Journal of Alloys and Compounds 709 (2017) 700e707

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Depressing of CueCu bonding temperature by composting Cu

nanoparticle paste with Ag nanoparticles
Junjie Li a, b, Xing Yu a, Tielin Shi a, b, Chaoliang Cheng a, Jinhu Fan a, Siyi Cheng a,
Tianxiang Li a, Guanglan Liao a, b, Zirong Tang a, b, *
a
State Key Laboratory of Digital Manufacturing Equipment and Technology, Huazhong University of Science and Technology, Wuhan, PR China
b
Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, we proposed a depressing bonding temperature method for CueCu bonding with nano-
Received 10 February 2017 particle paste. The paste was prepared by composting dominant Cu nanoparticles with Ag nanoparticles
Received in revised form of lower sintering temperature, where the average nanoparticle size of Cu and Ag was 61.02 and
20 March 2017
69.25 nm, respectively. The reliable bonding was successfully achieved at the temperature of 250  C, the
Accepted 20 March 2017
Available online 22 March 2017
pressure of 1.12 MPa and the protection of Ar-H2 gas mixture comparing with pure Cu nanoparticles
paste. An optimal resistivity of sintered Cu-Ag composite nanoparticle paste can achieve 1.99  10 7 U m
with the 2:1 molar ratio of Cu to Ag, and the largest shear strength of the bonded Cu-Cu joint can reach
Keywords:
CueCu bonding
25.41 MPa. The underlying sintering mechanism of the composited nanoparticles was discussed. It
Cu and Ag nanoparticles suggests the compositing with Ag nanoparticles is a practical strategy towards lowering the bonding
Composite nanoparticle paste temperature for Cu-based interconnect. The experimental process can be easily implemented, the
Sintering bonding temperature and the performance can satisfy the packaging requirements of current 3D-IC. The
3D-IC developed Cu-Ag composite nanoparticle paste is also promising for packaging of other thermal and
force sensitive chips.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction the interconnection interface achieve low resistivity, good resis-

With the sustainable development of integrated circuits and
semiconductor technology, the trend of decreasing the chip size has
pushed to the limit of Moore's law [1]. To face this challenge, the
advanced three-dimensional integrated circuits (3D-IC) packaging
technology is widely proposed in the research field of microelec-
tronics for achieving high density integrated circuits with high
performance, low power consumption, small factor and low cost
[2e5]. In 3D-IC packaging, the CueCu bonding technology is
regarded as a critical part. However, the classical Sn based solders
show some defects with the scaling down of interconnection, such
as the electromigration phenomenon and the Sn overflow induced
bump bridge failure in fine-pitch bonding [6e9].
In order to solve these problems, researchers pay much interest
on high performance interconnection materials recent years, such
as Cu and Ag. Compared to Sn based materials, Cu and Ag can help
* Corresponding author. 1037 Luoyu Road, Wuhan, 430074, PR China.
E-mail address: zirong@hust.edu.cn (Z. Tang).
tance to electromigration, high electrical and thermal conductivity
[10,11]. However, due to the high melting temperature of Cu and Ag,
the bonding temperature by using these materials is always high
[12]. To meet the demands of practical application, reducing the
bonding temperature is an urgent need. With the advancement of
nanotechnology, the sintering temperature of nanoparticles can be
reduced to a low value by the size effect of nanomaterials [13,14].
CueCu bonding by using the sinterable nanoparticle paste can
achieve a significant depression of bonding temperature, which is
much lower than the melting temperature of bulk materials. As
reported, by using the Ag nanoparticle paste, the CueCu bonding
temperature could be reduced to less than 300  C [15e17]. How-
ever, because of the high cost of Ag, it is not suitable for large scale
use as an interconnection media. On the other hand, with Cu
nanoparticle paste, the CueCu bonding temperature can be greatly
reduced, but it is still difficult to achieve a low bonding temperature
less than 350  C [18], since the lower sintering and bonding tem-
perature requires the Cu nanoparticles with much smaller size,
which results in the high cost of synthesis and storage for Cu
nanoparticles. Therefore, CueCu bonding by using the pure Cu

