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Materials Science and Engineering B 162 (2009) 9298

Contents lists available at ScienceDirect

Materials Science and Engineering B


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

Effect of nano Ni additions on the structure and properties of Sn9Zn and


SnZn3Bi solders in Au/Ni/Cu ball grid array packages
Asit Kumar Gain a , Y.C. Chan a, , Winco K.C. Yung b
a
b

Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong
Department of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

a r t i c l e

i n f o

Article history:
Received 20 July 2008
Received in revised form 11 March 2009
Accepted 18 March 2009
Keywords:
Nano doping
Ball grid array solder joints
Shearing force
Microstructure

a b s t r a c t
The effect of nano Ni additions in Sn9Zn and Sn8Zn3Bi solders on their interfacial microstructures
and shear loads with Au/Ni/Cu pad metallization in ball grid array (BGA) applications were investigated.
After the addition of nano Ni powder in Sn-based lead-free solders, there were no signicant changes in
the interfacial microstructure. But, in the solder region a very ne Zn-rich phase was observed. Also on
the fracture surfaces a ne ZnNi compound was found. After the addition of nano Ni powder in Sn-based
solders, the shear loads were increased due to a renement of the microstructure and in addition, ductile
fracture surfaces were clearly observed. The shear loads of the plain Sn9Zn and Sn8Zn3Bi solders after
one reow cycle were about 1798 g and 2059 g, respectively. After the addition of nano Ni powder, their
loads were about 2172 g and 2212 g, respectively, after one reow cycle and their shear loads after eight
reow cycles were about 2099 g and 2081 g, respectively.
2009 Elsevier B.V. All rights reserved.

1. Introduction
The importance of reow soldering in electronic packaging is
increasing due to the rapid growth of the electronic industry in
recent years. Traditionally, SnPb solders were extensively used
for interconnections in electronic components due to their unique
combination of mechanical properties, superior wetting properties,
moderate melting temperatures and low cost [13]. Environmental and health concerns over the toxicity of lead combined with
strict legislation to ban the use of lead-based solders have provided
an inevitable driving force for the development of lead-free solder
alloys [4,5]. Therefore, establishing a lead-free solder has become
a critical issue. In fact many research groups have been focused
on developing new solders. But new solders must fulll several
requirements such as wettability, a suitable melting temperature,
good mechanical properties, good resistance to mechanical and
thermal fatigue, corrosion resistance, good electrical properties,
good for health and the environment, availability and low material
cost [6,7]. Recently, several types of new Pb-free Sn-based solders
such as SnZn, SnAg and SnAgCu have attracted the attention
of the electronics industry [8]. Among them the eutectic or near
eutectic SnZn solders have been recognized as candidates for Pbfree solder materials due to their low cost and low melting points.
The melting point of the eutectic Sn9 wt.% Zn solder is 198 C which
is close to that of the conventional SnPb (183 C) [9] eutectic alloy

and is much lower than that of other Sn-based alloys e.g. SnCu
(227 C), SnAg (221 C) and SnAgCu (217 C) [10]. However, some
important issues such as inferior wettability, easy oxidation and
micro-void formation have been encountered to limit the practical
use of these solder alloys [11]. It is well known that the poor oxidation resistance of the SnZn eutectic alloy is due to the oxidation of
the Zn, which exists in both the primary and eutectic phases. If the
amount of the Zn phase in the SnZn eutectic alloy can be reduced
or xed by forming IMCs, it is expected that the oxidation resistance
can be improved [12]. Therefore, much research has been focused
on the addition of alloying elements such as copper, nickel, silver,
antimony, bismuth, etc. Among them, Ni has been considered as a
suitable alloying element in lead-free solders due to the formation
of stable ZnNi binary phases as well as improving the wettability.
Furthermore, the Ni alloying element effectively enhances the formation of additional intermetallic compounds which improve the
mechanical properties.
In this study as a new approach, nano Ni powders were
embedded on the BGA substrate and used to attach Sn9Zn and
Sn8Zn3Bi lead-free solder balls which were reowed using a
reow machine. The inuence on the intermetallic morphology,
shear strength and fracture surfaces between these solders and
the Au/Ni/Cu BGA substrate were systematically investigated as a
function of the number of reow cycles.
2. Experimental procedure

Corresponding author. Tel.: +852 27887130; fax: +852 2788 7579.


