Journal of Alloys and Compounds 629 (2015) 118–123

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Journal of Alloys and Compounds

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

Enhanced pressure-free bonding using mixture of Cu and NiO

nanoparticles
Toshikazu Satoh ⇑, Toshitaka Ishizaki
Toyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan

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

Article history: Pressure-free bonding using mixed Cu–NiO nanoparticles was examined. The effect of mixing NiO nano-
Received 27 October 2014 particles with Cu nanoparticles on bonding strength was identified for a NiO content between 0.005 and
Received in revised form 12 December 2014 2 wt%. The bonding layer, which presented a high bonding strength, was thin and dense. The Ni in the
Accepted 27 December 2014
bonding layer was segregated at the surface and at grain boundaries of crystalline Cu grains as a metallic
Available online 9 January 2015
Cu–Ni alloy. These results suggest that the effect of the NiO addition is caused by the enhancement of
sintering by surface diffusion in the bonding layer, resulting from sufficient removal of surface oxides
Keywords:
on the Cu nanoparticles through their reaction with the NiO nanoparticles.
Metals and alloys
Nanostructured materials
Ó 2015 Elsevier B.V. All rights reserved.
Sintering
Diffusion
Microstructure

1. Introduction have a low thermal conductivity, making it difficult for them to

Recently, there has been considerable interest in improving
hybrid electric vehicle technologies, which require electric propul-
sion systems with high current, high voltage, and low power loss
semiconductor devices. At present, these systems rely exclusively
on silicon-based power; however, silicon power devices are rapidly
approaching maturity. One area of development is Si-based power
device performance, which is limited in high power density and
high temperature environments. Thus, the next-generation power
electronic systems will require radical power-management solu-
tions based on new electronic materials. Recently, wide bandgap
semiconductors such as SiC and GaN have emerged as potential
alternatives to Si because of their ability to achieve a compara-
tively higher power density [1].
Devices made from these semiconductor compounds are opera-
ble at temperatures greater than 473 K, and potentially up to
573 K, which is higher than the present Si-based devices. Never-
theless, such temperatures are too high for the solders that are cur-
rently used [2]. Among the different materials currently used for
soldering, the Pb-rich solder (Pb–5 Sn) can possibly endure these
aforementioned high temperatures. However, the Pb-rich materi-
als have an inherent disadvantage in their toxicity. In fact, emerg-
ing regulations have demanded the elimination of Pb use in
electronic assemblies. Furthermore, the Pb-rich soldering materials
⇑ Corresponding author. Tel.: +81 561 71 7592.
E-mail address: toshi@mosk.tytlabs.co.jp (T. Satoh).
effectively release heat. This in turn leads to a fatigue-based
degradation induced by the stress accumulated from thermal
cyclic loading. Therefore, it has become imperative to develop a
bonding material that is Pb-free as well as able to endure high
temperatures.
Recently, with the advance of nanotechnology, Ag nanoparticles
have been studied as novel bonding materials [3–9], due to the fact
that the high surface energy available on the nanoscale offers an
advantageous, significantly lower sintering temperature than Ag’s
melting point (1236 K). As a quantitative example, it has been
reported that Ag nanoparticles with an average 20 nm diameter
can be sintered at 523 K to increase their size to >1 mm [10]. In
addition to these advantages, Ag displays the lowest electrical
resistivity and highest thermal conductivity among metals. Despite
these advantages, Ag is still not considered suitable for practical
applications because of its high cost and low resistivity towards
ion migration [11].
On the other hand, Cu is considerably cheaper than Ag while
possessing a similar electrical resistivity and thermal conductivity,
yet with a strong durability towards ion migration. With the added
nanoscale functionalities, Cu nanoparticles could be considered an
alternative bonding material. In our earlier study, we developed a
novel strategy to synthesize Cu nanoparticles capped with fatty
acids and amines, which obtained a high bonding strength even
at a low (573 K) processing temperature [12]. Although such nano-
particles generally require an additional high pressure to establish
strong bonding, high pressures are not desirable as part of the

