SCIENCE CHINA

Technological Sciences
July 2013 Vol.56 No.7: 1740–1748
doi: 10.1007/s11431-013-5261-y

Metallurgical challenges in microelectronic 3D IC packaging

technology for future consumer electronic products
K. N. TU1,2* & TIAN Tian2
1
Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon Tong, Kowloon, Hong Kong
(on sabbatical leave from UCLA);
2
Department of Materials Science and Engineering, University of California at Los Angeles, Los Angeles, CA 90095, USA

Received April 25, 2013; accepted May 13, 2013; published online May 20, 2013

Metallurgical challenges in controlling the microstructural stability of Cu and solder microbumps in 3D IC packaging technol-
ogy are discussed. Using uni-directional <111> oriented nanotwinned Cu, the controlled growth of oriented Cu6Sn5 on the
nanotwinned Cu and its transformation to Cu3Sn without Kirkendall voids have been achieved. In order to join a stack of Si
chips into a 3D device, multiple reflows of solder microbumps may be required; we consider localized heating to do so by the
use of self-sustained explosive reaction in multi-layered Al/Ni thin films of nano thickness. It avoids re-melting of those solder
joints which have been formed already in the 3D stacking structure.

3D IC packaging, microbump, localized heating

Citation: Tu K N, Tian T. Metallurgical challenges in microelectronic 3D IC packaging technology for future consumer electronic products. Sci China Tech
Sci, 2013, 56: 17401748, doi: 10.1007/s11431-013-5261-y

1 Introduction chips. In today’s flip chip technology, the diameter of a

As the trend of miniaturization of large-scale-integration of
2D circuits on Si chips is approaching the limit of Moore’s
law, microelectronic industry has been looking for ways to
extend the limit. At the moment the most promising way is
3D IC by merging together the chip technology and the
packaging technology. Roughly speaking, the essence in 3D
IC is the stacking of chips, which requires vertical inter-
connection between two of them. In consumer electronic
products such as cell phones, the packaging technology is
what enables human to interact with the semiconductor de-
vices.
There is not yet a Moore’s law for the packaging tech-
nology. Instead, if we just consider the diameter of solder
joints, which are used to interconnect circuit conductors or
*Corresponding author (email: kntu@ucla.edu)
solder joint is about 100 m, and the diameter of solder
microbumps, which are being developed for 3D IC now is
about 10 m. It is possible that the diameter can be reduced
to 1 m, thus there is ample room for reduction in the near
future for 3D IC. Indeed, the market survey company, Yole
Development in Lyon, France, has projected recently that
the 3D IC market in 2017 will reach US$38B, which is
about 3 to 4% of the global semiconductor market of
US$1trillion, and 3D IC has ten times faster growth than the
global semiconductor industry. It means there will be new
jobs in consumer electronic products industry.
To stack Si chips in 3D, the microelectronic industry is
developing the through-Si-via (TSV) technology and mi-
crobump technology [1–3]. The latter is used to join the
vertical vias between two TSV chips in stacking. Figure 1
depicts a schematic diagram of the cross-section of TSV.
The top is a flip-chip, which is connected to a TSV chip
with solder microbumps. Below the top flip chip, two TSV

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 Tu K N, et al. Sci China Tech Sci July (2013) Vol.56 No.7 1741

