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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 23989
www.rsc.org/materials PAPER
Antioxidative effect of lactic acid-stabilized copper nanoparticles prepared in
aqueous solution
Dunying Deng, Yuanrong Cheng, Yunxia Jin, Tianke Qi and Fei Xiao*
Received 29th July 2012, Accepted 25th September 2012
Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F

DOI: 10.1039/c2jm35041f

Copper nanoparticles are an alternative for the currently used silver and gold nanoparticles in inkjet
printing of conductive patterns because of the low cost and high electrical conductivity. However, a
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serious impediment to using copper nanoparticles for conductive inks is their spontaneous oxidation.
This paper describes a simple, large-scale and high-throughput (0.2 M) process for the synthesis of
copper nanoparticles in aqueous solution at room temperature in a short reaction period. The well-
dispersed antioxidative copper pastes were prepared by dispersing the nanoparticles in an ethanol
solution of lactic acid, and then depositing on glass slides. The resistivity of the conductive copper film
was 14.0
4.5 mU cm after annealing at 200  C for 30 min in nitrogen, which was about eight times of
the resistivity of bulk copper (1.7 mU cm). The copper nanoparticles and films were characterized by
TEM, UV-vis, SEM, XRD and XPS. Lactic acid-stabilized copper nanoparticles showed relatively
better disperse stability and resistance to oxidation than the other carboxylic acids. Furthermore, the
copper film after annealing at 200  C for 30 min in nitrogen showed antioxidative characteristics. It was
experimentally proven that lactic acid could react with the copper oxides surrounding copper
nanoparticles to form copper lactate, which was then reduced to copper in the annealing process.

Introduction undesirable oxidation.6–9 However, most of the synthetic

Printed electronics have become a research focus due to the
distinct characteristics such as small size, flexibility, thinness, and
portability. It has shown great potential in daily use such as
RFID tags, smart cards and displays. Silver inks, the currently
favoured inkjet printable metal inks, have been developed
recently in order to manufacture low-cost disposable electronics
such as smart packaging, RFID tags, and digital calendars.
Different forms of silver inks have been used for inkjet printing
conductive traces, such as the solution of organosilver
compounds which can be reduced to metal at low temperature
and the suspension of silver nanoparticles which can melt at a
much lower temperature than the melting point of bulk mate-
rial.1–4 However, owing to the electromigration at relatively high
temperature and humidity conditions as well as cost-benefit
issues, silver as a conductive material cannot be used on a large
scale.5
Printable copper inks are a desirable alternative because of
their good conductivity, low cost and reduced electromigration
effect. Thus far, copper nanoparticles for conductive inks have
been primarily synthesized in organic solvents with capping
agents in an inert atmosphere to prevent aggregation and
Department of Materials Science, Fudan University, 220 Handan Road,
Shanghai 200433, P. R. China. E-mail: feixiao@fudan.edu.cn; Fax: +86-
21-65103056; Tel: +86-21-65642110
methods of copper nanoparticles are not economically feasible
because of the low throughput, poor scalability and serious
agglomeration. Besides, it is very difficult to obtain pure copper
nanoparticles with the conventional reduction method, because
the reduction of Cu salt tends to stop at the Cu2O stage when
water molecules exist in the reaction medium.10 At the same time,
the synthesized copper nanoparticles can easily be oxidized in air.
The presence of copper oxides will increase the sintering
temperature of nanoparticles and reduce the electrical conduc-
tivity. To solve the problem, which in general is based on mini-
mizing the exposure of the copper nanoparticles to oxygen, a
protective layer such as carbon-based materials (carbon and
graphene), surfactants (PVP, C6–C18 alkanethiols) and metals
(Cu–Ag core–shell) is formed on the surface of the particles.8 In
addition, in order to avoid the oxidation during post-heat
treatment, the copper film is annealed in a reductive atmosphere
of carboxylic acid and alcohol with nitrogen as a carrier gas.11,12
This makes the annealing process more complicated. Therefore,
it is critical to develop an economically feasible process to
produce copper nanoparticles on a large scale and avoid oxida-
tion in the post-processing.
The synthesis of copper nanoparticles in high concentration
using hypophosphite as reductant and PVP or PVP/CTAB as
capping agent have been reported previously.13–15 Large amounts
of ethylene glycol were used as solvent in the process and the
reaction temperature was higher than 90  C. As water is a cost