http://dx.doi.org/10.1016/j.jallcom.2017.03.220
0925-8388/© 2017 Elsevier B.V. All rights reserved.
 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707
nanoparticle paste is difficult to achieve the strict demands of 3D-IC
packaging for thermal sensitive chips.
In this work, we proposed a low temperature CueCu bonding
method by using the Cu-Ag composite nanoparticle paste. The
composite nanoparticle paste was prepared by mixing Cu nano-
particles, Ag nanoparticles and organic solutions. With the Cu-Ag
composite nanoparticle paste, a compact and reliable CueCu
bonding joint could be achieved at a low bonding temperature of
250  C, under the bonding pressure of 1.12 MPa and the protection
of Ar-H2 (5% H2) gas mixture.
2. Experimental section
2.1. Materials
Copper sulfate pentahydrate, sodium hypophosphite hydrate,
ethylene glycol, tertiary butanol, acetic acid, acetone and ethanol
were purchased from Sinopharm Chemical Reagent Co. Ltd. Ag
nanoparticles and Polyvinylpyrrolidone (PVP) were purchased from
Aladdin reagent Co. Deionized water was used throughout all
experimental process. All chemical reagents were of analytical
grade and without any subsequently treatment.
2.2. Preparation of nanoparticle pastes
The Cu nanoparticles were synthesized with simple routes for
preparing nanoparticle pastes. In the typical process, a beaker
containing 1 g copper sulfate pentahydrate and 20 ml ethylene
glycol was heated to 90  C in an oil bath with magnetic stirring,
Fig. 1. The SEM image of (a) Cu nanoparticles and (b) Ag nanoparticles; the size distribution of (c) Cu nanoparticles and (d) Ag nanoparticles.
701
while another three-mouth flask containing 2 g sodium hypo-
phosphite hydrate, 6 g PVP and 80 ml ethylene glycol was heated to
90  C with mechanical stirring. After all agent dissolved completely,
the solution in the beaker was poured into the three-mouth flask
rapidly, and the heating was last for another 25 min with contin-
uously stirring. The final reacted dispersion was washed by ethanol
and deionized water via centrifugation for at least 5 times. The Cu
nanoparticles were collected by vacuum drying at 30  C for 6 h.
Nanoparticle pastes were prepared by mixing 65 wt% solid
fillers and 35 wt% organic solvents through vacuum mixer at
2500 rpm for 5 min. To investigate the sintering and bonding
performance of Cu-Ag composite nanoparticle paste, the nano-
particle pastes containing only pure Cu or pure Ag nanoparticles as
solid fillers had also been taken into account for comparison. The
mixture of tertiary butanol and a small amount of ethanol was
selected as organic solvents for the nanoparticle paste, which could
be completely volatilized below 85  C.
2.3. Sintering and bonding processes
To investigate the electrical performance of sintered nano-
particle pastes, the non-conductive glass slides were used as the
substrates, while the sintering samples were prepared by uniformly
coating the nanoparticle pastes on substrates. The sintering process
was proceeded by heating the sintering samples to 250  C for
60 min without any pressure. On the other hand, the CueCu
bonding samples were prepared by two pieces of Cu substrates and
a coated nanoparticle paste layer. The sizes of upper and lower Cu
substrates were 3  3  1 mm3 and 6  6  1 mm3 respectively, and
702 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707

the substrates were washed by acetic acid and acetone to remove

the metal oxides and organic impurities. The bonding process was
proceeded by heating the bonding samples to 250  C for 60 min
with a low bonding pressure of 1.12 MPa. In the whole sintering and
bonding process, Ar-H2 (5% H2) gas mixture was introduced to
prevent oxidation.