to join all the chips together in stacking. With multiple re-

flows, we expect that the microbump can become IMC
completely. The challenge is to control the IMC formation
in multiple reflows.
To slow down the Cu-Sn reaction to form IMC, a diffu-
sion barrier of Ni has been added to the UBM. It is of inter-
est to show that the Ni can also reduce Sn whisker for-
mation as shown in Figure 2. Without Ni, the Pb-free solder
Figure 1 Schematic diagram of the cross-section of a stacking of three bump grows Sn whisker at room temperature storage, Fig-
chips with vertical connections. It is not the cross-section of a real 3D ure 2(a), which can become an electrical short. With Ni, the
device, rather it depicts the essence in 3D stacking of chips by the use of solder bump surface remains smooth at ambient temperature,
TSV and solder microbumps. In the diagram, a flip-chip is on top of two
TSV chips, which have vertical vias joined by microbumps. The bottom of
Figure 2(b). Since fine pitch interconnection is the main
the lower TSV chip is joined to a polymer based substrate by a set of much trend today, this kind of protrusion on the solder surface is
larger ball-grid-array (BGA) solder balls. Most of the 3D structure is em- definitely of serious reliability concern.
bedded in epoxy underfill for mechanical strengthening. The arrows in the Since Sn has a body-centered tetragonal crystal structure,
diagram show the path of electric current for electromigration tests.
it has anisotropic properties, for example, its conductivity is
different between the c-axis and the a or b-axis in a unit cell,
chips are shown here, but it could be 8 to 10 chips in a real
3D stacking. In the vias, Cu, W, or heavily doped poly-Si
are being considered as the via materials, and it seems that
Cu vias are more popular. Today, the vias diameter is about
10 m. Joining the Cu vias are microbumps, which are
Pb-free solder. Owing to the change in dimension and in
geometry, the yield and reliability issues in 3D IC packag-
ing will have new metallurgical challenges. The change in
dimension is because the diameter of via is about 10 m, so
does the diameter of microbumps. The change in geometry
is due to f 3D vertical integration. We ask what are the met-
allurgical challenges?
When the solder joint diameter is reduced by 10 times,
from 100 m to 10 m, the volume is reduced by 1000
times. If we consider an extreme case in which the grain
size is assumed to be 10 m, the microbump will have only
one grain, but the flip chip solder joint will have 1000
grains. In the latter, we can assume the properties of the
solder joint to be isotropic because of the large number of
randomly oriented grains, but in the former, we cannot.
When there is only one grain in a bump, its properties will
depend strongly on the grain orientation. So the first chal-
lenge is the control of microstructure of microbumps.
Furthermore, while the size of microbump is reduced, the
temperature and time of its processing are unchanged, for
example, the temperature and time of reflow (melting of the
solder bump) will be more or less the same as that in pro-
cessing flip chip solder joints of 100 m in diameter. The
consequence is that the relative amount of intermetallic
compound (IMC) formation between the solder and un-
der-bump-metallization (UBM) will be greatly increased.
Also while we reduce the thickness of solder, we do not
reduce the UBM thickness in proportion. Besides, the Cu
vias in TSV are reservoirs for Cu in solder reactions. More
importantly, to stack up multiple chips, we may need multi-
ple reflows because each chip may need a reflow to join, Figure 2 (a) Without Ni, the Pb-free solder bump grows Sn whisker at
which will enhance metallurgical reactions. It is unclear if room temperature storage; (b) with Ni, the solder bump surface remains
the use of a single reflow or one processing step will be able smooth at ambient.
1742 Tu K N, et al. Sci China Tech Sci
and it tends to deform by twinning. In transforming Sn to
Cu-Sn IMC, the IMC has anisotropic crystal structure too.
This is a serious concern because it means that among a
large number of microbumps on a TSV chip, the properties
of each of the microbumps can be different when the bump
size is small and contains just one or a few grains [4, 5].
From the viewpoint of reliability, it could mean a wide dis-
tribution in failure time, so some of the microbumps could
have early failure. In manufacturing microelectronic devices,
early failure should be avoided. How to avoid that is anoth-
er challenge.
Before we move on, it is worth mentioning that
70Cu30Sn is bronze, which was invented in China several
thousand years ago. Solder reaction between Cu and Sn is
nothing new. However, it is quite amazing to learn that a
research group that monitors the publications related to sol-