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 23989–23995 | 23989

effective and environmental friendly solvent, to prepare copper
nanoparticles in aqueous solution is very attractive. However,
the obstacle for the aqueous synthesis is the enhanced surface
oxidation of the copper nanoparticles. Copper nanoparticles in
high concentration have been synthesized by the reduction of
cupric chloride with hydrazine in aqueous CTAB solution.16 The
copper nanoparticles were capped by a mass of CTAB molecules
that TGA showed 70% weight losses below 600  C. Besides, the
XRD results showed that the copper nanoparticles were easily
oxidized after sintering. Recently, the poly(allylamine)-stabilized
colloidal copper nanoparticles and polyacrylate-assisted copper
nanoparticles were synthesized in aqueous solution, respec-
tively.17,18 However, further research about the oxidation of the
Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F
copper nanoparticles has rarely been reported.
In this study, a simple, large-scale and high-throughput
process for the synthesis of copper nanoparticles in aqueous
solution was developed by chemical reduction of copper salts.
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The copper nanoparticles were redispersed into an ethanol
solution of carboxylic acids, and then deposited on glass slides.
The antioxidative conductive copper films were obtained after
sintering in nitrogen. The mechanism of lactic acid on the
reduction of copper oxide was experimentally studied.
Experimental
Materials
Copper(II) acetate monohydrate, cetyltrimethylammonium
bromides (CTAB), polyvinylpyrrolidone (PVP, K-30), hydrazine
hydrate solution (50%), acetic acid, propionic acid, oleic acid,
glycolic acid, lactic acid and ammonia water were purchased
from Sinopharma Chemical Reagent Co., Ltd. All chemicals
were used as received without further purification.
Characterization
Thermogravimetric analysis (TGA) was carried out using a
thermal gravimetric analysis instrument (SHIMAZU, DTG-
60H) with a heating rate of 10  C min1 in nitrogen. UV-vis
absorption spectra were recorded on a Hitachi U-4100 spectro-
photometer. TEM were performed on a Hitachi H600 trans-
mission electron microscope. The crystal structures were
determined by X-ray diffraction (XRD) using a Rigaku D/max-
rB advanced X-ray diffractometer with Cu Ka radiation. Fourier
transform infrared (FT-IR) spectra were recorded on a Nicolet
Nenus 470 FTIR spectrophotometer operating at a resolution of
4 cm1. X-ray photoelectron spectroscopy (XPS) was recorded
on a Kratos axis ultra DLD photoelectron spectrometer using Al
Ka X-ray as the excitation source. The microstructure of the
sintered copper film was analyzed using a field-emission scanning
electron microscope (JEOL, JEM-6701F). The thickness of the
film was measured using a surface profiler (Tencor instruments,
alpha-step 200). The resistivity of the copper film was measured
by using a Shanghai Qianfeng SB100A/2 four-point probe meter
and calculated by the following equation:19
p V
r¼  t
ln 2 I
where I, V, and t represent the current, voltage and thickness of
film, respectively.
23990 | J. Mater. Chem., 2012, 22, 23989–23995
View Article Online
Synthesis of copper nanoparticles
Copper nanoparticles were synthesized by chemical reduction of
copper ions in aqueous solution at room temperature in nitrogen.
Copper acetate monohydrate (0.1 mol), CTAB (13 mmol) and
PVP (0.4–1.0 mmol) were dissolved in 500 mL of deionized
water. The solution was stirred with a magnetic stirrer for 20 min
to ensure that the copper acetate monohydrate, CTAB and PVP
were dissolved completely. The pH of the solution was adjusted
to 10.0 by adding ammonia water with continuous stirring.
Hydrazine hydrate solution (0.2 mol) was added into the solu-
tion, the color of the solution turned from deep blue to brown
within 3–5 min, indicating the formation of copper nano-
particles. 4.8 g of copper nanoparticles were obtained after
centrifugation, washing with methanol and drying under vacuum
for 2 h.
Preparation of copper films
Copper nanoparticles obtained above were dispersed in ethanol
by ultrasonication for 1 h to prepare the copper nanoparticle
pastes (10 wt%). Carboxylic acids were added into the solution in
3 wt% to assist the redispersion. The copper pastes were depos-
ited on glass slides by a drop-coating method, dried under
vacuum for 1 h, and then annealed in nitrogen at a suitable
temperature for 30 min. The film thickness was controlled by
dropping a fixed amount of copper pastes on the glass slides
within a fixed area.
Results and discussion
Synthesis and characterization of copper nanoparticles
By using PVP and CTAB as the double capping agents, copper
nanoparticles were synthesized in aqueous solutions on a large-
scale (500 ml) and with high-throughput (0.2 M) at room
temperature in a short reaction period. In the case of using
CTAB or PVP as the only protective agent, visible particles were
generated and deposited on the bottom of reactor. The homo-
geneous and stable brown solutions were obtained only when
both CTAB and PVP were used. It was reported that the
coupling interaction between the two surfactants made the
copper nanoparticles suspended in the solution well.15 We believe
that the electrostatic repulsion of the cationic CTAB and the
steric hindrance of PVP restrict the growth of copper nano-
particles cooperatively. Thermal gravimetric analysis (TGA)
reveals that the amount of the adsorbed capping agents on the
synthesized copper nanoparticles is about 16% as shown in
Fig. 1a. After washing with methanol and drying under vacuum,
the copper nanoparticles show sharp weight losses in the range of
50–150  C and 250–400  C (Fig. 1b), which are related to the
evaporation of residual solvent and the decomposition of
capping agents, respectively. The amount of the residual capping
agent and solvent on the copper nanoparticles is approximately
6.5% by weight estimated by TGA. Thus, 4.8 g of copper
nanoparticles prepared from 0.10 moles of copper acetate
corresponds to a reaction yield of 70%.
UV-vis absorption peaks are sensitive to the size of metal
nanoparticles. The absorption bands for copper nanoparticles
have been reported to be in the range of 550–600 nm.20 Fig. 2
This journal is ª The Royal Society of Chemistry 2012
 View Article Online
Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F

