2002 Annual Report Conference on Electrical Insulation and Dielectric Phenomena

Electric-Field-InducedAccumulation and Alignment of Carbon Nanotubes

X. Liu'.', J.L. Spencer', A.B. Kaiser' and W.M. Amold'

'Victoria University of Wellington, NEW ZEALAND
'Industrial Research Limited. Lower Hun NEW ZEALAND

Abstract: Multi-walled carbon nanotubes were grown

by chemical vapor deposition. It was found that, fol-
lowing suspension of the nanotubes in a solvent, they
could be accumulated and aligned by an inhomogene
ous radio-frequency electric field in the high-field
regions of an interdigitated electrode structure. In-
creasing capacitance and conductance of the structure,
which were monitored by dielectric spectroscopy,
correlated with onset and densification of micro-
scopically visible accumulations of aligned tubes on
the electrodes. Sudden and drastic increases in con-
ductance ('bridging") were. observed in some cases.

Introduction
Since the discovery of nanotubes in 1991 [l],
their unique structure and superior electronic and
mechanical properties have caused some excitement.
Application of these properties often requires align-
ment and/or positioning of the tubes, which has been
accomplished both mechanically and electrically [Z-51.
Carbon nanotubes can be viewed as rolled-up graphite
sheets. Accordingly, they should act as pseudo-one
dimensional conductors with high polarizability along
one axis. They will be attracted to regions of high
electric field, independent of the field polarity. Al-
though described earlier as electrophoresis [4,51, this
behavior is dielectrophoresis [6,7] (see Ref. [8] for
true a.c. electrophoresis).A sufficiently high field will
also align long, polarizable tubes. In this work a radio-
frequency field was used to attract and align the tubes.

Materials and Methods

Nanotube Synthesis
Multiwalled carbon nanotubes (MWCNT) were
synthesized at 800-950°C by chemical vapor deposi-
tion (CVD) from acetylene in argonhydrogen carrier
gas mixture. The tubes were grown on a silica plate
from iron cluster catalysts derived by pyrolysis of
ferrous phthalocyanine [91 or of ferrocene [lo].
MWCNT were removed from the plate by razor blade Figvre 1: Transmission elemm micrograph of MWCNT p w n an
and then characterised by electron microscopy (EM). fernus phthalocyanin&ved imn clusters. hset is a higher-
Both transmission (TEM at 100kV. Philips EM 400, magnification view of thc lower sstion of the bundle. The avemgc
Figs. 1 and 2) and scanning (SEM at 5.0kV, Philips diameter and length of the tubs am 40 rn and 15 pm, mpectively.
SEM 505) electron microscopy were used.

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 Figure 3 Transmitted-tight videomicrograph of bundles of MWCNT
collected in the high-field regions between planar gold interdigitated
electrodes (here appearing solid black) having 20-micron spacing after
19 minutes exposure to 2.0V peak at 4.15MHz. These MWCNT had
been prepared on a femus phthalocyanine-derivedFe catalyst.

Figure 2 Tmmissian elecmn micmgraph of MWCNT grown on

f-ene-derived iron clusters The avenge diameter of theis nanotute
sample is 60 nm,but other batches are typically 1oOnm.

Nanotube Suspension
As-grown MWCNTs were suspended by mixing
them in the ratio 1.0 mg (MWCNT): lml (absolute
ethanol) : 15 p1 (1% Triton X-I00 in water, a non- Figure 4 Scanning electmn micrograph of bundles of MWCNT as in
ionic surfactant). After 30 minutes in an ultrasonic Fig. 3 (ferrous phthalayaninpderived Fe catalyst), but Of a different
bath, 15 pl of the suspension were mixed with lml area of the DE. Preparation for SEM required evaporation of the
ethanol and a further 15 pl 1% Triton X-100. A fur- solvent and spumsoating with 4nm of gold. The gold elecoodes. of
ther 15 minutes ultrasonication gave the working spacing 20 mimns, appear light grey in the SEM.
suspension.

The inter-digitated electrode array (DE) was de-

scribed before [ll-131. Video microscopy used a
Nikon inverted microscope with 2OX or 40X objec-
tives, a colour CCD camera and an SVHS video re-
corder.

Alignment Procedure
2.0 volts peak sine-wave at 4.15 MHz was applied
across the D E , having feature size and electrode sepa-
ration of 20 microns. 15 pl of the solvent (blank) or of Figure 5: Transmitted-light videomicrograph of aggregates of
the suspension were added and observations made for MWCNT collected on gold interdigitated electrodes (here appearing
20-70 minutes. During the collection and alignment, solid black) having 20-micmn spacing affer 7 minutes expasure to
videomicroscopy gave images such as shown in Fig. 3. 2.0V peak at 4.15MHz. These MWCNT had been prepared on a
The structures produced were also investigated by fernenderived Fe catalyst.
SEM (Fig. 4)after complete evaporation of solvent.