der materials and technology found that there are over
13000 journal publications related to them.
We must emphasize that the key advantage of solder joint
technology is that it is a low temperature (about 250°C)
process in non-vacuum ambient and it can achieve metallic
joints in thousands of them simultaneously and uniformly.
Overall, we can say it is a very forgiving technology. For
this reason, we cannot but keep Sn as the basic joining met-
al until a better replacement is found.
At this moment, the 3D IC packaging technology is un-
der intensive development and the processing steps and
methods are in a fluid state. Therefore, in this brief review,
we cannot be very specific in technology because the
roadmap is still under development, rather our comments
are generally based on science of materials. We shall con-
centrate on the challenges of how to control the microstruc-
ture in microbumps in order to have a uniform microstruc-
ture in all the microbumps. We will not cover reliability
issues since no mass production of 3D IC is available yet,
nevertheless it is expected to come out soon.
2 Microstructure control in a large number of
microbumps
To overcome the anisotropic grain size effect mentioned in
the above, there are three ways to do so. The first is to use
amorphous alloys which have no crystallographic orienta-
tion. The second is to use nanoscale grain size materials;
even 0.1 m grain size will give 1000 grains in a bump of 1
m in diameter. The third is to control the microstructure in
a microbump to have uni-directional growth so that grains
in all the microbumps (thousands of them) have the same
crystallographic orientation. The last one seems to be the
choice in the near future.
2.1 Amorphous solder
On amorphous alloy, it is well known that from the kinetic
July (2013) Vol.56 No.7
point of view, an alloy system which has a very deep eutec-
tic point tends to have the liquid-to-solid transition without
structural change. One example is 82Ni18P eutectic alloy.
Indeed amorphous Ni(P) alloy can be formed by electroless
plating, and it has been widely used to form hard coating on
razor blades. It is reported that 38Sn62Au alloy and Sn-60
to 70 at. % Bi alloy can exist in amorphous state in nano-
size particles. Whether these amorphous alloys will be sta-
ble at bulk size has not been studied. Especially, when they
react with Cu to form IMC, the stability should be consid-
ered.
2.2 Lower melting point of nano grain size solder
On nanoscale grain size, there has been an active effort to
use the effect of nano grain size to reduce the melting point
of Pb-free solder so that the reflow temperature can be low-
ered. This is because the reflow temperature of Pb-free sol-
der is about 30°C above that of the eutectic SnPb solder, so
it requires a polymer-based substrate to have a higher glass
transition temperature with manufacturing cost adding. The
concept of lower melting point of nano size particles is at-
tractive. Nevertheless, there are two difficulties in the ap-
plication to solder joints. The first is oxidation of nano size
Sn particles. The second is that the melting temperature of
nano size particles has a distribution because the nano parti-
cles have a size distribution. It is against the basic concept
of using eutectic alloy in solder joints, because the eutectic
has a single melting point so that the melting or solidifica-
tion of all solder joints can occur simultaneously and uni-
formly. We discuss the melting below.
At the melting point, the Gibbs free energies of the crys-
talline and the liquid phases are equal. The melting transi-
tion of a large number of nanoscale crystalline particles may
become gradual over a temperature range, depending on the
distribution of the nanoparticle size in the sample. Experi-
mentally, we tend to measure the melting of a sample con-
sisting of a large number of nanoparticles, rather than just
one nanoparticle. Assuming that the melting temperature
has an average value within a certain temperature range, we
shall define this value as the temperature at which the Gibbs
free energies of the two phases are equal [6].
In Figure 3, a plot of the Gibbs free energy versus tem-
perature of the liquid and solid states for a pure bulk phase
having a flat interface is depicted by the two solid curves.
We assume that the bulk sample has a radius r = ∞. The
two solid curves cross each other at the melting point Tm (r
= ∞).
For solid state nanoparticles of radius r, the Gibbs free
energy curves are represented by the broken curves, which
is parallel to the solid curve of r = ∞, and the energy dif-
ference between the two curves for the solid phases is a
Gibbs-Thomson potential energy of ps  2 s s / rs ,
where  s is the interfacial energy between the solid and
 Tu K N, et al. Sci China Tech Sci July (2013) Vol.56 No.7 1743

