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as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode) [30]. The cyclic voltammogram of the Ag electrode gives three oxidation peaks at electrode potentials 0.2 V, 0.3 V, and 0.55 V (vs. SCE), which corresponds to surface oxidation
products AgOH, Ag2O, and AgO, respectively [30]. For the silver nanowire-deposited stainless steel electrode, the third oxidation peak overlaps with the oxidation peak of stainless steel while the first two oxidation peaks are not affected. The intensity of the oxidation peaks for the surface oxide layer is closely
related to the surface area of silver, and therefore can be used to estimate the
surface area of the silver nanowire array. All measurements were taken on the
first cycle of the cyclic voltammogram to avoid surface reconstruction during
the oxidationreduction cycling. The total surface area of the silver nanowire
array is obtained by comparing the peak area of the first two oxidation peaks
for the silver nanowire and that of the polished silver plate. For polished silver
plate, it was assumed that the real surface area is 2.5 times the geometrical area
(i.e., a surface roughness factor of 2.5) [30]. The weight of the nanowires on the
stainless steel was calculated from the total charge associated with the electrodeposition from the potentiostatic deposition curve assuming 100 % electroplating efficiency. The estimated specific surface area of the silver nanowire array is
10 m2/g, and this number is close to the theoretical calculation based on the
geometrical surface area for nanowires with a diameter of 30 nm (12.7 m2/g). It
is noted that our estimate assumes 100 % electroplating efficiency and thus the
estimated value of 10 m2/g is likely to be the lower bound of the surface area.
Received: June 18, 2001
Final version: September 24, 2001

[1] C. R. Martin, Chem. Mater. 1996, 8, 1739.

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64

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Carbon Nanowalls Grown by Microwave Plasma

Enhanced Chemical Vapor Deposition**
By Yihong Wu,* Peiwen Qiao, Towchong Chong, and
Zexiang Shen
Both fullerenes and carbon nanotubes represent unusual
forms of carbon in the nanometer regime.[1] Their unique crystalline structures and dimensionality bring about carbon with
new mechanical, chemical, and electronic properties.[25] In
some senses, fullerenes can be thought of as zero-dimensional
carbon, whereas nanotubes apparently exhibit a quasi onedimensional structure. Although conventional graphite forms
hexagonal plate-like crystals with very weak bonding between
graphene layers, it is a surprising fact that so far there has
been no report on the growth of well-separated graphene
sheets (or two-dimensional carbon) on other substances. In
this communication, we report the well-controlled growth of
two-dimensional carboncarbon nanowalls.
The growth of carbon nanowalls was found during the
growth of carbon nanotubes. Our original motivation was to
grow carbon nanotubes for scanning probe applications. To
this end, various types of substrates coated with different
types of catalysts were tried in order to optimize the growth
process. These included Si, stainless steel, Cu, GaAs, and sapphire substrates coated with NiFe, CoFe, FeMn, and CoCrPt
catalysts. All the substrates were conductive except for sapphire. The catalysts, with typical thicknesses ranging from 20
to 100 nm, were deposited in a sputtering system with a base
pressure of 3 109 torr. The growth of the nanotubes was
performed in a microwave plasma enhanced chemical vapor
deposition system (MPECVD),[613] which was equipped with
a 500 W microwave source and a traverse rectangular cavity
to couple the microwave to a quartz tube for generating the
plasma. Inside the quartz tube are two parallel plate electrodes, placed 2 cm apart in the longitudinal direction of the
tube, and these were used to apply a DC bias to promote the
growth and alignment of the nanotubes. The gases used were
mixtures of CH4 and H2. Typical flow rates of the H2 and CH4
were 40 and 10 sccm, respectively. Before CH4 was introduced to the quartz tube in order to commence the growth of
the nanotubes, the substrate was pre-heated to about 650
700 C (limited by the microwave power) in hydrogen plasma

[*] Prof. Y. Wu,[+] P. Qiao,[+] Prof. T. Chong[+]

