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Antioxidative Effect of Lactic Acid-Stabilized Copper Nanoparticles Prepared
Antioxidative Effect of Lactic Acid-Stabilized Copper Nanoparticles Prepared
Antioxidative Effect of Lactic Acid-Stabilized Copper Nanoparticles Prepared
aqueous solution
Dunying Deng, Yuanrong Cheng, Yunxia Jin, Tianke Qi and Fei Xiao*
Received 29th July 2012, Accepted 25th September 2012
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
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.
This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 23989–23995 | 23989
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effective and environmental friendly solvent, to prepare copper Synthesis of copper nanoparticles
nanoparticles in aqueous solution is very attractive. However,
Copper nanoparticles were synthesized by chemical reduction of
the obstacle for the aqueous synthesis is the enhanced surface
copper ions in aqueous solution at room temperature in nitrogen.
oxidation of the copper nanoparticles. Copper nanoparticles in
Copper acetate monohydrate (0.1 mol), CTAB (13 mmol) and
high concentration have been synthesized by the reduction of
PVP (0.4–1.0 mmol) were dissolved in 500 mL of deionized
cupric chloride with hydrazine in aqueous CTAB solution.16 The
water. The solution was stirred with a magnetic stirrer for 20 min
copper nanoparticles were capped by a mass of CTAB molecules
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23990 | J. Mater. Chem., 2012, 22, 23989–23995 This journal is ª The Royal Society of Chemistry 2012
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This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 23989–23995 | 23991
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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
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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-
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-
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. Downloaded by UNIVERSIDAD SAO PAULO on 7/17/2018 7:14:11 PM. View Article Online
Fig. 6 XRD patterns of copper pastes (before annealing) and films (after Fig. 8 FT-IR spectrum of the blue solution of lactic acid with the
annealing). (a) Copper paste without lactic acid, (b) copper paste with lactic oxidized copper nanoparticles.
acid, (c) copper film without lactic acid, (d) copper film with lactic acid.
Fig. 9b and c. The results confirm that lactic acid reacts with the
was present on the surface of the annealed copper films, XPS
copper oxides surrounding copper nanoparticles to form copper
analysis was performed. Fig. 7 shows the Cu2p3/2 spectrum with
lactate that is then reduced to copper in the annealing process as
peak fitting of the copper films after annealing at 200 C for 30
described by the following equations:
min in nitrogen. The insets show the Cu2p doublet spectrum. The
obvious peak around 934.8 eV is attributed to CuO (Fig. 7a),
2CH3CHOHCOOH + CuO / Cu(CH3CHOHCOO)2 + H2O
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 Cu(CH3CHOHCOO)2 / Cu + 2CO2 + H2 + 2CH3CHO + ..
2p3/2 binding energy for pure Cu, Cu2O and CuO is 932.1, 932.6
and 934.6 eV, respectively.6 Electrical properties of the sintered copper films
To understand the effect of lactic acid in the preparation of the
copper film, the following experiments were conducted. A certain The electrical properties of the copper films are further studied.
amount of lactic acid was added to the copper nanoparticles that Fig. 10 shows the resistivity of the films after annealing in
had been oxidized as shown in Fig. 9a. A light blue lactic acid nitrogen for 30 min at different temperatures in the absence/
solution was obtained after ultrasonication and centrifugation. presence of lactic acid, respectively. In the absence of lactic acid,
Fig. 8 shows the FT-IR spectrum of the light blue lactic acid the resistivity of the film decreases from 7800 500 mU cm to 600
solution. The peaks at 1607 cm1 and 1410 cm1 are attributed 100 mU cm as the temperature increases from 150 C to 300 C.
to the asymmetric and symmetric stretching of the conjugate The decrease of resistivity with the increase of sintering
carboxylate. The carbonyl stretching of the free lactic acid is at temperature may be due to the sintering of copper nanoparticles
1750 cm1. The light blue lactic acid solution was deposited after decomposition of the stabilizers. However, the resistivity of
on glass slides and sintered in nitrogen for 30 min at 200 C and the film annealed at 350 C cannot be measured and the surface
250 C, respectively. The XRD patterns of the obtained films are of film looks black, probably due to the oxidation of copper
shown in Fig. 9. Compared with Fig. 9a, the (111) diffraction of nanoparticles at high temperature. The SEM images of the film
Cu2O disappears and only the diffractions of copper exist in sintered at different temperatures in Fig. 11 confirm the sintering
of the nanoparticles at elevated temperatures.
Fig. 7 Peak fitting of the Cu2p3/2 spectrum of copper film after Fig. 9 XRD pattern of the reaction products of lactic acid and the
annealing at 200 C for 30 min. The insets show the Cu2p doublet oxidized copper nanoparticles. (a) Oxidized copper nanoparticles, (b)
spectrum. (a) Without lactic acid, (b) with lactic acid. sintered at 200 C, (c) sintered at 250 C.
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Cu-to-Cu joining for electronic component assembly instead of 8 S. Magdassi, M. Grouchko and A. Kamyshny, Materials, 2010, 3,
soldering. 4626.
9 V. Engels, F. Benaskar, D. A. Jefferson, B. F. G. Johnson and
A. E. H. Wheatley, Dalton Trans., 2010, 39, 6496.
Acknowledgements 10 J. Yang, Y. Zhou, T. Okamoto, T. Bessho, S. Satake and M. Okido,
Chem. Lett., 2006, 35, 1190.
This study was supported by National Science and Technology 11 K. Woo, Y. Kim, B. Lee, J. Kim and J. Moon, ACS Appl. Mater.
Major Project with Contract nos. 2009ZX02038 and Interfaces, 2011, 3, 2377.
12 I. Kim and J. Kim, J. Appl. Phys., 2010, 108, 102807.
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This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 23989–23995 | 23995