mation per atom qm and the entropy change per atom

liquid liquid

( qm   TdS Tmbulk  dS Tmbulk   Sl  S s  ), we obtain

solid solid

qm
Sl  S s 
Tmbulk

Figure 3 A plot of the Gibbs free energy versus the temperature of the
liquid and solid states for a pure bulk phase having a flat interface and
nanosize particles of radius r.
ambient and is independent of size. We are typically inter-
ested in the melting point of nanoparticles in air or vacuum
in a short time so we can ignore the effect of sublimation or
the effect of vapor phase. We ask if they are heated to some
constant temperature below Tm (r = ∞); will the nanoparti-
cles melt?
For liquid nanoparticles of radius r, the Gibbs free ener-
gy curve is represented by the other broken curve. The en-
ergy difference between the two curves for the liquids is a
Gibbs-Thomson potential energy of pl  2 l l / rl , where
 l is the interfacial energy between the liquid and ambient.
Typically, the solid state curve for nanoparticles inter-
sects the liquid state curve for r = ∞ at a lower temperature,
Tm  rs  , indicating that the melting point of the nanoparti-
cles is lower than that of the bulk solid having a flat surface.
How much lower the melting point will depend on the val-
ues of  and r for the solid and liquid states. We present an
analysis below.
First, the equilibrium condition at the melting point of
the nano solid and nano liquid particles is given as
 sbulk Tmbulk  T   2 s s / rs
 
 lbulk Tmbulk  T  2 l l / rl .
Expanding the chemical potentials into a Taylor series of
T, including only the first-order terms (for not a large size
effect) and accounting for the fact that the derivative of the
chemical potential with respect to temperature is minus en-
tropy, we obtain
 sbulk Tmbulk   S s T  2 s s / rs
 
 lbulk Tmbulk  Sl T  2 l l / rl .
T / Tmbulk    2 s s / rs  2 l l / rl  / qm
2 s s   l l rs 
 1  . (3)
qm rs   s s rl 
By considering the conservation of the number of atoms
in the nanoparticle,  4 / 3 rs3 / s   4 / 3 rl3 / l , we
have
2      2 /3 
T / T bulk
 s s 1  l  l   . (4)
m
qm rs   s  s  
 
In eq. (4), if we take l = s and l = s, the bracket term
becomes zero and the nanoparticles show no decrease in
melting temperature. Typically, we can assume that l = s;
thus, we must assume that s > l, as depicted in Figure 3.
Using the following reasonable values for a metal
 s  1.5 J/m 2 ,  l  1 J/m 2 , s  l  10 29 m 3 ,
qm  2  10 20 J, r  10 8 m,
we obtain T / Tmbulk  0.05. Thus, the absolute value of
the melting temperature lowering, ∆T, is approximately 50
degrees for a metal with a melting point of approximately
1000 K. Equation (4) shows that ∆T depends on r, it means
when there is a distribution of r of the nano particles in the
sample, there is a distribution of the melting point in the
sample.
The lowering of the melting point due to the small radii
of the solids was studied previously in the analysis of the
morphological instability of solidification during the growth
(1) of dendritic microstructures in bulk materials. This lowering
is a subject that was studied in depth by Mullins and
Sekerka [7].
It is known that nanosize grains of Cu3Sn formed in sol-
der joint reactions. Nevertheless, Kirkendall voids accom-
pany the transition from Cu6Sn5to Cu3Sn, but we can avoid
the void formation using nano-twinned Cu. Especially in
uni-directional growth of Cu6Sn5 in solder joint reactions, it
is reported that we can achieve it with the oriented (111)
(2) nano-twinned Cu [8].