2.4. Characterizations and measurements

The morphological features of Cu nanoparticles, Ag nano-

particles, sintered nanoparticle pastes, CueCu bonding interfaces
and fracture surfaces were observed by scanning electron micro-
scope (FEI Nova Nano SEM 450). XRD patterns of Cu and Ag
nanoparticles were determined by High-resolution X-ray diffrac-
tometer (PANalytical PW3040/60). The electrical performance of
the sintered nanoparticle pastes was measured by 4-Point Probes
Resistivity Measurement System (PROBES TECH RTS-8), and the
shear strength of Cu-Cu joints was measured by Micro Materials
Testing Platform (DAGE-4000Plus Bond).

3. Results and discussion

3.1. Characterization of Cu and Ag nanoparticles

Fig. 1 shows the SEM images and size distributions of synthe-

sized Cu nanoparticles and commercial purchased Ag nano-
particles. From SEM images of nanoparticles, we can observe that
both Cu and Ag nanoparticles are homogeneous dispersed without
hard agglomerates. The size of Cu nanoparticles is relatively uni-
form, and the morphology of Cu nanoparticles is presented as
quasi-spherical shapes. Besides, the Ag nanoparticles present wider
range of sizes than Cu nanoparticles, and some Ag nanoparticles
larger than 140 nm could be clearly observed in the SEM image. The
size distributions of Cu nanoparticles and Ag nanoparticles (Fig. 1(c)
and (d)) were analyzed by the Nano Measurer software. As illus-
trated in distribution graphs, the size distribution of Cu nano-
particles is more concentrated with respect to that of Ag
nanoparticles. The size range of Ag nanoparticles is wider, while the
calculated average size of Ag nanoparticles (69.25 nm) is also larger
than that of Cu nanoparticles (61.02 nm). Obviously, the calculation
results based on the distribution graphs are in correspondence with
the previous observation results.
To analyze the purity of Cu and Ag nanoparticles, the XRD pat-
terns (Fig. 2) were measured. As illustrated in Fig. 2(a), the sharp
diffraction peaks are appeared at the diffraction angle of 43.297,
50.433 , 74.130 , 89.931 and 95.139 , which respectively represent
the (111), (200), (220), (311) and (222) planes of Cu crystal. Ac-
cording to the peaks, the synthesized Cu nanoparticles can be
determined as single crystal Cu without any impurities. For com-
mercial purchased Ag nanoparticles, the main characteristic
diffraction peaks are observed at 38.116 , 44.277, 64.426 , 77.472 ,
81.536 and 97.888 , which can be determined as the (111), (200),
(220), (311), (222) and (400) planes Ag crystal. Therefore, the Cu
and Ag nanoparticles used in this work are with high purity.
3.2. Morphology and electrical property of sintered nanoparticle
pastes
The sintering performance of nanoparticle pastes plays a deci-
sive role in the reliability of CueCu bonding [19,20]. Fig. 3(a) and (b)
respectively show the morphological changes of sintered Cu and Ag
nanoparticle pastes under 250  C by SEM. From the images, surface
melting phenomenon of sintered Cu nanoparticles can be clearly
observed. Under the effect of surface tension and surface melting,
the nanoparticles around 50 nm disappeared and the adjacent
Fig. 2. The XRD patterns of (a) Cu nanoparticles and (b) Ag nanoparticles.
nanoparticles fused into larger particles. However, large area
melting and coalescence did not occur for the sintering of Cu
nanoparticles. Unlike the properties exhibited by Cu nanoparticles,
the Ag nanoparticles showed better sintering performance at
250  C. The morphological features of Ag nanoparticles showed
significant changes after sintering, where large area of coalescence
were observed. Therefore, with similar particle sizes, Ag nano-
particles can achieve more obvious morphological changes and
better sintering effect than Cu nanoparticles at low sintering tem-
perature. According to the excellent sintering properties and
fluidity presented by Ag nanoparticles, the sintering performance
of Cu based nanoparticle paste might be enhanced by introducing
Ag nanoparticles [21,22].
Based on the observation and analysis above, a new type of
nanoparticle paste is developed by composting Cu nanoparticles
with Ag nanoparticles in this work. In order to investigate the effect
of Ag nanoparticles on the sintering properties of Cu nanoparticle