Fig. 1 TGA curves of copper nanoparticles obtained in nitrogen. (a) As

prepared, (b) after washing.
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Fig. 3 TEM images and particle size distribution of copper nano-

particles stabilized with different amounts of PVP. (a) 0.4 mmol L1, (b)
1.0 mmol L1.

methanol, a tiny peak indexed as the (111) diffraction of Cu2O

appeared, associated with slight oxidation of metallic copper.
Generally, due to the high percentage of surface area, nano-
particles are readily oxidized in air. Because of the protection of
both PVP and CTAB, the freshly prepared copper nanoparticles
in this work show a significantly oxide-free, stable FCC copper
phase. However, slight oxidation occurs on the surface of copper
nanoparticles after most of PVP and CTAB are removed by
washing with methanol.
Fig. 2 UV-vis spectra of copper nanoparticles stabilized with different
amount of PVP. (a) 0.4 mmol L1, (b) 1.0 mmol L1.
Characterization of copper nano pastes and films
After removal of the protecting agent (PVP/CTAB), the
displays the UV-vis spectra of colloidal copper nanoparticles synthesized copper nanoparticles are easily oxidized. Thus, the
from the original reaction mixture with different amounts of inkjet-printed copper interconnectors have to be sintered in
PVP. It can be seen that the position of the absorption band various reductive atmospheres.11,12 To simplify the preparation
changes with the amount of PVP used. When the concentration of nano copper pastes and the post-heat process of the printed
of PVP is increased from 0.4 to 1.0 mmol L1, the absorption copper films, carboxylic acids, such as glycolic acid and lactic
peak is slightly shifted from 587 to 578 nm, suggesting the acid, are employed as the protecting and reducing agent in the
decrease of the nanoparticle size. process of copper nanoparticles redispersion. Carboxylic acids
TEM images further confirm the relationship between the size
of copper nanoparticles and the amount of PVP used. As shown
in Fig. 3, the size of particles is about 20–30 nm when the PVP
concentration is 0.4 mmol L1. As the PVP concentration is
increased to 1.0 mmol L1, the size of the particles is less than
10 nm and the size distribution is more uniform. Therefore, the
size and the uniformity of copper nanoparticles can be improved
by increasing the concentration of PVP.
The crystallographic characteristics of the copper nano-
particles was analyzed by XRD. Fig. 4 displays the XRD
patterns of the copper nanoparticles with 2q values between 25
and 80 . The freshly prepared copper nanoparticles without
washing show three characteristic peaks at 43.2 , 50.3 and 74.1
for the marked indices of (111), (200) and (220), respectively
(Fig. 4a). These characteristic peaks confirm the formation of a
face-centered cubic (FCC) copper phase without significant Fig. 4 X-ray diffraction patterns of copper nanoparticles. (a) As
oxides or other impurity phases. However, after washing with prepared, (b) washed by methanol.

