Electrochemistry Communications 4 (2002) 8085

www.elsevier.com/locate/elecom

Fabrication of carbon microelectrodes with an eective

radius of 1 nm
Shengli Chen, Anthony Kucernak

Department of Chemistry, Imperial College of Science Technology and Medicine, London, UK SW7 2AZ
Received 6 November 2001; received in revised form 13 November 2001; accepted 14 November 2001

Abstract
A method for producing insulated nanometer-sized carbon electrodes is presented. These electrodes are produced using electrochemical etching of carbon bers followed by deposition of electrophoretic paint. A new deposition approach for insulating the
tips, the so-called ``inverted deposition'' technique, is introduced. This technique allows complete insulation of the whole body of the
etched carbon ber except for the very tip, leaving an electrochemical active area with eective diameters as small as a few nanometers. The process overcomes pinhole formation that can be a problem with the normal electrophoretic paint deposition process.
The fabricated electrodes show ideal steady-state voltammetric behavior. The voltammetric response corresponding to the reduction
of hexacyanoferrate(III) and hexaammineruthenium(III) is investigated on these small electrodes in the absence and presence of
supporting electrolyte. For these two multiple-charged ions the steady-state voltammetric behavior in the absence of supporting
electrolyte is found to deviate from expected behavior, especially at very small electrodes. 2002 Elsevier Science B.V. All rights
reserved.
Keywords: Nanometer-sized electrode; Carbon ber; EDP insulation; Absence of supporting electrolyte

1. Introduction
During the last two decades there has been widespread and growing interest in fabricating and characterizing electrodes with nanometer dimensions due to
the novel applications of such ultrasmall devices and the
unique electrochemistry at the interface between individual nanoelectrodes and the electrolyte [14]. Preparation of ultrasmall electrodes involves two crucial steps.
First, a commercially obtained microwire of the electrode material has to be signicantly thinned down to
form a tapered tip with the end of nanometer dimensions. This thinning task is generally accomplished by
various etching techniques [1,59]. The other crucially
important step is insulation of the whole of the surface
of the etched wire except the very apex of the tip, thus
exposing only a very tiny electrochemically active area
to the electrolyte. Several research groups have reported
*

Corresponding author. Tel.: +44-20-74945831; fax: +44-2075945804.

E-mail address: a.kucernak@ic.ac.uk (A. Kucernak).

within the literature the fabrication of individual Pt

electrodes having electrochemically active radii as small
as several tens of nanometers, and even down to a few
nanometers [1,2,5,6]. The achievement of exposing a tip
with electroactive radii of only a few nanometers relies
on ecient insulation methods. Several methods have
been previously used, for instance, translating the etched
tips through a molten glass bead at controlled speed [1]
or the use of a laser micropipette puller [2]. Compared to
these approaches the method employing electrophoretic
deposition of a polymer paint (EDP) [5,6,10] seems to be
particularly straightforward and practical since no
complicated experimental setup is required.
Although carbon microband electrodes have been
produced with one dimension less than 50 nm [11], and
uninsulated carbon ber electrodes 10100 lm long and
with tip diameters of ca. 100 nm have been produced
[12], no one has reported fabrication of carbon electrodes having electroactive surfaces of equivalent radii
less than about 100 nm. Moreover, as carbon is a versatile electrode material that can undergo various
chemical and electrochemical modications it is possible

1388-2481/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 8 - 2 4 8 1 ( 0 1 ) 0 0 2 7 8 - 8