E-mail address: eeycchan@cityu.edu.hk (Y.C. Chan).
0921-5107/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2009.03.010

To prepare 0.76 mm diameter solder balls, Sn9Zn (Showa


Denko JUFFIT-E 9ZSN10 M) and Sn8Zn3Bi solder pastes were

A.K. Gain et al. / Materials Science and Engineering B 162 (2009) 9298

Fig. 1. Schematic diagram of a solder ball attachment on a exible substrate.

taken out from the refrigerator where they had been held for 1 h
at a temperature between 4 C and room temperature. Then, the
solder paste was printed on an alumina substrate using a stainless
steel stencil with a thickness of 0.15 mm and reowed in a reow
oven (BTU VIP-70N) at 245 C.
A solder mask-dened copper bond pad on the exible substrate
of a Au/Ni/Cu BGA package was used as a base for electrodeposi-

93

tion of Ni and Au. The solder mask-opening diameter was 0.6 mm


with a 7 m thick Ni layer at the ball pad. The average thickness
of the Au layer was 0.5 m. Lead-free solder balls with a diameter
of 0.76 mm, were placed on the nano Ni powder (20 nm in diameter, Shenzhen Junye Nano Material Co., China) embedded preuxed
Au/Ni/Cu bond pad of the substrates as shown in Fig. 1 and reowed
at a temperature of 245 C with a belt speed 60 cm/min in a convection reow oven (BTU VIP-70N). The ux used in this study was
a commercial rosin activated (RA) ux.
To characterize the microstructures, the reowed samples were
cross sectioned and mounted in a resin, then ground by different
grit sizes of emery papers and polished with 0.5 m Al2 O3 powder.
Finally, the interfacial morphology at the solder alloy/BGA substrate
interface was observed using a scanning electron microscope (SEM,
Philips XL 40 FEG) with the back-scattered electron (BSE) imaging
mode and an energy dispersive X-ray spectrometer (EDX, International, model no. DX-4) was utilized to determine the chemical
composition of the intermetallic compounds (IMCs). Before SEM
observation, the samples were sputter coated with Au to avoid
effects due to charging.
To measure the shear strength, ball shear tests were performed
on the reow samples using a shear testing machine (PTR-1000,
Rhesca Co. Ltd., Japan) with a 50 m shear tool height and 500 m/s
shear speed. The average strength of 20 solder balls with the minimum and maximum values removed was taken for each condition.
After ball shear testing, the fracture surfaces and compositions were
investigated thoroughly using SEM and EDX techniques.

Fig. 2. SEM micrographs of (a) SnZn and (b) nano Ni added SnZn solder joints after one reow cycle.

Fig. 3. SEM micrographs of (a) SnZn3Bi and (b) nano Ni added SnZn3Bi solder joints after one reow cycle.

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A.K. Gain et al. / Materials Science and Engineering B 162 (2009) 9298

Fig. 4. SEM micrographs of nano Ni added (a and b) SnZn and (c and d) SnZnBi solder joints after eight reow cycles.

3. Results and discussion


Fig. 2 shows back-scattered electron micrographs of interfaces
between (a) a plain SnZn solder and (b) a Sn9Zn solder containing
Ni nano particles and the Au/Ni/Cu ball-grid-array (BGA) substrate
after one reow cycle. After the nano Ni powder addition, there was
no signicant change in the intermetallic compound layer at the

Fig. 5. Shear loads of joints with nano Ni additions to SnZn and SnZn3Bi compared with joints not containing Ni nano additions as a function of the number of
reow cycles.

