APPLIED PHYSICS LETTERS

VOLUME 73, NUMBER 16

19 OCTOBER 1998

Significantly enhanced creep resistance in low-melting-point solders

through nanoscale oxide dispersions
H. Mavooria) and S. Jin
Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974

~Received 1 May 1998; accepted for publication 20 August 1998!

Nanosized, nonreacting, and noncoarsening oxide dispersoids have been incorporated into solder
alloys to create an improved solder structure with an ultrafine grain size of ;20005000 and
significantly enhanced mechanical properties. As much as three orders of magnitude reduction in the
steady-state creep rate has been achieved. These solders also exhibit improved ~45 times higher!
tensile strength at low strain rates and improved ductility under high strain rate deformation. It is
demonstrated that with a dispersion of TiO2 particles, the PbSn eutectic solder with a low melting
point of 183 C can be made more creep resistant than the 80Au20Sn eutectic solder with a much
higher melting point of 278 C. @S0003-6951~98!04342-3#

for single-mode optical fiber interconnections with a tolerance of 1 mm or multimode optical interconnections with an
alignment position tolerance of about 510 mm!, higher
melting-point ~m.p.! solders such as the 80Au20Sn eutectic
~m.p. 278 C! are often utilized to ensure dimensional ~alignment! stability. However, high soldering temperatures can
degrade the properties of optical fiber and other optoelectronic components such as lasers, light-emitting diodes
~LEDs!, photodetectors, or waveguide devices. So, it is
highly desirable to have a solder that has a low melting point
yet exhibits a strong creep resistance. A high mechanical
strength is also helpful to prevent component misalignment
during handling or inadvertent shock deformation. The approach used in this research was to start with the commonly
used 63Sn37Pb eutectic solder ~m.p. 183 C! and modify
its microstructure with nanosized, noncoarsening dispersoid
particles to improve its mechanical properties. Since microstructural instability is a well-known problem with the eutectic 63Sn37Pb, the stability of the modified microstructure
was evaluated. The creep properties of the modified 63Sn
37Pb solder were compared with those of the dispersoid-free
PbSn eutectic as well as those of the higher-melting-point
80Au20Sn eutectic ~which is one of the most creepresistant solders known!.
In the present study, a solder structure with a relatively
uniform dispersoid particle distribution was fabricated using
an approach of particle coating and repeated plastic deformation for rearrangement of the particles. This avoids the complicated, and costly, conventional powder attrition method.
The samples were prepared using powders of the eutectic 63Sn37Pb solder ~35 mm average diameter!, nanosized
TiO2 ~nominally 50 !, and Al2O3 ~nominally 100 !. A
control solder specimen without the dispersoid solder addition was also processed in exactly the same manner. These
powders were thoroughly dispersed in ethanol with vigorous
shaking and mixed in the desired proportions ~3% by volume
of dispersoid!, with constant stirring, to form a slurry of
SnPb particles coated with the finer oxide particles, as illustrated schematically in Fig. 1. The amount of ethanol and the
viscosity of the slurry were controlled to minimize gravityinduced segregation of the oxide particles. After drying, they

Strong creep resistance of bonds or joints is of paramount importance in optoelectronic packaging because of
the need for maintaining positional accuracy of the components over extended periods of time. Time-dependent,
gradual misalignment results in a reduced transmission intensity or in some cases, even a complete loss of lightwave
communication signals.
Creep damage in a solder joint can be reduced by
strengthening the solder. It is well known that metals and
alloys can be strengthened by the presence of fine secondphase particles. Such particles may be introduced to solder
either by precipitation from supersaturated solid or liquid
solution ~e.g., eutectic composition! or by external addition
of foreign, often insoluble, particles as dispersoids. The very
fact that precipitates are often formed through mass transport
of the constituent elements from supersaturated solid solution indicates that relatively rapid, time-dependent, diffusional coarsening of precipitates is inevitableespecially at
temperatures T.0.5T m , where T m is the melting temperature of the alloy in degrees kelvin. Foreign dispersoid particles introduced within solder alloys, on the other hand,
would not coarsen easily. In addition to strengthening the
solder against creep deformation, the dispersed particles can
serve as obstacles to grain growth and coarsening of the solder microstructure.
Agglomeration and coarsening of the particles are frequently encountered problems that lead to nonuniform dispersions or large particle clumps, that are ineffective as
strengthening agents. As a result of these issues, relatively
large amounts of dispersoid additions ~e.g., 10%40% by
volume of Cu6Sn5 intermetallic compound powders in
PbSn solders! have been used in the past to obtain any
appreciable strengthening or creep resistance.14 Magneticfield alignment of molten composite solder was utilized to
obtain a relatively uniform distribution of micron-sized iron
dispersoid particles in the BiSn eutectic solder, and improved strengthening and creep resistance.5,6
For applications requiring creep resistant joints79 ~e.g.,
a!

Electronic mail: hareesh@lucent.com

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Appl. Phys. Lett., Vol. 73, No. 16, 19 October 1998

H. Mavoori and S. Jin

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FIG. 2. Comparison of the PbSn solder microstructures before and after

aging at 120 C for 48 h: ~a! without dispersoid; before aging, ~b! without
dispersoid, after aging, ~c! with 3% by volume Al2O3 ~100 !, before aging,
and ~d! with Al2O3, after aging.
FIG. 1. Powder mixing and plastic flow approach for dispersoid distribution
in a solder matrix.

were compacted in a die ~cold pressing at room temperature!

