). In Non-Ferrous Met. Ternary Systems; Springer: Berlin, Germany, 2007; pp. 47–62.
33. Massalski, T.B. The Al´Cu (Aluminum-Copper) system. Bull. Alloy Phase Diagr. 1980, 1, 27–33. [CrossRef]
34. Kotadia, H.R.; Mokhtari, O.; Bottrill, O.M.; Clode, M.P.; Green, M.A.; Mannan, S.H. Reactions of
Sn-3.5Ag-Based Solders Containing Zn and Al Additions on Cu and Ni(P) Substrates. J. Electron. Mater.
2010, 39, 2720–2731. [CrossRef]
35. Chauhan, P.S.; Choubey, A.; Zhong, Z.W.; Pecht, M.G. Copper Wire Bonding; Springer: New York, NY,
USA, 2014.
36. Haseeb, A.S.M.A.; Leong, Y.M.; Arafat, M.M. In-Situ Alloying of Sn-3.5Ag Solder during Reflow through
Zn Nanoparticle Addition and Its Effects on Interfacial Intermetallic Layers. Intermetallics 2014, 54, 86–94.
[CrossRef]
37. Oliver, W.C.; Pharr, G.M. Measurement of hardness and elastic modulus by instrumented indentation:
Advances in understanding and refinements to methodology. J. Mater. Res. 2004, 19, 3–20. [CrossRef]
38. Fischer-Cripps, A.C. Nanoindentation, 3rd ed.; Springer: New York, NY, USA, 2011; pp. 2–126.
39. Meyers, M.A.; Chawla, K. Mechanical Behavior of Materials, 2nd ed.; Cambridge University Press: Cambridge,
UK, 2008.

© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).