interface. In both samples, the AuZn3 based scallop-shaped intermetallic compound was clearly observed. In general, Ni particles
react with Zn and formed ZnNi metallic compound. But, in the
present study, the ZnNi compound were not detected at the interface in low magnication BSE micrographs because the formation
of the ZnNi binary compound may be very ne due to the initial
particle size of the Ni powder. On the other hand, in the solder ball
region, a needle-shaped Zn phase, as indicated by arrowheads, was
homogeneously distributed in the Sn matrix in both samples. However, after the addition of the nano Ni powder, the needle-shaped
Zn phase size was dramatically changed and become very ne. The
difference in microstructure between the plain SnZn solder and
the solder containing Ni nano particles found may be due to the
reaction of Ni and Zn. In addition, some micro-voids were found in
the plain SnZn solder at their interfaces as indicated with arrowheads in Fig. 2(a). However, after addition of the nano Ni, no such
defects were found at their interfaces. The absence of micro-voids
in this case may be because the diffusion process is changed by the
presence of the nano Ni particles which may block the formation of
kirkendall voids.
Fig. 3 shows back-scattered electron micrographs of interfaces
between (a) a plain SnZn3Bi solder and (b) a Sn8Zn3Bi solder containing Ni nano particles and the Au/Ni/Cu ball-grid-array
(BGA) substrate after one reow cycle. From the BSE images, the
scallop-shaped AuZn3 compound was found at the interfaces. However, in the solder region a ne Bi phase was detected, as indicated
with arrowheads, in both samples. But, the sizes of the Zn-rich
phase became ner after the addition of the nano Ni powder. A
plausible explanation here for the ner Zn-rich phase is that it is
heterogeneously nucleated on the nano Ni particles.

A.K. Gain et al. / Materials Science and Engineering B 162 (2009) 9298

95

Fig. 6. SEM fracture surfaces of (a and b) SnZn and (c and d) nano Ni added SnZn solder joints after one time reow and (e and f) nano Ni added SnZn solder joints after
eight reow cycles.

Fig. 4 shows back-scattered electron micrographs of nano Ni


added (a and b) Sn9Zn and (c and d) Sn8Zn3Bi solder joints after
eight reow cycles. In the interfacial regions as shown in Fig. 4(a and
c), it is clear that the scallop-shaped AuZn3 layer thickness was not
signicantly increased as compared to the one reow cycle solder
joints shown in Figs. 2(b) and 3(c) and well adhered at the interfaces. In general, with an increase in the number of reow cycles
as well as reow time the scallop-shaped AuZn3 phase oated and
moved away from the interfaces [13]. Fig. 4(b and d) were taken
from solder ball regions of nano Ni added Sn9Zn and Sn8Zn3Bi
solder joints after eight reow cycles, respectively. In the solder
ball region, a ne needle-shaped Zn-rich phase was observed in
the plain Sn9Zn solder. However, in the plain Sn8Zn3Bi solder,
a ne needle-shaped Zn-rich and Bi phase were observed.

Since solder joints are often subjected to mechanical loading


during processing and system use, the mechanical properties of the
solder joints such as shear strength and creep resistance are important for their reliability. Therefore, ball shear tests were performed
to evaluate the effect of the interfacial reactions on the reliability of
the solder joints with the addition of nano Ni powder. Fig. 5 shows
the change of average interfacial strength of Sn-based lead-free solder joints depending on the number of reow cycles. On the whole,
the shear loads did not change much in the nano Ni added Sn-based
solders due to the formation of ne microstructures. From the bar
diagram, it is clear that the shear loads of both types of Sn-based solder joints were increased with the addition of nano Ni powder. The
shear loads of the plain Sn9Zn and Sn8Zn3Bi after one reow
cycle were about 1798 g and 2059 g, respectively. However, after the

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A.K. Gain et al. / Materials Science and Engineering B 162 (2009) 9298

Fig. 7. SEM fracture surfaces of (a and b) SnZnBi and (c and d) nano Ni added SnZnBi solder joints after one time reow and (e and f) nano Ni added SnZnBi solder
joints after eight reow cycles.