http://dx.doi.org/10.1016/j.jallcom.2014.12.224
0925-8388/Ó 2015 Elsevier B.V. All rights reserved.
 T. Satoh, T. Ishizaki / Journal of Alloys and Compounds 629 (2015) 118–123 119

semiconductor device packaging process. Therefore, in recent

years, significant efforts have been made to realize pressure-free
bonding or low-pressure bonding [3,13–16].
Our research revealed that a thin Ni layer applied to the base
materials, such as on Cu and Al plates, enabled pressure-free bond-
ing of Cu nanoparticles [16]. The high bonding strength that
resulted from the insertion of a Ni layer was due to the increased
interfacial bonding strength between the Cu nanoparticle layer
and the base material as the Cu closely adhered to the Ni layer.
However, the insertion of this Ni layer only affected the interfacial
bonding strength, while the strength within the Cu nanoparticle
bonding layer is considered far lower than one with high pressure
applied during the bonding process. As the aforementioned bond-
ing of the Cu layer to the Ni layer likely resulted from the active
surface diffusion of Cu atoms from the Cu nanoparticles, mixing
Ni into the Cu nanoparticle bonding layer is expected to increase
bonding strength by promoting the diffusion of Cu atoms. Our
recent research demonstrated that mixing Ni or Ni-based alloy
nanoparticles into the Cu nanoparticle bonding layer improved
the bonding strength of pressure-free bonding [17,18].
Further, the formation of the Cu layer on the Ni layer is trig-
gered by the development of a NiO and CuO solid solution, with
the origin of both surface oxides accompanied by a Cu valence
Fig. 1. The shear strength of the Cu plates bonded using the mixed Cu–NiO
change, from the monovalent to the bivalent form [19]. The gener-
nanoparticles plotted relative to the NiO content.
ation of this solid solution facilitates the reduction of the surface
oxides, promoting surface diffusion. It is therefore expected that
adding NiO particles to the Cu nanoparticle bonding layer instead increasing NiO content in the mixture, reaching a maximum bond-
of the Ni or Ni-based alloy particles would also improve the pres- ing strength of 30.5 MPa at 1 wt% of NiO. After this point, the bond-
sure-free bonding strength. Therefore, we examined the mixing of ing strength decreased abruptly with increasing NiO concentration,
NiO nanoparticles (up to 10 wt%) with the Cu nanoparticles for lowering the bonding strength below the Cu nanoparticles alone
pressure-free bonding. In this article, we will report on the pres- once the NiO content was higher than 2 wt%. The observed range
sure-free bonding properties of mixed Cu–NiO nanoparticle layers. of NiO content that increased bonding strength was significantly
lower than that of the Ni and Ni-based alloy nanoparticles [17,18].
2. Materials and methods In this article, the bonding layer thickness is defined as an aver-
age thickness of both ends of the bonding layer in a cross-sectional
The Cu nanoparticles used in this work, surface-modified by using decanoic acid optical micrograph. Fig. 2 shows the thickness of the mixed Cu–
(CH3(CH2)8COOH) and decylamine (CH3(CH2)9NH2), were synthesized following our NiO nanoparticle bonding layer plotted against the NiO content
previously reported procedure [20], combined with commercial NiO nanoparticles
obtained from Sigma–Aldrich. The average particle sizes of the Cu and NiO nanopar-
in the mixture. For the low content of NiO up to 2 wt%, the thick-
ticles were 230 and 50 nm, respectively. After mixing the Cu and NiO nanoparticles, ness of the mixed Cu–NiO nanoparticle bonding layer was thinner
a mixed Cu–NiO nanoparticle paste was obtained by mixing a-terpineol (CH3(C6-
H8)C(CH3)2OH) and decanol (CH3(CH2)8CH2OH) with the nanoparticles by using a
planetary centrifugal mixer. 50 ll of each solvent was used per gram of the mixed
Cu–NiO nanoparticles. The NiO nanoparticle content in the Cu–NiO nanoparticle
mixture was varied between 0 and 10 wt%. The influence of the NiO nanoparticle
content on the printing properties of the mixed Cu–NiO nanoparticle paste was
insignificant.
Circular and rectangular Cu plates, with sizes of /5 mm  2 mm and
22  10  3 mm, respectively, were bonded using the mixed Cu–NiO nanoparticle
paste. A 40 nm thick Ni film was deposited by sputtering on each Cu plate as an
adhesive layer. A 150 lm thick Cu–NiO nanoparticle paste was applied to a /
5 mm region of the rectangular Cu plate’s Ni-coated surface by a bar-coating
method involving the use of a metal mask, and then the Ni-coated circular Cu plate
was placed on top of this paste. The stacked sample was then loaded into the fur-
nace and fired under a H2 atmosphere at 623 K for 300 s. No additional pressure
was applied to the bonding plane besides the weight of the circular Cu plate
(0.35 gf).
The sample’s bonding strength was examined by performing a shear test.
Procedure of the shear test was explained in elsewhere [16]. The bonding layer’s
structure was analyzed by scanning electron microscopy (SEM) and scanning trans-
mission electron microscopy-energy dispersive X-ray spectroscopy (STEM–EDS).
Accelerating voltages for SEM and STEM–EDS were 15 kV and 200 kV, respectively.