Department of Electrical and Computer Engineering
National University of Singapore
4 Engineering Drive 3, Singapore 117 576 (Singapore)
E-mail: elewuyh@nus.edu.sg
Prof. Z. Shen
Department of Physics, National University of Singapore
10 Kent Ridge Crescent, Singapore 119 260 (Singapore)

[+] Second address: Data Storage Institute, National University of Singapore,

5 Engineering Drive 1, Singapore 117 608, Singapore.
[**] The authors thank J. J. Qiu and K. B. Li for their assistance in the deposition of the catalyst layers and P. Luo for her help with the SEM observations.

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Adv. Mater. 2002, 14, No. 1, January 4

Fig. 1. Typical SEM images of a) carbon nanotubes grown on conductive substrates (in this case NiFe (40 nm) coated Cu); b) carbon nanowalls grown on
NiFe (40 nm) coated sapphire substrates; c) tubular structures that were also
observed occasionally in nanowall samples. Scale bars: 100 nm.

substrates. In this specific sample, the nanotube diameter is

about 30 nm. Under almost identical conditions, however, the
nanostructures grown on sapphire substrates showed very little resemblance to the nanotubes grown on conductive substrates: they are well-aligned carbon sheets with a thickness in
the range of several nanometers. Hereafter we refer to them
as carbon nanowalls. Figure 1b shows a typical SEM image of
the carbon nanowalls grown on NiFe (40 nm) coated sapphire
substrates. The distribution of the nanowalls is remarkably

Adv. Mater. 2002, 14, No. 1, January 4

uniform over the whole substrate surface area (typically

1 1 cm2). Occasionally, we could also see some isolated
tubular structures like the one shown in Figure 1c. As can be
seen from Figures 1b and c, carbon whiskers are formed on
part of the nanowall surfaces.
To shed light on how these structures were initially
formed, SEM images were taken of the films at different
growth stages. In order to eliminate the influence of the
starting materials, the SEM images were taken from the
same sample but at different locations (different stages of
growth were achieved by placing the substrate at a non-optimum location on the lower electrode). The 20 nm thick
Ni80Fe20 coated substrate was first heated in pure hydrogen
plasma for about 8 min before the introduction of methane,
used for growing the carbon films. As shown in Figures 2a
and b, the catalyst islands can be seen clearly at the initial
stage of the growth. Carbon ribbons started to grow across
some of the islands and eventually developed into wall-like
structures when all the ribbons met with one another (see
Figs. 2c and d). The top edges of the nanowalls are either
folded double layers or unfolded single layers, as shown in
Figures 2e and f, respectively. This suggests that some of the
nanowalls are hollow shells with nanometer scale spacings.
The Raman spectra of typical nanowall samples were found
to have four peaks with frequencies (full widths at half maximum): 220 (70), 1335 (32), 1584 (16), 1617 (10) cm1. The
position of the 1584 cm1 peak falls well within the range of
a series of peaks that have been observed for carbon nanotubes,[14] though the origin of the peak at 1617 cm1 is not
clear at the moment. The peak at 220 cm1 is similar to the
breathing mode of single-wall nanotubes, but with a much
higher frequency.[14] The emergence of the 220 cm1 peak
agrees well with the SEM observations, which showed that
the flakes have folded tops (Figs. 2e and f), suggesting that
a hollow cavity exists inside the flakes. Using the theory developed for calculating the breathing mode frequency of
carbon nanotubes,[14] the spacing of the cavity was estimated to be about 1 nm (though further studies are needed
to understand the origin of this peak). This is a reasonable
value because the thickness of the flake shown in Figure 1f
is less than 10 nm. The peak at 1335 cm1 is very close to
the D band of polycrystalline diamonds. A diamond layer
might be formed below the graphite because microwave
plasma CVD itself is also one of the techniques used for
producing diamonds.
The question as to what could be the possible reasons for
the formation of the nanowalls naturally arose after nanowalls were found on sapphire substrates but not on other
types of substrates. It was understood at the beginning that
differences in the surface morphology after the pre-heating
were unlikely to be the main reason, because, after pre-heating, all the surfaces showed almost the same type of morphologysimilar to that shown in Figure 2a. Excluding the
morphology factor, the next suspect was naturally the electrical conductivity of the substrate because nanowalls were