addition of nano Ni powder, their shear loads were about 2172 g and
2212 g, respectively. On the other hand, the shear loads of Sn9Zn
and SnZn3Bi solders after eight reow cycles were about 1667 g
and 2007 g, respectively, and after nano Ni addition their shear loads
were about 2099 g and 2081 g, respectively.
After measuring the interfacial strength, the fracture surfaces of
the solder joints were examined using a scanning electron microscope (SEM). Fig. 6 shows fracture surfaces of the Sn-based solders.
From these fractographs, it is clear that the Sn9Zn solder showed
brittle fracture with a smooth surface after one reow cycle as
shown in Fig. 6(a and b). However, after the addition of nano Ni
powder, the fracture mode of the SnZn solder was dramatically
changed. From Fig. 6(cf), it is conrmed that the fracture surface of the plain Sn9Zn solder exhibited a typical ductile fracture

with dimpled surfaces. On the other hand, the fracture mode of


the plain Sn8Zn3Bi solder gave semi-ductile behavior after one
reow cycle as shown in Fig. 7(a and b). However, a typical ductile fracture with a very rough dimpled surface was found after the
addition of nano Ni powder as shown in Fig. 7(cf). However, with
an increase in the number of the reow cycles, the ductile behavior
and the number of dimples were increased in both nano Ni added
solders due to an increase in the reaction time between Zn and Ni.
In both nano Ni added samples, a ne particle-like compound was
clearly observed as indicated with arrowheads in Figs. 6(cf) and
7(cf).
Fig. 8 shows the EDS prole and elemental analysis of a nano
Ni addition Sn-based solder joint which was taken from the region
marked P in Fig. 6(c). From the EDS prole and elemental analysis, it

A.K. Gain et al. / Materials Science and Engineering B 162 (2009) 9298

97

Fig. 8. EDS prole and elemental analysis of Ni addition Sn-based solder joints.

Fig. 9. Schematic diagrams of the oxidation of SnZn alloys. (a) ZnO formed on the Sn grain boundaries near free surface causes cracks and (b) formation of intermetallic
compounds on the grain boundaries.

is conrmed that the particle-like compound consisted of a ZnNi


binary phase.
The exposure of SnZn solder to humidity/heat conditions promotes Zn and O segregation to the grain boundaries. Lee et al.
[14] reported that water vapor and oxygen diffuse into alloys along
the grain boundaries and correspondingly Zn diffuses to the grain
boundaries forming ZnO and most of the ZnO phase is located
near the top surface. During the reaction of Zn to ZnO, the stress
induced by the volume expansion forming ZnO, especially along
the Sn boundaries, increases which cause cracks along those boundaries. As a result, there is a serious degradation of the joint strength
for SnZn alloys due to the formation of ZnO at interfaces as
shown schematically in Fig. 9(a). To minimize the formation of
cracks as well as to improve the oxidation resistance of the Snbased solders, nano Ni powder was added to aid the formation of
intermetallic compounds in the grain boundaries and later on to
block the penetration of the water vapor and oxygen which in turn
reduces the ZnO formation along the grain boundaries as shown in
Fig. 9(b).
4. Conclusions
The interfacial microstructure and shear strength between plain
Sn9Zn and Sn8Zn3Bi solders and nano Ni powder added Sn9Zn
and Sn8Zn3Bi solders with Au/Ni/Cu BGA substrates were investigated as a function of the number of reow cycles. In all samples,
AuZn3 based scallop-shaped intermetallic compound was clearly
observed. However, the addition of nano Ni powder increased the
shear strength in both Sn9Zn and Sn8Zn3Bi samples due to
a ner microstructure. The shear failure loads of the plain SnZn
solder and the SnZn solder containing nano Ni powder after one
reow cycle were about 1798 g and 2172 g, respectively, and the fail-

ure loads of the plain SnZn3Bi solder and the SnZn3Bi solder
containing nano Ni powder were about 2059 g and 2212 g, respectively. On the other hand, the shear failure loads of the plain SnZn
solder and the SnZn solder containing nano Ni powder after eight
reow cycles were about 1667 g and 2099 g, respectively, whilst the
failure loads of the plain SnZn3Bi solder and the SnZn3Bi solder containing nano Ni after eight reow cycles were about 2007 g
and 2081 g, respectively. After the addition of nano Ni powder, the
fracture mode was signicantly changed to become more ductile
and ne ZnNi compound particles were found in the fracture surface.
Acknowledgements
The authors acknowledge the nancial support provided by City
University of Hong Kong for the project 9041222 CERG grant of Hong
Kong Research Grants Council and RGC ref. no. 111307 (Development of a nano-activator doped surface modier for SnZn based
lead-free soldering). Professor Brian Ralph is thanked for proof
reading the manuscript.
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