3. Results

Fig. 1 shows the sample bonding strength plotted relative to the

NiO content in the mixture. The addition of a small quantity of NiO
nanoparticles (0.05 wt%) in the bonding layer improved the
bonding strength compared to Cu nanoparticles without the NiO Fig. 2. Thickness of the mixed Cu–NiO nanoparticle bonding layer plotted against
nanoparticles. The bonding strength increased gradually with an the NiO content.
120 T. Satoh, T. Ishizaki / Journal of Alloys and Compounds 629 (2015) 118–123
than that of the Cu only bonding layer, and it had a gradually
increasing tendency with increasing NiO quantity. Because the
dependence of the thickness on the NiO content is opposite to that
of the bonding strength shown in Fig. 1, it is believed that the
bonding strength and bonding layer thickness have an inverse rela-
tionship with the NiO content.
Cross-sectional SEM images taken near the interface between
the mixed Cu–NiO nanoparticle bonding layer and the Cu base
plate are shown in Fig. 3. The Ni layer was so thin that it could
not be identified in the images. The bonding layer directly con-
nected to the base plate without producing any additional interfa-
cial phases in any of the interfaces. Additionally, structural defects
including cracks and micro-voids were observed inside all bonding
layers. Major cracks were observed in the mixed Cu–NiO bonding
layers of 0.01–1 wt% NiO content (Fig. 3(b), (c), and (d)). On the
other hand, the micro-voids were larger and more frequently
observed in the Cu only and Cu-10 wt% NiO bonding layers
(Fig. 3(a) and (e)) over the others. These results indicate that the
bonding layer exhibiting a higher bonding strength and decreased
thickness has a larger amount of cracks and lower amount of
micro-voids.
Fig. 4 shows the STEM image and EDS maps of the Cu-2 wt% NiO
nanoparticle bonding layer. The distribution of O was uniform,
with a limited dependence on morphology, as shown in Fig. 4(a)
Fig. 3. Cross-sectional SEM images near the interface between the mixed Cu–NiO nanoparticle bonding layer and the Cu base plate; the NiO contents are (a) 0, (b) 0.01, (c) 0.1,
(d) 1, and (e) 10 wt%.
and (b). This result indicates that there are few oxide phases in
the bonding layer. As shown in Fig. 4(c), Cu was distributed in all
regions where there was any sort of substance in the STEM image
(Fig. 4(a)). In contrast, the Ni segregated at the grain boundaries
and on the crystalline Cu surface without maintaining a particulate
shape, as shown in Fig. 4(d). Fig. 5 shows EDS spectra taken from
the grain boundary (point A) and the intragranular (point B) region
in Fig. 4(a). O was scarcely detected in each spectrum. On the other
hand, the intensity corresponding to Ni Ka at the grain boundary
region (Fig. 5(a)) was much greater than that at the intragranular
region where Ni was scarcely detected. Ni/Cu atomic ratios at the
grain boundary and the intragranular region calculated from the
EDS spectra were 0.040 and 0.0015, respectively. It is inferred that
the metallic state of Ni segregated at the grain boundaries and sur-
face of the crystalline Cu.
4. Discussion
The improved bonding strength and changes in the bonding
layer through mixing the NiO and Cu nanoparticles were described
in Section 3. The mechanism of this bonding strength improvement
will be discussed here.
The bonding strength increased as the bonding layer thickness
decreased, as described in Section 3. Therefore, the bonding
 T. Satoh, T. Ishizaki / Journal of Alloys and Compounds 629 (2015) 118–123
Fig. 4. (a) STEM image and EDS maps of the Cu-2 wt% NiO bonding layer for (b) O, (c) Cu, and (d) Ni.
strength was plotted against the thickness of the bonding layer in