at 196 MPa pressure to form 50 mm310 mm35 mm pellets.
These were then subjected to repeated compressive mechanical deformation ~mean-compressive stress of 915 MPa! at
120 C in an inert argon atmosphere. Each mechanical deformation step resulted in a reduction of thickness by a factor of
6, after which the flattened piece was cut into six pieces
lengthwise, the pieces stacked, and pressed again to get a
sixfold reduction in thickness. This process was repeated six
times ~see Fig. 1! to get a final calculated interdispersoid
spacing, in the thickness direction, of 8 @based on a thickness reduction of 35 m m3(1/6), 6 where 35 mm was the initial size of the 63Sn37Pb particles coated with the dispersoid, and hence, the initial maximum interdispersoid
spacing#. For maximum strengthening, it is desirable to have
the interdispersoid spacing reduced ~from the initial large
value! as much as possible, and at least in theory, reduced to
less than the average dispersoid diameter ~50100 in this
study!. The processing employed here was designed to
achieve this goal. While the interdispersoid spacing obtained
is larger than the calculated 8 spacing due to the plastic
flow of the matrix solder alloy and the limited number of
added dispersoid particles, a nanoscale, relatively random
dispersion with a particle size distribution of 50500 is
observed in scanning electron microscopy ~SEM! analysis.
The specimens were then given a recrystallization anneal
at 100 C for 1 h in an argon atmosphere to remove the
residual stresses introduced by deformation. The final recrystallized microstructure consisted of equiaxed grains with a
grain size of ;20005000 for the solder with Al2O3 dispersion and ;2 mm for the control solder without dispersion
@Figs. 2~a!2~d!#. Similar microstructural features are also
observed in the TiO2-containing solder. For comparison with
the well-known creep-resistant solder, specimens of 80Au

20Sn solder were given a recrystallization anneal for 1 h at

the same homologous temperature of T/T m ;0.82 ~178 C
for 80Au20Sn!.
A stable microstructure is desirable in engineering materials like solders because microstructural coarsening during
service often leads to degradation of properties such as crack
initiation and propagation through heterogeneously coarsened bands in near-eutectic PbSn solder joints during thermomechanical fatigue cycling.10 Also, grain growth in an
originally fine-grained solder would lead to a loss of benefits
obtained from the small grain size. The nanoscale Al2O3 and
TiO2 dispersoid particles in the present solders are expected
to act as pinning sites for the movement of grain boundaries
and dislocations and slow down grain growth rates significantly. To verify this, the solders were aged at 120 C ~a
relatively high homologous temperature of T/T m 50.86) for
48 h and the initial and final grain sizes compared. While the
grain size of the control solder without dispersoid increased
by 150% from 2 to 5 mm, the grain size of the Al2O3
dispersion-containing solder remained virtually constant at
about 20005000 ~Fig. 2!. A similar trend is observed in
the TiO2-containing PbSn solder. These results indicate that
the presence of the fine dispersoid particles essentially suppresses the grain coarsening even with the enormous driving
force in the ultrafine-grained structure.
Compressive creep tests under constant load were performed at two different temperatures ~80 and 100 C! and an
initial stress of 250 psi ~1724 kPa!. For each creep test, three
specimens of nominal dimensions 3.5 mm33.5 mm
34.5 mm placed at the vertices of a triangle were used with
the load applied via a plate-shaped weight making threepoint free-standing contact with the three specimens. This
technique provides results that are averaged over three specimens. A LVDT attached to this plate was used to measure
creep deformation, while a convection oven was used for
accurate temperature control. A 30 min time period was al-

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Appl. Phys. Lett., Vol. 73, No. 16, 19 October 1998

FIG. 3. Comparative creep deformation for the PbSn solder with and without dispersoids, and 80 Au20Sn solder.

lowed for equilibration at the desired temperature prior to

application of the load. The results are presented in Figs. 3
and 4. The dispersoid-containing 63Sn37Pb solders exhibit
significantly decreased creep deformation. As shown in Fig.
4, the steady-state creep rates of the TiO2 dispersoidcontaining solders are reduced by 23 orders of magnitude
as compared to the dispersoid-free solder, and are actually
lower than that of 80Au20Sn by 50%70% for 2530 h
test duration. As a result, these dispersoid-containing PbSn
eutectic solders show promise as lower-temperature alternatives to 80Au20Sn for creep-resistant applications such as
bonding of optoelectronic devices. The dispersoid technique
employed here may be utilized to improve the creep resistance of 80Au20Sn, Sn3.5Ag, or Sn57Bi solders ~which
already have a relatively high creep resistance to begin with
as compared to the PbSn eutectic! to obtain super creepresistant solders.
Shown in Fig. 5 are the tensile strengths of the
dispersoid-containing and dispersoid-free solders at various

H. Mavoori and S. Jin

FIG. 5. Tensile strength vs strain rate for the PbSn solder with and without
dispersoids.

strain rates. At 25 C, the dispersoid-containing solders are

about four times stronger than the dispersoid-free control
solder at low strain rate (431026 s21), while at high strain
rates (.231023 s21), the strengthening effect essentially
disappears. It is also interesting to observe that at these high
strain rates, the dispersoid-containing solders begin to exhibit greater ductility ~e.g., in tensile elongation! than the
dispersoid-free solders. This is tentatively attributed to the
pseudosuperplastic deformation behavior in the present
ultrafine-grained solders ~;20005000 grain size as compared to the ;2 mm size in the dispersion-free solders! with
the window of superplastic behavior being at the strain rates
of 231023 s21 or higher. Further research is required to
clearly understand the deformation mechanisms involved. At
any rate, these results suggest the possibility of controlling
the location of this high ductility window; e.g., by altering
the volume fraction of the dispersoid or the grain size and
making the new solders useful for high strain-rate applications, such as shock-resistant solders. Further research and
development is required to advance the soldering techniques
for these materials.
1

FIG. 4. Comparative steady-state compressive creep rates for the PbSn

solder with and without dispersoids, and the 80Au20Sn solder.

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