3746 Langmuir 2005, 21, 3746-3748

Large-Scale Synthesis of High-Quality Ultralong Copper

Nanowires
Yu Chang, Mei Ling Lye, and Hua Chun Zeng*
Department of Chemical and Biomolecular Engineering, Faculty of Engineering,
National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260
Received January 25, 2005. In Final Form: March 11, 2005

The present difficulties in synthesis of one-dimensional copper are short length, nonlinear morphology,
polydispersivity, poor crystallinity, low yield, and process complexity. In this work, we demonstrate that
high-quality ultralong copper nanowires (90-120 nm in diameter, 40-50 µm in length; aspect ratio
>350-450) can be synthesized in large scale with a facile aqueous reduction route at low cost. The prepared
copper nanowires can also be used as starting solid precursor for fabrication of polycrystalline oxide nanotubes
via direct oxidation in air.

Copper is one of the most important metals in modern can be synthesized in large scale with a facile aqueous
technologies.1,2 For future bottom-up nanotechnology reduction route at low temperatures.
(e.g., nano-optoelectronic industry), as a first step, fab- In each synthesis, 20-30 mL of NaOH (3.5-15 M) and
rication of one-dimensional (1D) nanomaterials of copper 0.5-1.0 mL of Cu(NO3)2 (0.10 M) aqueous solution were
(wires/cables/rods) has received considerable attention in added to a glass reactor (capacity 50 mL). Varying amounts
recent years, and a number of methods have been of ethylenediamine (EDA; 0.050-2.0 mL; 99 wt %) and
available, which include electrochemical reactions,3-8 hydrazine (0.020-1.0 mL; 35 wt %) were also added
vapor depositions,9,10 soft and hard template processes,11-13 sequentially, followed by a thorough mixing of all reagents.
reverse micellar systems,14-17 etc.18,19 Although the sig- The reactor was then placed in a water bath with
nificant research endeavor has been devoted, there is still temperature control over 25-100 °C (optimized at 60 °C)
lack of effective methods for large-scale production of high- for 15 min to 15 h; copper products were washed and
quality nanostructured copper, or metal nanowires in harvested with centrifugation-redispersion cycles and
general, with precise morphological control. Major syn- stored in a water-hydrazine solution to prevent oxidation.
thetic difficulties encountered in this area are short length, Further details on the synthesis can be found in Sup-
nonlinear morphology, polydispersivity, poor crystallinity, porting Information (SI-1). The crystallographic structure
low yield, and process complexity.3-19 Herein, we dem- of products was determined with X-ray diffraction (XRD;
onstrate for the first time that high-quality ultralong Shimadzu XRD-6000, Cu KR). The spatial, morphological,
copper nanowires (all free-standing: 90-120 nm in and compositional investigations were carried out with
diameter, 40-50 µm in length; aspect ratio >350-450) scanning electron microscopy and energy-dispersive X-ray
spectroscopy (SEM/EDX; JSM-5600LV), field-emission
SEM (FESEM/EDX; JSM-6700F), transmission electron