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65

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without a bias for 810 min. During both pre-heating and

growth, the process pressure was maintained at 1 torr. A DC
bias of 185 V was applied to the lower electrode on which
the substrate was mounted during the growth of the nanotubes, while the top electrode was grounded. The growth on
all the conductive substrates produced well-aligned carbon
nanotubes, with diameters ranging from 10 to 30 nm. As one
example, Figure 1a shows a scanning electron microscopy
(SEM) image of typical nanotubes grown on NiFe (40 nm)/Cu

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Although the mechanism responsible for

the growth of different types of carbon is
currently not well understood, it is postulated that the electric field plays an
important role. It has been reported that the
electric field is closely related to the
orientation or alignment of nanotubes in
MPECVD.[10,11] In our case, when the substrate was conductive, the electric field was
vertical to the substrate due to the DC bias.
Changing the substrate to an insulator
should have very little effect on the vertical
field, because the substrate is a dielectric
and occupied only one tenth of the total area
of the lower electrode. One thing that might
have changed is that the catalyst islands may
have been charged up due to the cutoff of
the electrical conduction between the substrate surface and the lower electrode. It is
very likely that the charge distributions were
non-uniform, due to the non-uniformity of
the island distribution after the pre-heating.
This, in turn, would have caused fluctuations
of the electrical potential on the sample surface. As a result, a strong traverse electric
field was built up across the neighboring
islands. For instance, a voltage difference of
0.1 V across two islands with a 0.1 lm spacing would generate an electric field with a
strength of 10 kV/cm. This is much stronger
than the vertical component of the field,
which was about 90 V/cm in our case. Therefore, it is most likely that the relative
Fig. 2. SEM images of the nanowalls at different growth stages and at different magnifications. ac) Inistrength of the vertical and traverse fields
tial to intermediate stages; d) after a growth of 5 min; e) a close-up view of a few nanowalls; f) a closehas played a dominant role in determining
up view of a single nanowall. Note that the tops of the nanowalls show a folded round shape instead of
a single graphene layer in this sample. Scale bars: 100 nm in (ac, e), 1 lm in (d), and 10 nm in (f).
the form of the carbon that has grown. Even
when it was on an insulating substrate, the
surface charges were still movable via the plasma or the bi-confirst found growing on sapphire, which is an insulator. In ortinuous catalyst. Therefore, the electrical contact to the subder to confirm this, we first used a piece of sapphire to isostrate surface reduced both the non-uniformity of charge distrilate the electrical conduction from the NiFe-coated Si subbution and the total amount of charge, leading to a reduction in
strate to the lower electrode: as a result, we obtained
the traverse component of the electric field. This eventually led
nanowalls instead of nanotubes! Secondly, a new, lower electo the growth of nanotubes.
trode was designed to have a metallic fixture so that the top
surface of the substrate was electrically connected to the botTable 1. Summary of the kinds of substrates and electrical connection methods
tom electrode, even when a sapphire substrate was used. In
that have been used to grow both nanotubes and nanowalls.
this case, the carbon grown on the sapphire substrates was in
the form of nanotubes rather than nanowalls! Similar types
of experiments have been done for other types of substrates
and electrical connections. The results are summarized in Table 1. This series of experiments demonstrates clearly that
nanotubes grow when there is electrical conduction from the
catalyst to the electrode, whereas nanowalls form when the
electrical conduction is cut off. Furthermore, carbon soot
mixed with tubes and walls (depending on the substrates
used) formed when there was no DC bias applied between
[a] Supported by a piece of sapphire.
the two electrodes.