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 23989–23995 | 23991
 View Article Online

can react with copper oxides to form organic copper salts which
will be reduced into elemental copper at a certain temperature.11
Carboxylic acids can also bind on the surface of copper nano-
particles to prevent them from oxidation.10
The as prepared copper nanoparticles were washed and
dispersed in ethanol by ultrasonication to prepare the copper
nanoparticles pastes in a concentration of 10 wt%. Carboxylic
acids (3 wt%) were added into the pastes to assist the redis-
persion. When acetic acid and propionic acid were used, the
copper nanoparticles pastes completely turned into green solu-
tion. In the case of oleic acid, the color of the pastes turned
greenish. There was no obvious color change during the redis-
Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F

persion of copper nanoparticles in the presence of glycolic acid

and lactic acid. The greenish color of the pastes implies the
formation of copper carboxylate. Although the acidity of gly-
colic acid and lactic acid are stronger than that of acetic acid,
propionic acid and oleic acid, the reactivity of copper nano-
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particles with different carboxylic acids in ethanol are not in the

order of the acidity. According to the color change of the pastes,
almost all copper nanoparticles are reacted and dissolved in the
ethanol solution of acetic acid and propionic acid, only a small
amount of copper nanoparticles are reacted with oleic acid, and
the copper nanoparticles are stable in the ethanol solution of
glycolic acid and lactic acid. We think that the solubility of the
copper carboxylates in ethanol plays an important role here.
Copper glycolate and copper lactate are difficult to dissolve in
ethanol, while copper acetate and copper propionate are soluble
in ethanol and the solubility of copper oleate is in between. The
small amounts of copper oxides on copper nanoparticles can
react with carboxylic acids to form the corresponding copper
carboxylate. If the copper carboxylate is soluble in the solvent,
then the freshly formed copper surface is easily oxidized to
copper oxides, which can further react with the carboxylic acids
to form the copper carboxylate. Eventually, the copper nano-
particles will be consumed. On the contrary, if the copper
carboxylate is not soluble in the solvent, it will coat on the
surface of the copper nanoparticles, thus protect the copper
nanoparticle from further oxidation. In addition to the solubility Fig. 5 TEM images and particle size distribution of copper nanoparticle
difference of the copper carboxylate, both glycolic acid and lactic pastes in the presence of different acids. (a) None, (b) oleic acid, (c)
acid have an additional hydroxyl group, which increase the glycolic acid, (d) lactic acid.
bonding ability of acids on the surface of copper nanoparticles to
further stabilize the copper nanoparticles from oxidation. temperature, further antioxidation experiments are focused on
The TEM images of the copper nanoparticles redispersed in the lactic acid-stabilized copper nanoparticles. The copper films
the ethanol solution of carboxylic acids are shown in Fig. 5. In were obtained by depositing the copper nano pastes on glass
the absence of carboxylic acids, the maximum diameter of the slides, drying under vacuum, and then annealing at a certain
dispersed copper nanoparticles reaches 50 nm with a wide size temperature. Fig. 6 shows the XRD patterns of copper films
distribution (Fig. 5a). In the presence of oleic acid, most of the before and after annealing at 200  C in nitrogen. There are the
copper nanoparticles are dispersed well in ethanol and parts of (111) diffraction of Cu2O in both the non-annealed copper paste
the copper nanoparticles aggregate (Fig. 5b). It has been reported and the annealed copper film without lactic acid (Fig. 6a and c).
that the oleic acid can be used as the capping agent to prevent the In the presence of lactic acid, the (111) diffraction of Cu2O
nanoparticles from aggregating.10 In the case of glycolic acid, disappears in the copper paste and film as shown in Fig. 6b and d.
most of the copper nanoparticles are gathered together, and only As discussed above, the Cu2O or CuO surrounding copper
the indistinct boundaries can be seen as shown in Fig. 5c. The nanoparticles can react with lactic acid forming copper lactate
copper nanoparticles are dispersed well in the ethanol solution of that is coated on the surface of copper nanoparticles in the
lactic acid with a diameter less than 30 nm and a narrow size redispersing process, and then reduced to copper in the annealing
distribution as shown in Fig. 5d. It seems that oleic acid and process.
lactic acid show a better dispersion effect than the other acids. Because the surface oxide layer is amorphous and small in
Considering that lactic acid has a relatively low boiling point volume, XRD may not be suitable for analyzing the trace surface
and can be easily removed from the copper surface at moderate oxide. For more in-depth investigation on whether oxide layer