Fig. 6. The previously described relationship between the bonding
strength and bonding layer thickness was confirmed. Since the Cu
nanoparticle bonding layer without any NiO particles follows the
same correlation that is indicated by a region enclosed with dashed
line in Fig. 6, the NiO nanoparticles contribute minimally to the
bonding strength.
The bonding layer displaying the higher bonding strength and
decreased thickness has a larger number of cracks and lower
amount of micro-voids, as shown in Fig. 3. The cracks are caused
by the bonding layer shrinkage associated with the sintering pro-
cess. In contrast, the decreased quantity of micro-voids originated
from the crystal growth of the Cu nanoparticles. It is therefore
likely that the sintering improved the bonding layer with the
higher bonding strength and lower thickness.
Next, the effect of the NiO nanoparticles mixed with the Cu
nanoparticles on the layer’s sintering behavior will be examined.
Sintering of the nanoparticle bonding layer generally starts with
the surface diffusion of metallic atoms originating in the nanopar-
ticles. However, the nanoparticles’ surface oxides inhibit an active
surface diffusion. Therefore, promoting a reduction of the surface
oxides stimulates the sintering. In the case of the Cu nanoparticle
bonding, reducing the Cu monovalent oxide phase (Cu2O) is con-
sidered important because its activation energy for reduction by
H2 is higher than that of CuO [21,22]. On the other hand, the metal-
lic state of Ni segregated at the grain boundaries and surface of the
crystalline Cu, as described in Section 3. Cu existed at the region
where Ni segregated as shown in Fig. 4(c), and the Ni/Cu atomic
ratio was 0.040 at the grain boundary region. This value does not
seem to be large enough to indicate that that there are any grain
121
boundary phases of metallic Ni itself, even if electron beam spread-
ing within the sample is considered. On the other hand, the Cu–Ni
system is isomorphous [23]. Ni is therefore considered to form a
Cu–Ni solid solution, although the existence of an extremely thin
Ni layer at the grain boundary cannot be denied. If this hypothesis
is correct, the Ni atoms originating from the NiO nanoparticles dif-
fused to the Cu nanoparticle surfaces in addition to alloying and
reducing. The NiO forms a solid solution with CuO rather than
Cu2O [24], and along with CuO, it is reduced more easily than
Cu2O [25–27]. Therefore, the alloying and reduction of the NiO
and Cu2O, described in Eqs. (1) and (2), were proposed in our pre-
vious article [19].
NiO þ xCu2 O ! NiðCux ÞO1þx þ xCu ð1Þ
NiðCux ÞO1þx þ ð1 þ xÞH2 ! NiðCux Þ þ ð1 þ xÞH2 O ð2Þ
When the Cu2O phase on the Cu nanoparticles is removed by these
reactions, the metallic Cu and Ni–Cu solid solution produced by
these reactions are expected to actively diffuse from the Cu nano-
particles, promoting the bonding layer sintering. The distribution
of Ni in the bonding layer, shown in Fig. 4(d), supports the above
model. Moreover, the effect of mixing the Ni and Ni-based alloy
nanoparticles with the Cu nanoparticles is expected to be caused
by the reactions in Eqs. (1) and (2) as well. Although the surface
oxide of the nanoparticles contributes to this reaction, the volume
ratio of the surface oxide to the nanoparticle would be small
[17,18]. In contrast, the entire volume of the NiO nanoparticles
mixed into the Cu nanoparticles could be involved in the reaction.
As a result, it is believed that the effective NiO nanoparticle content
122 T. Satoh, T. Ishizaki / Journal of Alloys and Compounds 629 (2015) 118–123
Fig. 5. EDS spectra taken from point (a) A and (b) B in Fig. 4(a).
is considerably smaller than that of Ni and Ni-based alloy
nanoparticles.