S. Chen, A. Kucernak / Electrochemistry Communications 4 (2002) 8085

to produce exible surfaces ranging from purely inert to

highly active. Nanometer-sized carbon electrodes could
be of great signicance in both fundamental and applied
electrochemistry, especially in electrocatalytic and electroanalytical studies. In this paper, we report results on
the preparation of carbon electrodes having eective
radii down to approximately 1 nm by using electrochemical etching of carbon bers followed by a new
EDP coating technique.
2. Experimental
2.1. Materials and chemicals
Graphitized carbon bers (PANEX33 CF, 95%
Carbon, unsized) were obtained from Zoltek (MO,
USA). Colloidal graphite was obtained from Agar Scientic, UK (type (G303). Cathodic electrophoretic paint
(Clearclad HSR, LVH coating, UK) was used to coat
the bers as insulation. The reagents used were:
K3 FeCN6 (BDH AnalaR), KCl (BDH Analar),
RuNH3 6 Cl3 (Aldrich), and NaOH (Aldrich). All solutions were prepared with Milli-Q water.
2.2. Apparatus
Square wave AC voltages of 50 Hz frequency were
generated with a function generator (Jupiter 2000) and
used to accomplish electrochemical etching of carbon
bers. Electrodeposition of the paint was performed
using a general DC power supply. Both the etching and
EDP steps were conducted in a single chamber electrochemical cell using a two-electrode conguration with a
large graphite rod serving as auxiliary electrode. Electrochemical measurements were conducted using an
AutoLab PGSTAT20 potentiostat with the ECD module (Eco Chemie, Netherlands). Voltammetric measurements utilized a two-electrode conguration with a
calomel reference electrode as auxiliary separated from
the working electrode through a Luggin capillary. A
video camera (RS components, UK) and a micromanipulator (Edmund Scientic, USA) were used to position and monitor the tip during experiments. SEM
images were obtained on a JEOL JSM-T220A scanning
electron microscope.
2.3. Electrode construction
Individual single bers (56 mm in length and 3:6 lm
in radius) were attached to one end of a copper wire (0.5
mm in radius) with a drop of colloidal graphite. The
copper-ber assembly was left to cure in air at room
temperature for several hours. Before etching, the ber
was successively rinsed with ethanol and water. The
copper-ber assembly was then mounted on a mi-

81

cromanipulator and gently translated into the etching

solution (0:01 mol dm 3 NaOH) with about 0.51 mm
of the ber immersed. An AC voltage was applied between the ber and a glassy carbon rod auxiliary electrode for a dened period. After etching, the ber was
rinsed with water to remove any residual alkaline solution and left to dry prior to the insulation step. No eect
of the position of the auxiliary electrode was determined.
Cathodic electrophoretic paint was used as this
avoids any potential oxidative dissolution of the substrate. After deposition, spray rinsing was used to remove any loose solution from the ber. A glassy carbon
auxiliary electrode was used, and again, no eect of
auxiliary electrode position was obvious. The copperber assembly was then heated at 195 C for about
30 min to let the deposited lm cure. This heat cure
process hardens the lm and fuses the resin particles
together forming an insulating lm. Repeated deposition and cure steps were performed to obtain electrodes
with smaller eective radii. Deposition voltages of 57 V
were employed for 6090 s in the rst deposition and for
2040 s in the following deposition steps.
The nal step is to seal the copper-ber assembly into
a glass tube with epoxide resin. Only the insulated carbon ber was allowed to protrude from the epoxy sealed
glass tube. Electrodes can be re-used and have lifespans
of a few weeks depending on the history of usage.
3. Results
3.1. Fabrication of nanometer carbon electrodes
3.1.1. Electrochemical etching of carbon bers
As a crucial starting step, the electrochemical etching
process of the carbon bers was investigated. The
etching progress was monitored by visual inspection
under microscope and by recording the currents owing
during the etching process. It was found that the amplitude of the applied square wave voltage is critical to
the resultant shape of the ber. Fiber tips with a sharp
tapered end can be produced by two kinds of etching
mechanisms. At higher etching voltages (ca. 5:5 Vp-p ),
thinning is rapid at the air/solution interface although
much slower on the immersed portion of bers. The AC
current owing through the ber averages about 10 lA
and the etching process takes about 500 s at which point
the ber breaks at the air/solution interface and the
etching current drops to zero. The resulting tip shows a
conical shape and has a nanometer-sized end. Shallow
tapered tips can also be obtained by using a lower
voltage (ca. 45 Vp-p ), where the immersed portion of
the carbon bers undergoes almost uniform etching with
time. The AC current averages about 5 lA, and the
etching process takes about 900 s. Fig. 1 gives an SEM