23992 | J. Mater. Chem., 2012, 22, 23989–23995 This journal is ª The Royal Society of Chemistry 2012

Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F
Fig. 6 XRD patterns of copper pastes (before annealing) and films (after
annealing). (a) Copper paste without lactic acid, (b) copper paste with lactic
acid, (c) copper film without lactic acid, (d) copper film with lactic acid.
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was present on the surface of the annealed copper films, XPS
analysis was performed. Fig. 7 shows the Cu2p3/2 spectrum with
peak fitting of the copper films after annealing at 200  C for 30
min in nitrogen. The insets show the Cu2p doublet spectrum. The
obvious peak around 934.8 eV is attributed to CuO (Fig. 7a),
while the peak fitting of the copper film with lactic acid does not
show any indications for the presence of CuO (Fig. 7b). The Cu
2p3/2 binding energy for pure Cu, Cu2O and CuO is 932.1, 932.6
and 934.6 eV, respectively.6
To understand the effect of lactic acid in the preparation of the
copper film, the following experiments were conducted. A certain
amount of lactic acid was added to the copper nanoparticles that
had been oxidized as shown in Fig. 9a. A light blue lactic acid
solution was obtained after ultrasonication and centrifugation.
Fig. 8 shows the FT-IR spectrum of the light blue lactic acid
solution. The peaks at 1607 cm1 and 1410 cm1 are attributed
to the asymmetric and symmetric stretching of the conjugate
carboxylate. The carbonyl stretching of the free lactic acid is at
1750 cm1. The light blue lactic acid solution was deposited
on glass slides and sintered in nitrogen for 30 min at 200  C and
250  C, respectively. The XRD patterns of the obtained films are
shown in Fig. 9. Compared with Fig. 9a, the (111) diffraction of
Cu2O disappears and only the diffractions of copper exist in
Fig. 7 Peak fitting of the Cu2p3/2 spectrum of copper film after
annealing at 200  C for 30 min. The insets show the Cu2p doublet
spectrum. (a) Without lactic acid, (b) with lactic acid.
This journal is ª The Royal Society of Chemistry 2012
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Fig. 8 FT-IR spectrum of the blue solution of lactic acid with the
oxidized copper nanoparticles.
Fig. 9b and c. The results confirm that lactic acid reacts with the
copper oxides surrounding copper nanoparticles to form copper
lactate that is then reduced to copper in the annealing process as
described by the following equations:
2CH3CHOHCOOH + CuO / Cu(CH3CHOHCOO)2 + H2O
Cu(CH3CHOHCOO)2 / Cu + 2CO2 + H2 + 2CH3CHO + ..
Electrical properties of the sintered copper films
The electrical properties of the copper films are further studied.
Fig. 10 shows the resistivity of the films after annealing in
nitrogen for 30 min at different temperatures in the absence/
presence of lactic acid, respectively. In the absence of lactic acid,
the resistivity of the film decreases from 7800
500 mU cm to 600