However, the diffusion coefficients of Cu and Ni in the Ni–Cu
solid solution are reportedly dependent on its composition. In
the literature, the diffusion coefficients of Cu and Ni in Ni-
78.5 at.% Cu at 623 K were 7.2  1024 m2/s and 2.2  1023 m2/s,
respectively; whereas those in Ni-13 at.% Cu at 623 K were
1.1  1026 m2/s and 1.8  1029 m2/s, respectively [28]. Since
the Cu–Ni system is isomorphous as previously described, these
diffusion coefficients indicate that the diffusion velocities of both
Cu and Ni in the Cu–Ni solid solution decrease as the Ni content
increases. Therefore, it is considered that an excess of NiO nanopar-
ticles mixed with the Cu nanoparticles inhibits sintering of the
bonding layer, even if the Cu2O phase at the Cu nanoparticle sur-
face is sufficiently removed.
The effect of mixing NiO nanoparticles with Cu nanoparticles on
the bonding strength is likely controlled by the balance between
the Cu nanoparticle’s surface oxide removal with the composition
of the Ni–Cu solid solution produced during the surface oxide
reduction process discussed above. In other words, increasing the
NiO content would increase the removal of surface oxides, promot-
ing sintering in the bonding layer; whereas it would also increase
the Ni concentration in the Ni–Cu solid solution, which inhibits
sintering. According to the aforementioned model, the removal of
Fig. 6. The shear strength of Cu plates bonded using the mixed Cu–NiO nanopar-
ticles plotted relative to bonding layer thickness.
Cu nanoparticle surface oxides begins with the reaction between
NiO and Cu2O. Thus, it is considered that the optimal NiO nanopar-
ticle content is affected by the particle size and dispersion, as these
affect the number of reaction sites. In addition, the volume ratio of
Cu2O in a Cu nanoparticle with its surface modified by organic mol-
ecules is expected to be small [12]. Therefore, a higher bonding
strength resulting from the addition of a small amount of NiO
nanoparticles is anticipated if the NiO nanoparticles are smaller
and uniformly dispersed.
5. Conclusions
Mixtures of Cu and NiO nanoparticles were examined in order
to improve the pressure-free nanoparticle bonding, with the
obtained results discussed below.
Mixing NiO nanoparticles with Cu nanoparticles improved the
bonding strength. The NiO content that showed a higher bonding
strength than Cu nanoparticles alone was between 0.005 and
2 wt%. The bonding strength and thickness of the bonding layer
showed an inverse relationship with the NiO content. The bonding
strength increased as the thickness of the bonding layer decreased,
and the relationship between these two was approximately
expressed by a power function, independent of the NiO concentra-
tion. The morphology of the mixed Cu–NiO nanoparticle bonding
layer became denser as the bonding layer decreased in thickness,
with the bonding strength increased. The Ni in the bonding layer
became segregated at the surfaces and grain boundaries of crystal-
line Cu grains in the form of a metallic Cu–Ni alloy.
These results reveal the effect of improved bonding strength by
adding NiO nanoparticles to the Cu nanoparticle bonding layer. It is
suggested that this reinforcing mechanism of the bonding layer
begins with the formation of a NiO–CuO solid solution, originating
between the NiO nanoparticles and surface oxides of the Cu nano-
particles, followed by a subsequent removal of surface oxides and
then active surface diffusion.
Acknowledgement
The authors would like to thank Hisano Sugano and Asami
Nishikawa for their assistance during the experimental work.
 T. Satoh, T. Ishizaki / Journal of Alloys and Compounds 629 (2015) 118–123 123

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