Considering the equality of the bulk chemical potentials

for the solid and liquid at the bulk melting temperature, the
first terms on both sides of the above equation cancel out.
Using the Clausius relation between the heat of transfor-
2.3 Uni-directional growth of Cu and Cu-Sn interme-
tallic compound
When (100) or (111) oriented bulk single crystal Cu was
1744 Tu K N, et al. Sci China Tech Sci
wetted with molten solder for the study of IMC formation,
the oriented Cu6Sn5 with roof-top shape or prism-type was
observed [9, 10]. On the (100) oriented single crystal Cu,
the oriented Cu6Sn5 grains are elongated along two perpen-
dicular directions. On the (111) oriented single crystal of Cu,
the oriented Cu6Sn5 grains are elongated along three pref-
erential directions with 120° separation. The orientation
relationship between Cu6Sn5 and (100) Cu and (111) Cu
were determined and published [9, 10]. They will not be
repeated here.
Since the twin plane in Cu is the (111) plane and if we
can have this plane to be parallel to the substrate surface
during deposition or electroplating, we have a uni-direc-
tional growth of (111) oriented nano-twinned Cu film or a
very highly textured Cu film on a substrate. We might say
that the uni-directional growth of <111> oriented nano
twins is the second best choice to the first choice of a bulk
single crystal for the oriented IMC growth. On the (111)
oriented nano-twinned Cu, we can have similarly the ori-
ented growth of Cu6Sn5 as that on (111) oriented single
crystal of Cu.
The formation and mechanical properties of nanotwins in
bulk Cu has been well studied [11, 12]. The <111> oriented
nano-twin Cu thin films have been obtained by sputtering
[13, 14]. However, microelectronic industry prefers electro-
plating than sputtering due to cost. In electroplating, we can
use a seeding layer to enhance the nucleation of <111> ori-
ented Cu nuclei on a given substrate, for example on a Si
wafer. Then the oriented growth of <111> nano twins can
be enhanced by a high rate of rotation of the Si wafer or the
rotation of electrolyte during plating. The axis of rotation is
the surface normal of the wafer and it is also the normal of
the (111) twin plane.
The effect of rotation is to keep the surface temperature
of the wafer cool and constant. In addition, since it produces
a shear force between the rotating wafer and the plating
solution, it will remove any gas bubble formation on the
film surface. In addition, it will create instability of Cu ada-
toms on the Cu film surface, the (111) plane, so that the
probability of twin nucleation is enhanced due to stacking
fault.
Figure 4 shows focused-ion-beam (FIB) images of both
the top-view and cross-sectional view of an oriented and
nano-twinned Cu film. On the cross-section, columnar Cu
grains are shown, and in each grain there are layered paral-
lel planes, which are the nano-twins and they are parallel to
the film surface or the wafer surface. Since the twin plane is
(111), we have the oriented <111> nano-twins. X-ray dif-
fraction spectrum of the sample showed only a very strong
<111> reflection and <222> reflection of Cu. On the top
view of the surface as shown in Figure 4, there are cones on
each columnar grain, which are formed by the stacking of
multi-layers of (111) planes having smaller and smaller di-
ameter going from the base of each cone to the top of the
cone.
July (2013) Vol.56 No.7
Figure 4 Focused-ion-beam (FIB) images of both the top-view and
cross-sectional view of an oriented and nano-twinned Cu film.
Figure 5(a) shows an optical image of the cross-section
of a microbump joint. Figure 5(b) shows the FIB cross-sec-
tional view of a microbump joint formed with the oriented
nano-twin Cu as UBM on both the top and bottom sides.
The layered microstructure in both the top and the bottom
UBM are the oriented nano-twins. The scallops are the
Cu6Sn5 IMC. In between the scallops, there is the remaining
of the un-reacted Pb-free solder. Then, between the scallops
and the nano-twinned Cu, there is a thin layer of Cu3Sn.
After a longer annealing, Figure 5(c) shows that the solder
has been converted completely to Cu6Sn5 and Cu3Sn. The
middle layer of Cu6Sn5 is sandwiched between two thicker