pastes, we prepared two different sets of Cu-Ag composite nano-
particle pastes. To simplify the presentation, we denominate Cu3-
Ag and Cu2-Ag nanoparticle paste, which respectively represent
the Cu-Ag composite nanoparticle paste with the Cu-Ag molar ratio
of 3:1 and 2:1. Fig. 3(c) shows the SEM image of the sintered Cu3-Ag
nanoparticle paste at 250  C for 60 min. With the addition of Ag
nanoparticles, the sintering phenomenon of Cu3-Ag nanoparticle
paste is more obvious than that of pure Cu nanoparticle paste. In
this case, the surface melting of Ag nanoparticles plays a role in
connecting the surrounding copper nanoparticles. However, a large
number of voids are also present in the sintered Cu3-Ag
 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707
Fig. 3. SEM images of sintered (a) Cu, (b) Ag, (c) Cu3-Ag and (d) Cu2-Ag nanoparticle pastes after sintering at 250  C; (e) and (f) are the corresponding XRD patterns of (c) and (d)
respectively.
nanoparticle paste. As the Cu-Ag molar ratio decreases to 2:1, the
voids in the sintered nanoparticle pastes are reduced due to the
better sintering performance of Ag and some melted Ag effectively
filled into some voids during the sintering process. Besides, as
shown in Fig. 3 (e) and (f), the peak variations in XRD patterns of
the sintered Cu-Ag composite nanoparticle pastes also reflect the
Ag ratio changes. The intensity of Ag signal in the XRD patterns of
Cu2-Ag nanoparticle paste are stronger than that in the Cu3-Ag,
which indicate the increase in Ag content.
Fig. 4 shows the color and the electrical changes of sintered
nanoparticle pastes with the variation of Ag content. Compared
with the sintered Cu nanoparticle paste, the color of the sintered
Cu-Ag composite nanoparticle pastes is lighter and the electrical
resistivity is lower. As shown in Fig. 4(b), the resistivity of the
sintered pure Cu nanoparticle paste was measured to be
15.66  10 7 U m. Meanwhile, with the addition of Ag, the re-
sistivity of the sintered Cu3-Ag nanoparticle paste decreases to
6.54  10 7 U m, which is 2.4 times lower than that of Cu nano-
particle paste. As the Cu-Ag atomic ratio decreased to 2:1, the re-
sistivity of the sintered Cu2-Ag nanoparticle paste was measured to
703
be 1.99  10 7 U m, closing to the value of sintered Ag nanoparticle
paste (1.20  10 7 U m). From the measurements, we can conclude
that the sintered Cu2-Ag nanoparticle paste can achieve the similar
sintering and electrical performances as the sintered Ag nano-
particle paste.
The above sintering phenomenon showed by Cu nanoparticles
and their composites can be explained by sintering theory. The
material transport and the neck formation of two adjacent particles
in a sintering process was induced by grain boundary diffusion,
surface diffusion and lattice diffusion, which were driven by the
reduction of interfacial energy [23]. Compared to lattice diffusion,
the activation energy for grain boundary diffusion and surface
diffusion is much lower. Meanwhile, the grain boundary diffusion is
always influenced by the size of particles, and the surface diffusion
can be achieved by the reduction of surface energy [24,25]. In this
work, the Cu and Ag nanoparticles are with similar size distribu-
tion, so the main factor affecting the sintering process of Cu and Ag
is the surface energy induced surface diffusion, while the surface
diffusion at the interface of two nanoparticles is a solid-liquid
physical process, which is always manifested by the surface
704 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707
Fig. 4. (a) Color and (b) electrical resistivity changes of sintered Cu, Cu3-Ag, Cu2-Ag
and Ag nanoparticle pastes at 250  C. (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)
melting and the fusion of nanoparticles [26,27]. Besides, the initial
surface energy of Ag is much lower than that of Cu, which can
induce a lower activation temperature for surface diffusion [28,29].
Therefore, the Ag nanoparticles have higher surface diffusivity at
the same temperature compared to the Cu nanoparticles, and the
fusion area of Ag nanoparticles is also larger, as illustrated in
Fig. 5(a) and (b). The more pronounced morphological changes and
lower resistivity of sintered Ag nanoparticle pastes showed in
Figs. 3 and 4 also verify this mechanism.