66

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Adv. Mater. 2002, 14, No. 1, January 4

Received: July 16, 2001

Final version: September 17, 2001

[1] M. S. Dresselhaus, G. Dresselhaus, P. C. Eklund, Science of Fullerenes and

Carbon Nanotubes, Academic Press, New York 1996.
[2] E. W. Wong, P. E. Sheehan, C. M. Lieber, Science 1997, 277, 1971.
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Synthesis and Characterization of Cu2O

Nanowires by a Novel Reduction Route**

possible to convert photons into excitons, which then travel

through small apertures or small dimension waveguides with
little loss by scattering or diffraction. At the end of the path,
the excitons can be converted back into photons.[1] Another
exciting development is a Cu2O related material, CuAlO2,
that was reported as the first transparent oxide showing
appreciable p-type conductivity (up to 1 S/cm).[2]
Cu/Cu2O layered nanostructured materials with interesting
optoelectronic properties have been prepared by electrodeposition.[3,4] Cu2O is a p-type semiconductor with a direct
bandgap of 2 eV, which makes it a promising material for the
conversion of solar energy into electrical or chemical energy.
Recently, it has been found that Cu2O submicrospheres can
be used as the negative electrode material for lithium ion batteries.[5]
Over the past few years, attention has been focused on the
research field of one-dimensional nanostructure materials,
such as nanowires and nanorods, because of both their fundamental importance and the wide range of their potential applications in nanodevices.[613] Semiconducting, one-dimensional, nano-sized materials are known to have many
interesting physical properties and great applications in optoelectronic devices, for example, nanowire light-emitting devices with extremely low power consumption.[6] In order to
obtain nanowires or nanorods of the desired materials, various
methods have been developed for the preparation of semiconducting nanowires. However, to the best of our knowledge,
high temperatures, special conditions, or tedious procedures
are required for these methods.[1424] Here, we report a novel
reduction route for preparing Cu2O nanowires in the presence
of a suitable surfactant, polyethylene glycol (PEG; Mw
20 000), at room temperature. This method requires no complex apparatus or techniques. The synthesis time is very short.
Figure 1 shows an X-ray diffraction (XRD) pattern of the
nanowires. The XRD spectrum of the Cu2O nanowires contains five peaks that are clearly distinguishable. All of them
can be perfectly indexed to crystalline Cu2O, not only in peak
position, but also in their relative intensity. The peak positions

By Wenzhong Wang, Guanghou Wang,* Xiaoshu Wang,

Yongjie Zhan, Yingkai Liu, and Changlin Zheng
Cuprous oxide and related materials are the subject of
much current interest. It has been reported that excitons can
propagate coherently through single crystalline Cu2O. It is

[*] Prof. G. H. Wang,[+] Dr. W. Z. Wang,[+] Y. J. Zhan, Y. K. Liu,

C. L. Zheng
National Laboratory of Solid State Microstructure and Department
of Physics, Nanjing University
Nanjing 210 093 (China)
E-mail: wangqun@nju.edu.cn
Dr. X. S. Wang
Center for Materials Analysis, Nanjing University
Nanjing 210 093 (China)

[+] Second address: Structure Research Laboratory, University of Science

and Technology of China, Hefei, Anhui 230 026, China.
[**] This work was supported by the National Natural Science Foundation of
PR China (No. 29 890 210, 10 023 001, 10 074 024).

Adv. Mater. 2002, 14, No. 1, January 4

Fig. 1. The XRD pattern of a sample of Cu2O nanowires prepared by a reduction route in the presence of PEG at room temperature.

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In summary, we have reported for the first time, the growth

of carbon nanowalls. Nanowalls may find applications in field
emission displays and energy storage due to their large surface
areas. It has been pointed out both theoretically and experimentally that the electric field may play an important role in
determining the form of the carbon deposited by MPECVD.
Modification of the equipment is underway so as to achieve
more flexible control of the carbon growth, through controlling
the local electric field. This type of nanostructure may find applications in batteries, light-emitting and conversion devices,
catalysts, and other areas requiring high surface area materials.