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 Simultaneous Dielectric Spectroscopy
An electrical bridge circuit that permits simultaneous
dielectropboresis and dielectric spectroscopy was used E
Y
n
as described before [13]. Parallel capacitance and
conductance of the D E were measured with a t10
HF'4194A impedeuce analyser, which also subtracted g! 20
the values of the bridge and the DE-with-solvent- .-Ucal
only. Hence the data presented are increases in paral-
lel capacitance and conductance due to the presence of
s
z
the nanotubes. 'U 10
lQ
n
Results 9
The accumulation of nanotubes was followed by
microscopy, and also electrically, as a function of 0
- , ! o
time. A measurement frequency of 185% was cho- 0 10 20 30 40 50 00 70
sen as being relatively free of electrode artifacts and of Time from start [minutes]
measurement spurii caused by the presence of residual Figure 7: Capacitance and condunance inneases as in Fig. 6, but the
4.15MHz collection voltage. expimenr had 3 rimes the duration. The initial decrrase in conduc-
Depending on the method used to prepare the nano- m c e was seen on several occasions but is as yet unexplained.
tubes, one of two sorts of behavior were observed.

Tubes from Fe(II)-Phthlocyanine Catalyst

600
When suspensions of MWCNT prepared on a fer-
rous phthalocyanine-derivedFe catalyst were subjected ii
to the RF field, the D E capacitance began to increase eal
at once. This continued for tens of minutes (for typical U)
lQ
plots, see Figs. 6 and 7). The D E conductance was
usually observed to also increase with time, but some-
6
times showed an initial, temporary decrease (visible in 'zcU 00
.-5U
lQ
n
0
8
0 40
10 100 400
Conductance .
Frequency [kHz]
Figure 8: Low-Frequencypart of the admiaVlQ spechum at the end of
the experiment shown in Frg. 6. Nae that bod, the capgcimce and
Frequency axes are logarithmic and that the capgcitam closely follows
a l/flaw.The spgrmm was raLen with the 4.15MHz field stiU applied.

Fig. 7 only). The increases in capacitance and conduc-

0 I . . . . , . . . . , . . . . , . . . .0 , . . !
0 10 20
Time from start [minutes]
Figure 6: Typical timecourse of the changes of capacimce and
conductancedvring collection and ali-I of MWCNT on an D E
energised with 2.0V peak at 4.15MHz.
tance accompanied the appearance of just. resolvable
hair-like structures in the high-field regions of the
array, which eventually became the more visible bun-
dles apparent in Fig. 3. Frequency scans of such
preparations showed a strongly frequency-dependent
capacitance and conductance between lokHz and
about 0.4MHz (Fig. 8).

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 Tubes from Ferrocene Catalyst
In the case. of MWCNT prepared on a ferrocene-
derived Fe catalyst, similar behavior to that described
above was observed in the initial stages of collection.
In some cases the conductance then rose very suddenly
and to relatively high values, together with an appar-
ent reduction in capacitance (Fig. 9). These events
suggest the Occurrence of highly-conductive bridge(s)
across the electrode gap.
10
40
0 10 20
Time from start [minutes]
Fgorr 9 C s p a c i t a n c e a n d c o n ~dueb to collecrion and
alignmslt d fmocenodm‘ved MWCNT on an rnE energised with
2.0v p k a t 4 . 1 5 ~Tile
~ ~sudden
. incrrasein Mnducmce limn 14m
ZOpS ocnmedmlessthan 7 sgonds.
Discussion
A good correlation was found between the increases
in conductance and capacitance and the accumulations
of nanotubes seen by both optical and electron micros-
copy. It is unlikely that the electrical signals seen
could have been due to heating or some elecaome
chanical distortion of the D E , because measurements
on nanotube-free solvent revealed voltage-dependent
responses less than 0.1% of those reported here. Fur-
ther, if heating were significant, a sudden rise in con-
ductance would be expected on application of the
field this was never observed.
It is interesting to compare the behaviors of the two
preparations of MWCNT. Accumulations of those
formed on Fe@)-phthalocyanine-derived catalyst were
slender and highly field-oriented (Figs. 3,4). These
caused a progressive increase in both admitttance
components, but no apparent ohmic contact. Rather,
the l/f behavior of the capacitance (Fig. 8) is consis-
tent with an interfacial-type of polarisation mecha-
nism. It appears that the current path to/ftom these
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nanotubes was through at least a thin layer of liquid
medium, rather than by direct contact.
By contrast, MWCNT formed on ferrocene-derivedFe
gave rise to denser, more compact aggregations on the
electrodes (Fig. 5). and these seemed capable of
forming “bridging” paths which were so highly con-
ductive as to reduce the capacitance signal (Fig. 9).
It may be that the reason for this difference lies in the
pronounced differences in tube thickness and folding
between these preparations (compare Figs. 1 and 2). or
else in intrinsic conductivity differences caused by
different levels of iron content or number of lamellae.
Acknowledgement
Lithography by G.C. Turner and Y.Yuan, as well as
support by the New Zealand FRST, are gratefully
acknowledged. X. Liu wishes to thank Industrial Re-
search Limited for support from a PGS&T project.
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Author address: W. Michael Arnold, Sensors &
Electronics Group, Industrial Research Ltd., Grace-
field Research Centre, Po Box 31-310, Lower HutL
New Zealand; Email: m.arnold@irl.cri.nz