Cu3Sn layers of nano-size grains. When the Cu6Sn5 scallops
from the upper and the lower UBM touched each other, they
joined to form columnar grains of IMC and surprisingly that
there does not seem to have a grain boundary between the
upper and the lower Cu6Sn5 grains. It is possible that a rapid
ripening or grain growth has occurred between them.
When Cu3Sn forms between Cu6Sn5 and Cu, Kirkendall
void formation has been reported [15]. Figure 6 is a
cross-sectional FIB/SEM image of Kirkendall voids in a
layer of Cu3Sn. This is because when one molecule of
Cu6Sn5 is converted to two molecules of Cu3Sn, the three Sn
atoms left behind will attract nine Cu atoms in order to form
three more molecules of Cu3Sn. The diffusion of nine Cu
atoms from the Cu UBM will require a reverse diffusion of
nine vacancies, which tends to form voids at the interface
between Cu3Sn and Cu as well as within Cu3Sn. Initially,
voids nucleated and formed at the interface. When Cu3Sn
grows thicker, the voids will be embedded into the Cu3Sn as
the interface moves into the Cu.
However, when Cu3Sn forms on nano-twinned Cu, very
few or no Kirkendall voids were observed. Figure 5(b) and
5(c) showed no Kirkendall voids. This is a significant
 Tu K N, et al. Sci China Tech Sci
Figure 5 (a) An optical image of the cross-section of a microbump; (b)
the FIB cross-sectional image of a microbump formed with the oriented
nano-twin Cu as UBM on both the top and bottom sides. In between the
UBMs, there are thin layers of Cu3Sn, scallops of Cu6Sn5, and the remain-
ing un-reacted Pb-free solder; (c) after a longer annealing, the
cross-sectional FIB image a sandwiched structure of Cu3Sn/Cu6Sn5/Cu3Sn.
There are no Kirkendall voids in the Cu3Sn.
July (2013) Vol.56 No.7 1745
Figure 6 A cross-sectional FIB/SEM image of Kirkendall voids in a
layer of Cu3Sn.
finding from the point of view of microbump reliability. It
was proposed that the steps and kinks on the interface be-
tween Cu3Sn and a (111) twin plane of Cu can serve as
sinks to absorb vacancies [7]. When no super-saturation of
vacancies occurs at the interface between the Cu3Sn and
nano-twinned Cu, there is no nucleation and growth of voids.
3 Multiple reflows in 3D IC packaging by local
heating
In the 3D stacking of multiple TSV chips, if we assume that
we have to perform solder joining of each chip, we may
need multiple reflows. At each reflow, the entire sample
will be heated above the melting point of the Pb-free solder,
this is undesirable because of thermal stress. Also those
joints formed in the very beginning will have to endure
multiple cycles of heating and cooling from the subsequent
reflows. They will melt again and again to enhance IMC
formation.
We recall that in flip chip technology, there are two lev-
els of solder joints. The first level is to join the Si chip to a
ceramic substrate and the high-Pb solder of about 95Pb5Sn,
which has a melting point about 300°C, has been used. The
second level is to join the ceramic substrate to a polymer
substrate and the eutectic SnPb solder, which has a melting
point of 183°C, has been used. During the second level
joining, the high-Pb solder will not melt. However, in 3D IC
having a stacking of several TSV chips, it is impossible to
have a hierarchy of solder materials that have several levels
of melting point because we just cannot find them. If only
one kind of Pb-free solder is used, how can we avoid multi-
ple melting and solidification is challenging.
3.1 Thermal compression bonding
Currently, microelectronic industry has utilized thermal
1746 Tu K N, et al. Sci China Tech Sci
compression to produce microbump joints on TSV chips
[16]. Figure 7 depicts a schematic diagram of the cross-
section of a pair of joints formed by thermal compression of
two pieces of Si chips face-to-face. On each chip, a thin
film of Ti serves as the adhesive layer to the Al interconnect
for the deposition of the Cu microbump, followed by a dif-
fusion layer of Ni and then a layer of SnAg solder. The
white arrows in the figure indicate the electrical current path
in electromigration testing of the pair of joints. The thick-
ness of each layer is given in the figure. Between the Ni and