(1) Joseph, G. Copper: Its Trade, Manufacture, Use, and Environ-
mental Status; ASM International: Materials Park, OH, 1999; pp 331- microscopy and selected area electron diffraction (TEM/
371. SAED; JEM-2010F), high-resolution TEM (HRTEM/EDX;
(2) Yong, C.; Zhang, B. C.; Seet, C. S.; See, A.; Chan, L.; Sudijono, JEM 3010, 300 kV), and X-ray photoelectron spectroscopy
J.; Liew, S. L.; Tung, C.-H.; Zeng, H. C. J. Phys. Chem. B 2002, 106, (XPS; AXIS-HSi, Kratos Analytical).20
12366-12368.
(3) Molares, M. E. T.; Buschmann, V.; Dobrev, D.; Neumann, R.; The formation of metallic copper in this work is based
Scholz, R.; Schuchert, I. U.; Vetter, J. Adv. Mater. 2001, 13, 62-65. on the following redox reaction under the basic condition.
(4) Gao, T.; Meng, G.; Wang, Y.; Sun, S.; Zhang, L. J. Phys.: Condens.
Matter 2002, 14, 355-363.
(5) Gillingham, D. M.; Müller, C.; Bland, J. A. C. J. Phys.: Condens. 2Cu2+ + N2H4 + 4OH- f 2Cu + N2 + 4H2O (1)
Matter 2003, 15, L291-L296.
(6) Pang, Y. T.; Meng, G. W.; Zhang, Y.; Fang, Q.; Zhang, L. D. Appl.
Phys. A 2003, 76, 533-536.
(7) Konishi, Y.; Motoyama, M.; Matsushima, H.; Fukunaka, Y.; Ishii, Figure 1 shows some FESEM and TEM images of copper
R.; Ito, Y. J. Electroanal. Chem. 2003, 559, 149-153. nanowires. The reductive conversion of Cu2+ to metallic
(8) Choi, H.; Park, S.-H. J. Am. Chem. Soc. 2004, 126, 6248-6249. copper in this process is 100%, which was indicated in
(9) Liu, Z.; Bando, Y. Adv. Mater. 2003, 15, 303-305. total disappearance of the light blue color (Cu2+; Sup-
(10) Liu, Z.; Bando, Y. Chem. Phys. Lett. 2003, 378, 85-88.
(11) Monson, C. F.; Woolley, A. T. Nano Lett. 2003, 3, 359-363. porting Information (SI)-1). Interestingly, the as-prepared
(12) Liu, Z.; Yang, Y.; Liang, J.; Hu, Z.; Li, S.; Peng, S.; Qian, Y. J. nanowire cake is lifted up to the top of solution (Figure
Phys. Chem. B 2003, 107, 12658-12661. 1A) due to the high density of solution and entrapping of
(13) Yen, M.-Y.; Chiu, C.-W.; Hsia, C.-H.; Chen, F.-R.; Kai, J.-J.; Lee,
C.-Y.; Chiu, H.-T. Adv. Mater. 2003, 15, 235-237. nitrogen bubbles (eq 1) among the nanowires after
(14) Pileni, M. P.; Gulik-Krzywicki, T.; Tanori, J.; Filankembo, A.; magnetic stirring. As shown in these images, the prepared
Dedieu, J. C. Langmuir 1998, 14, 7359-7363. nanowires are straight (Figure 1B,C), with constant
(15) Lisiecki, I.; Sack-Kongehl, H.; Weiss, K.; Urban, J.; Pileni, M.-P. diameters in the range of 60-160 nm (mostly in 90-
Langmuir 2000, 16, 8802-8806.
(16) Lisiecki, I.; Sack-Kongehl, H.; Weiss, K.; Urban, J.; Pileni, M.-P. 120 nm). The wires are ultralong, having lengths of more
Langmuir 2000, 16, 8807-8808. than 40 µm, which virtually corresponds to an aspect ratio
(17) Lisiecki, I.; Filankembo, A.; Sack-Kongehl, H.; Weiss, K.; Pileni, of greater than 350!
M.-P.; Urban, J. Phys. Rev. B 2000, 61, 4968.
(18) Li, Q.; Wang, C. Chem. Phys. Lett. 2003, 375, 525-531.
(19) Wang, Z. L.; Kong, X. Y.; Wen, X.; Yang, S. J. Phys. Chem. B (20) Lou, X. W.; Zeng, H. C. J. Am. Chem. Soc. 2003, 125, 2697-
2003, 107, 8275-8280. 2704.