100 mU cm as the temperature increases from 150  C to 300  C.
The decrease of resistivity with the increase of sintering
temperature may be due to the sintering of copper nanoparticles
after decomposition of the stabilizers. However, the resistivity of
the film annealed at 350  C cannot be measured and the surface
of film looks black, probably due to the oxidation of copper
nanoparticles at high temperature. The SEM images of the film
sintered at different temperatures in Fig. 11 confirm the sintering
of the nanoparticles at elevated temperatures.
Fig. 9 XRD pattern of the reaction products of lactic acid and the
oxidized copper nanoparticles. (a) Oxidized copper nanoparticles, (b)
sintered at 200  C, (c) sintered at 250  C.
J. Mater. Chem., 2012, 22, 23989–23995 | 23993

Published on 26 September 2012 on http://pubs.rsc.org | doi:10.1039/C2JM35041F
Fig. 10 Resistivity of the film sintered at different temperatures. (a)
Without lactic acid, (b) with lactic acid.
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Fig. 11 SEM images of microstructure of the films without lactic acid
annealed at different temperature. (a) 150, (b) 180, (c) 200, (d) 250, (e)
300, (f) 350  C.
In the presence of lactic acid, as the sintering temperature
increases from 150  C to 200  C, the resistivity decreases sharply
from (6.55
1.0)  105 mU cm to 14.0
4.5 mU cm, indicating
that lactic acid is removed and copper lactate is reduced to
copper. The electrical conductivity of the copper film obtained in
the research is about 12% of the conductivity of bulk copper,
which is comparable with the previous reported values 11 mU
cm 13 and 17 mU cm.21 The conductive paths between the nano-
particles have been established by the formation of inter-particle
necking, thus, the conductivity of the copper film remains nearly
unchanged at higher sintering temperatures. The inter-particle
necking formation is confirmed by SEM images of the film
surface after heat treatment at different temperatures as shown in
Fig. 12. After annealing at 150  C, the copper nanoparticles are
still surrounded by the organics. Most of the organics are
removed when annealed at 200  C and the nanoparticles start to
23994 | J. Mater. Chem., 2012, 22, 23989–23995
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Fig. 12 SEM images of microstructure of the film with lactic acid
annealed at different temperature. (a) 200  C (cross-section), (b) 150, (c)
180, (d) 200, (e) 250, (f) 300  C.
be sintered together. In contrast, significant inter-particle sin-
tering is observed at 250  C, and most of the particles are con-
nected with each other. At 300  C, all the nanoparticles are fused
together to form the conductive network throughout the entire
film. The resistivity difference between the film without and with
lactic acid is significant, which is mainly due to the antioxidation
effect and the low decomposition temperature of lactic acid. The
microstructure of the film cross-section reveals that the film is
composed of closely packed particles as shown in Fig. 11a. The
thickness of the film is about 20
1.5 mm measured by surface
profiler.
Conclusions
A simple, large-scale and high-throughput (0.2 M) process for
the synthesis of copper nanoparticles was developed in aqueous
solution at room temperature in a short reaction period. Mon-
odispersed spherical copper nanoparticles with a size less than
10 nm were synthesized in 70% yield, and the particles size
depended on the PVP amount. The antioxidative and well-
dispersed conductive copper pastes were prepared by dispersing
the copper nanoparticles in an ethanol solution of lactic acid. The
conductive copper films were obtained by depositing the copper
nano pastes on glass slides, drying and annealing at proper
temperatures. The resistivity of the conductive copper film was
14.0
4.5 mU cm after annealing at 200  C for 30 min in nitrogen.
We experimentally proved that lactic acid can react with the
copper oxides surrounding copper nanoparticles to form copper
lactate, which is then reduced to copper in the annealing process.
In addition to the potential application in printed electronics
industry, the copper nanoparticles pastes could also be used in
This journal is ª The Royal Society of Chemistry 2012

Cu-to-Cu joining for electronic component assembly instead of
soldering.
Acknowledgements
This study was supported by National Science and Technology
Major Project with Contract nos. 2009ZX02038 and
2011ZX02602.
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