SnAg, there is a thin layer of IMC of Ni3Sn4. In thermal
compression bonding, one chip is flipped over to face the
other. The operation temperature is about 260°C, and the
compression time is about 20 sec. Since there is a large
number of microbumps, easily over 1000 of them on each
TSV chip, the uniformity of the bump height is very critical
and a proper standoff-control is required during the bonding
process. Without a proper force or gap control, the solder in
some joints may be squeezed out and can touch the neigh-
bors to cause the failure of short circuit. Moreover, how to
keep a precise alignment during the bonding is also quite
challenging.
It is worth pointing out that in Figure 7, the thin solder
layer is joining two Cu pillars, not two Cu vias as depicted
in Figure 1. It is a promising SiP (system-in-package) way
to connect two active dices by face-to-face-bonding (i.e.
MEMS die and ASIC die in one package).
3.2 IMC joints
In IMC formation, typically there is a rather large volume
change, say between Cu-Sn (or Ni-Sn) IMC and pure Sn
plus pure Cu (or Ni). Under the constraint of constant gap
height between two chips, if there is residual Sn in the cen-
ter of the joint, the volume shrinkage caused by IMC for-
mation from both sides may lead to crack formation in the
middle of the joint or neck formation around the joint which
Figure 7 Schematic diagram of the cross-section of a pair of mcrobump
joints.
July (2013) Vol.56 No.7
is similar to a time-glass [16]. Meanwhile, underfill of
epoxy is needed to be introduced to strengthen the interfa-
cial bonding. Without underfill, the mechanical property of
the 3D structure is a critical issue since the IMC is brittle.
While the brittle IMC is undesirable, it is worth mentioning
that there is an advantage of IMC joint because of its higher
melting point than that of solder and thus the higher elec-
tromigration resistance. When the joint size is small, the
entire joint can be transformed into IMC in the first reflow,
the IMC will not melt in the subsequent reflows. Thus we
can join chips sequentially; one at a time.
3.3 Localized heating by using self-sustained explosive
reaction
We consider below the application of a localized heating to
reflow solder joints. By using multi-layered thin films of
nano layer thickness, we can have self-sustained explosive
reaction as a localized heat source [17–24]. It is a room
temperature compression bonding. The advantage of local-
ized heating is that we can use just one kind of solder in
stacking chips in 3D, without re-melting of those joints that
have already been formed. This is because they will not be
re-heated.
A schematic diagram of the multi-layered Al/Ni/Al/Ni
thin films is depicted in Figure 8. A periodic multilayered
thin film with nanometer thickness is energetically unstable
if the two types of thin films in the periodic structure can
react to form an IMC. When the period is in the order of
nanometers, the very high rate of interfacial reaction can
generate a large amount of heat that enables a self-sustain-
ing explosive reaction. It was found that a small amount of
external energy in the form of electrical spark, laser pulse,
or mechanical impact at room temperature will ignite a lo-
calized reaction by initiating interdiffusion and reaction in
the multi-layered structure at the point of spark or impact.
The heat release from the point of reaction is intensive
enough to lead to heat transfer by thermal diffusion laterally
along the multi-layered structure and to heat up the neigh-
boring region to a much higher temperature for a very fast
atomic interdiffusion and reaction. As the reaction proceeds,
Figure 8 Schematic diagram of a multi-layered Al/Ni/Al/Ni thin film for
self-sustained explosive reaction.
 Tu K N, et al. Sci China Tech Sci
more heat is generated and released. Consequently, a self-
sustained reaction or explosive reaction occurs. For example,
to ignite the reaction mechanically at room temperature, the
dropping of a pointed pencil on the surface of a mul-
ti-layered Al/Ni thin film will cause an explosive reaction.
Accompanying the explosive reaction, a flash light of or-
ange color can be seen, which is an indication of the reac-