For Cu-Ag composite nanoparticle paste, the addition of Ag
nanoparticles plays a decisive role in enhancing the diffusivity. As
Fig. 5. The sintering mechanism schematic diagram of (a) Cu-Cu, (b) Ag-Ag and (c) Cu-
Ag nanoparticles.
illustrated in Fig. 5(c), the high diffusivity of Ag nanoparticles
effectively accelerates the diffusion velocity at the interface of Cu
and Ag in the sintering process, and a stable interconnection can be
formed as the fusion area expanded. With the increase of Ag con-
tent, the highly sinterable Ag nanoparticles can provide adequate
interconnection with the insufficient sintered Cu nanoparticles.
Fig. 6 shows the TEM images of the sintered Cu-Ag nanoparticles
after sintering at 250  C. From image of Fig. 6(a) and the corre-
sponding 3 points EDX spectra of Fig. 6(c), we can infer that point 2
is in the diffusion layer of the sintered Cu-Ag nanoparticle joint. As
shown in Fig. 6(b), a large number of moire fringes appeared in the
diffusion layer. These moire fringes were formed by the overlapping
of the crystal growth striation of Cu and Ag, indicating the stable
interconnection of Cu and Ag after sintering [30]. Through the
observation of TEM images, we can infer that the previously pro-
posed sintering mechanism is practical and reliable.
3.3. Microstructure and shear strength of CueCu bonding joint
The CueCu bonding process was proceeded at the temperature
of 250  C for 60 min by using nanoparticle pastes, under a low
bonding pressure of 1.12 MPa. Fig. 7 shows the cross-sectional
microstructure of CueCu bonding interfaces by using different
nanoparticle pastes. From Fig. 7(a), we can infer that the bonding
joint is incompact. Numbers of defects and voids exist in the
bonding interface, while the outline of Cu nanoparticles can also be
observed. The main reason for the appearance of this kind of
morphological features is the insufficient sintering of Cu nano-
particles at 250  C. In contrast, the bonding interface by using the
well sinterable Ag nanoparticle paste is highly compact and almost
free of defects, as shown in Fig. 7(b). For the CueCu bonding by
using the Cu3-Ag nanoparticle paste, the defects in CueCu bonding
interface showed in Fig. 7(c) are significantly less than that in
Fig. 7(a), since the highly surface meltable Ag nanoparticles can
effectively fill the surrounding voids during the bonding process.
However, the existence of small defects demonstrates that the Ag
content is not enough to provide sufficient filling effect. With the
decreasing of Cu-Ag atomic ratio, the CueCu bonding joint by using
the Cu2-Ag nanoparticle paste presents a more compact structure,
and almost no defects and voids could be detected. From the
observation, we can infer that the Cu-Cu joint with Cu2-Ag nano-
particle paste may achieve a similar shear strength as the joint with
pure Ag nanoparticle paste.
The shear strength of bonding joints was determined by moving
the test head with the speed of 10 mm/min, as shown in Fig. 8(a).
Meanwhile, the measurement results in Fig. 8(b) illustrate the ef-
fect of the addition of Ag nanoparticles on enhancing the shear
strength. By introducing Ag nanoparticles, the shear strength of Cu-
Cu with Cu3-Ag nanoparticle paste achieved 14.26 MPa, about two
times higher than 7.32 MPa strength of the joint with pure Cu
nanoparticle paste. For the Cu-Cu joint with Cu2-Ag nanoparticle
paste, the shear strength increased to 25.41 MPa, almost close to
the value of 27.03 MPa by using the pure Ag nanoparticle paste.
Therefore, CueCu bonding by using Cu2-Ag nanoparticle paste can
reach a relatively high bonding strength, which is suitable for
practical use in 3D-IC packaging [6,31].
Fig. 9(a)e(d) shows the fracture morphologies of bonding joints
by using different nanoparticle pastes. From the SEM images, we
can observe that there is no obvious substantial destruction in the
bonded fracture structures when the bonding joints were achieved
by using Cu nanoparticle pastes. Most of these structures only show
the morphological changes of the sintered nanoparticles under the
bonding pressure, and some of the voids resulted from insufficient
sintering can also be observed in the fracture structure of the joint
with Cu nanoparticle paste. After bonding with the Cu3-Ag
 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707 705