10.1021/la050220w CCC: $30.25 © 2005 American Chemical Society

Published on Web 03/29/2005
Letters Langmuir, Vol. 21, No. 9, 2005 3747

Figure 1. (A) As-prepared Cu nanowires in mother liquor. (B, C) FESEM images of general and detailed views of Cu nanowires.
(D) TEM image of Cu nanowires.

each case, furthermore, there is an optimal molar ratio

between the two chemicals. With a moderate amount of
EDA, both wire- and disklike morphologies could be
obtained. When EDA was overused, however, the axial
1D growth of nanowires could be switched totally to a
radial expansion (i.e., a 2D growth). Figure 3 reports XRD
patterns and a disklike morphology of Cu at 100%
morphological yield under such a condition (SI-5). The
single-crystal disks also have 〈110〉 orientations, as
determined by the SAED method (Figure 3B). Quite
commonly, a seed area (holelike) in the center of the disk
can be identified, revealing the above 2D growth mech-
anism. The observed growth preference can be attributed
to steric hindrance and charge restriction of copper
complexes in the starting solution, such as [Cu(OH)4]2-,
[Cu(EDA)(OH)2], and [Cu(EDA)2]2+ etc.,21 on a growing
crystal plane, and to synergetic effects of ligand (EDA)
and electrolyte (NaOH) on adsorption and deactivation of
the grown part of a product morphology.
X-ray photoelectron spectroscopy (XPS) results for our
air-dried Cu nanowires are reported in Figure 4A. Cuprite
Cu2O (about 54% among total surface copper) was found
Figure 2. (A) HRTEM image of a Cu nanowire. (B) Location on the wire surfaces, on the basis of an analysis for the
of examined area (indicated with a frame) in (A). (C) A bead-
line model of the Cu (110) surface. (D) SAED pattern of a Cu
binding energies of Cu 2p3/2 (932.4 eV for Cu0 and
nanowire (inset). 932.2 eV for Cu+; reference C 1s was set at 284.7 eV;
SI-6)22 and O 1s (530.2 eV for the anion O2- in the cuprite)23
photoelectrons and the HRTEM image of Figure 2B in
The nanowires obtained are single crystalline with high
which a rough surface region of Cu nanowires can be seen.
lattice perfection (e.g., the lattice fringe d111 ) 2.10 (
Nonetheless, this surface oxidation can be prevented by
0.05 Å), as shown in Figure 2A and B. The growth direction
storing the nanowires in dilute hydrazine solution. Apart
of these wires is along the 〈110〉 (Figure 2C), on the basis
from their electric conductor applications, the copper
of selected area electron diffraction (SAED) analysis
nanowires prepared can also be used as a solid precursor
(Figure 2D; also SI-2). Our XRD study shows that all the
for fabrication of other nanostructures. As exampled in
prepared copper samples have a face-centered cubic (fcc)
panels B and C of Figure 4, straight polycrystalline CuO
structure (SG: Fm3 h m; JCPDS card no. 03-1005), and the
nanotubes, which retain the original shape of Cu nano-
lattice constant of this cubic phase ao is equal to 3.615 Å
wires, have been fabricated from direct metal oxidation.
(SI-3). The chemical composition of the nanowires was
A significant fraction of pristine Cu could be converted to
further confirmed with EDX spectroscopy technique
CuO after heating in air at 300 °C in just 10 min (SI-7).
(SI-4).
It is thought that the preformed surface Cu2O may provide
Our experiments (SI-1) indicate that a high concentra-
good starting points for metal out-diffusion, during which
tion of NaOH is essential to prevent the copper ions from
copper moves preferentially toward the surface region
forming copper hydroxide precipitates. On the other hand,
while oxygen anions on the surface are relatively immobile.
a certain amount of EDA is also indispensable to control
The hollowing mechanism of copper can also be explained
product morphology. The interplay between NaOH and
EDA had been recognized in this work. For example, with (21) Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 4th
a high concentration of NaOH, the needed amount of EDA ed.; John Willey & Sons: New York, 1980; Chapter 21, pp 689-821.
is small, while for a lower concentration of NaOH, the (22) Espinós, J. P.; Morales, J.; Barranco, A.; Caballero, A.; Holgado,
J. P.; González-Elipe, A. R. J. Phys. Chem. B 2002, 106, 6921-6929.
amount of EDA has to be increased accordingly in order (23) McCafferty, E.; Wightman, J. P. Surf. Interface Anal. 1998, 26,
to obtain high regularity for the 1D product (SI-1). In 549-564.
3748 Langmuir, Vol. 21, No. 9, 2005 Letters

Figure 3. (A) XRD patterns of Cu nanowires and disks. (B) FESEM image of a large Cu disk; the white arrow indicates the seed
area in the center. Inset of (B) shows the [110] zone diffraction spots of a Cu disk.

Figure 4. (A) XPS spectra of O 1s and Cu 2p3/2 photoelectrons of air-dried Cu nanowires. (B) TEM image of polycrystalline CuO
nanotubes formed by oxidizing in air at 400 °C for 10 h. (C) SAED pattern of CuO nanotubes formed in air at 400 °C for 3 h
(not shown).

with the Kirkendall-type diffusion process.24 Taking Acknowledgment. The authors gratefully acknowl-
advantage of their interior space,24,25 the polycrystalline edge the financial support of the Ministry of Education,
CuO (a p-type semiconducting oxide) nanotubes may find Singapore.
new applications in photocatalytic reactions such as water
splitting with visible lights.
In summary, using low-cost starting chemicals, large- Supporting Information Available: Tables of ex-
scale synthesis of high-quality ultralong copper nanowires perimental conditions for selected samples and figures showing
can be achieved under mild conditions. The prepared the color changing point at 30-45 min, the [001] zone diffraction
copper nanowires can also be used as starting solid spots of Cu nanowires, XRD patterns of some selected copper
precursor for fabrication of polycrystalline oxide nanotubes metal products, an EXD spectrum of copper nanowires, FESEM
via direct oxidation in air. images of Cu disks, and surface analysis of air-dried copper
nanowires. This material is available free of charge via the
(24) Yin, Y.; Rioux, R. M.; Erdonmez, C. K.; Hughes, S.; Somorjai,
Internet at http://pubs.acs.org.
G. A.; Alivisatos, A. P. Science 2004, 304, 711-714.
(25) Liu, B.; Zeng, H. C. J. Am. Chem. Soc. 2004, 126, 8124-8125. LA050220W