tion temperature. It is a localized heating, limited by the
location and size of the multi-layered thin films. The re-
leased heat can serve as a heat source to trigger other chem-
ical reactions, as in the reflow of low melting point solder
[25]. The nanotechnology of multilayered nano-thick thin
films can have applications as ignition materials in distance.
In Figure 8, the Al layer of 2l thickness is sandwiched
between two Ni layers, each having a thickness l, which we
assume to be 10 nm. By repeating this sandwiched struc-
ture, we can obtain a multilayered Al/Ni/Al/Ni structure
having an Al/Ni period of 4l = 40 nm in thickness. We as-
sume that interdiffusion and reaction occur by the diffusion
of Ni into Al because the melting temperature of Al is
660°C, which is much lower than that of Ni, over 1400°C.
This is because both Al and Ni are face-centered cubic met-
als, at a given reaction temperature, there are significantly
more equilibrium vacancies in Al than in Ni, so Ni diffuses
into Al.
We further assume that during the explosive reaction, the
reaction temperature is close to the melting point of Al, so
the atomic diffusivity in Al will be approximately 10-8
cm2/sec. Assuming a diffusion-controlled explosive reaction,
the time needed for interdiffusion and reaction in the multi-
layered structure will be [5]
l2 (10 6 cm)2
  8 2  10 4 sec .
D 10 cm / sec
This reaction is assumed to be exothermic, so no heat
will be transferred in the direction normal to the two inter-
faces, the y-direction, as shown in Figure 8. Thus, the heat
generated by the reaction between Al and Ni will be trans-
ferred only in the x-direction. During this time, the heat
transfer will travel a distance λ in the x-direction, where
a2l 2
  a 2 
D electroplated uni-directional <111> oriented nanotwinned
and a 2 is the thermal diffusivity in the heat transfer equa-
tion below.
T 2 T
 a2 2 .
t x
The unit of a 2 is cm2/sec, which is the same as that of the
atomic diffusivity, D. In heat transfer, the heat flux equation
is given as
July (2013) Vol.56 No.7 1747
T
J heat   , (8)
x
where Jheat is the heat flux in joule/cm2-sec and  is the
thermal conductivity in joule/°K-cm-sec. The unit of ther-
mal conductivity is often expressed in units of watt/°K-cm.
If we change the thermal energy of a joule to the electrical
energy of an eV and divide the electrical energy by time, we
have watt, which is the unit of power. It is known that a 2 =
/Cp, or   a 2 C p  , where Cp is the heat capacity per
unit mass in joule/°K-m0 and  = m0/ is the mass density,
where m0 is the atomic mass and  is the atomic volume.
For metals, if the Dulong-Petit law holds, we have Cp =
3k/m0. Thus, a 2 =/3k. For metals, we typically have
a 2 = (0.1 – 1) cm2/sec. In eq. (5), we have assumed that
l2 2
  . (9)
D a2
Taking τ = 10-4 sec, using eq. (9), we find that  
a 2  10 2 cm, which is the distance of heat transfer.
Thus, the velocity of the explosive propagation or flame
velocity can be estimated as
 a2 D
v   100cm / sec . (10)
 l
Furthermore, if melting occurs, the diffusivity will be
5
10 cm2/sec, and the velocity will be approximately 10 to
100 m/sec. This calculated velocity is in very good agree-
ment with the measured velocity of reaction propagations.
[19] The velocity is inversely proportional to the layer
(5) thickness and proportional to the square root of the product
of the thermal diffusivity and atomic diffusivity (the inter-
diffusion coefficient).
4 Summary
In this brief review, several metallurgical challenges related
to the control of microstructural stability in microbumps in
3D IC packaging technology are discussed. Starting from
(6)
Cu, we obtain the controlled growth of oriented Cu6Sn5 on
the nanotwinned Cu and its transformation to Cu3Sn without
Kirkendall voids. In order to join all the microbumps to
form a 3D stacking of chips, multiple reflows may be re-
(7)
quired, which is undesirable because of thermal stress and
re-melting of those joints formed already. We consider the
use of nanotechnology of multi-layered thin films of nano
thickness to achieve localized heating by the self-sustained
explosive reaction.
1748 Tu K N, et al. Sci China Tech Sci
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