Fig. 6. (a) The TEM image of the sintered Cu-Ag nanoparticles after sintering at 250  C. (b) The partially magnified HRTEM image of (a). (c) The corresponding EDX spectra of point 1,
2 and 3 in (a).

Fig. 7. The cross-sectional SEM images of CueCu bonding interfaces by using (a) Cu, (b) Ag, (c) Cu3-Ag and (d) Cu2-Ag nanoparticle pastes.
 Fig. 8. (a) The schematic diagram of shear force measurement; (b) the shear strength of bonding joints with different nanoparticle pastes.

Fig. 9. Fracture morphologies of CueCu bonding joints by using (a) Cu, (b) Cu3-Ag, (c) Cu2-Ag and (d) Ag nanoparticle pastes. (e) to (h) illustrates the corresponding EDX spectra of (a) to (d).
 J. Li et al. / Journal of Alloys and Compounds 709 (2017) 700e707
nanoparticle paste, the strength of the had been effectively
enhanced, and a small amount of ductile deformation structures
was appeared in the fracture surface of Cu-Cu joint. However, as
analyzed before, the Ag nanoparticles were not enough to provide
sufficient interconnection and filling, which resulted in the rela-
tively incompact fracture surface structure. On the other hand, the
fracture structures of the joints by using Cu2-Ag and Ag nano-
particle pastes present distinct ductile deformation characteristics.
A large area of elongated rift-like topography appears, which also
demonstrates that the bonding joint is effective and firm.
Fig. 9(e)e(h) shows the corresponding Energy Dispersive X-Ray
(EDX) spectra of Fig. 9(a)e(d). With the decreasing of Cu-Ag atomic
ratio, the intensity of Ag signal is more pronounced, and the
measured atomic ratio of Cu and Ag from EDX also confirms ho-
mogeneity of Cu-Ag composite nanoparticle pastes. Besides, almost
no other element can be detected except Cu and Ag, which dem-
onstrates that no oxides is produced and the organic solvent is
completely evaporated in the bonding process.
4. Conclusions
In summary, we have prepared a new type of Cu-Ag composite
nanoparticle paste, where the Cu nanoparticles were synthesized
with an average size of 61.02 nm. The morphological change and
the electrical resistivity of sintered nanoparticle pastes have been
investigated after sintering at 250  C for 60 min. The sintered Cu2-
Ag nanoparticle paste shows good sintering morphology, and the
electrical resistivity of it can reach 1.99  10 7 U m, closing to the
resistivity of the sintered Ag nanoparticle paste.
By using the Cu, Ag and Cu-Ag composite nanoparticle pastes,
the CueCu bonding process was performed at 250  C, with the
protection of Ar-H2 gas mixture, and under a low bonding pressure
of 1.12 MPa. From the measurements and observations, the bonding
joint with Cu2-Ag composite nanoparticle paste shows compact
structure in the cross-sectional interface and obvious ductile
deformation in the fracture. The tested shear strength can achieve
25.41 MPa, closing to the joint with Ag nanoparticle paste.
Comparing to the pure Ag nanoparticle paste, the Cu2-Ag nano-
particle paste can provide similar sintering performance, electrical
property and bonding strength at the same process condition.
Therefore, the cost-effective Cu2-Ag nanoparticle paste is more
promising to be widely used in 3D-IC packaging.
Acknowledgements
This work is supported by the National Basic Research Program
of China with Project No. 2015CB057205, and the Program for
Changjiang Scholars and Innovative Research Team in University
(Grant No. IRT13017).
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