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S. Chen, A. Kucernak / Electrochemistry Communications 4 (2002) 8085

Fig. 1. SEM image of an etched carbon ber.

image of a carbon ber etched in this lower potential

range, and shows a tip radius below 50 nm. Higher
resolution SEM images of carbon ber tips are dicult
to obtain due to vibration of the ber. In contrast to the
two cases mentioned above, at high potentials
(> 6 Vp-p ), etching and scission of the ber at the air
solution interface is very fast and produces a blunt,
unsharpened ber. The AC current is about 70 lA and
current ows for about 100 s before the ber breaks o.
3.1.2. EDP insulation of the etched carbon ber
The EDP method involves two separate stages:
electrophoretic deposition of paint onto the tip surface
followed by a curing step at high temperatures during
which the paint particles fuse together. Since some
shrinkage of the deposited lm will occur accompanying the heating process, the insulating lm tends to
retract slightly from the tip apex, allowing the surface
of the tip apex to be exposed in a natural and spontaneous way without the need for any manual intervention. This is a major advantage of the EDP method
in making nanometer-sized electrodes compared to
other insulating techniques. However, the shrinkage
process also brings about some complexities. In order
to be able to expose the tip end during the heating
stage, a thin paint layer must be deposited. Otherwise,
a fully insulated electrode would be produced even
after the subsequent heating stage. In contrast, if the
coating layer is too thin, pinholes tend to be left in the
lm, probably caused by rough protrusions on the
surface of the ber. These pinholes will provide an
additional Faradaic current contribution, bringing
about uncertainties in the voltammetric response.
To reduce the likelihood of pinhole formation, while
still exposing only the very tip of the ber, we have

Fig. 2. Schematic of the inverted deposition arrangement, (a); photomicrograph of ber tip just penetrating the surface of the EDP solution, (b). The bright region is due to low angle light reecting o of the
meniscus. Copper wire, 1; electrophoretic paint solution, 2; light
source, 3; meniscus, 4; carbon ber, 5; carbon colloid contact, 6.

developed the so-called ``inverted deposition'' process.

Rather than immersing the ber in a tip-down fashion as
commonly performed by others, the ber is immersed in
the EDP solution, inverted and translated so that the
sharp tip just breaks through the solution surface. As
shown in Fig. 2(a), the tip apex remains in contact with
the solution by a very thin liquid meniscus. Such an
arrangement will lead to virtually no deposition on the
very end of the tip, and an increase in deposition density
as one moves away from the tip. Fig. 2b shows an
overhead photomicrograph taken with side illumination. Light reects o the meniscus, and produces a
small bright patch in the photograph (4). 1 The ber (5)
can dimly be seen within the EDP solution. The extent
to which the meniscus is formed can easily be controlled
by translating the ber. The extent to which the meniscus is formed is expected to control the rate at which the
polymer thins as it approaches the tip. The heat cure
process will expose the very end of the tip without
leaving pinholes on the main ber because of the relatively thick coating layer deposited on that section of the
electrode. By employing this process it is relatively easy
to produce insulated carbon ber electrodes having radii
1

This micrograph shows the case in which the ber is translated so

that a meniscus is just formed a fully formed meniscus results in a
bright patch which covers half the area photographed.

S. Chen, A. Kucernak / Electrochemistry Communications 4 (2002) 8085

down to tens of nanometers or even smaller. Attempts

were made to obtain SEM images of the insulated tips
with such tiny electroactive areas. However, no clear
interface between the polymer insulation and the exposed carbon ber tip surface can be seen on such images, probably due to both the electrode and coating
materials having carbon as the component with the
highest atomic number, and thus showing similar scattering eciency. However, what can be seen from the
SEM images of insulated tips is a smooth, defect-free
insulation layer.
3.2. Electrochemical characterization
3.2.1. Steady-state voltammetric behaviors of carbon
nanometer electrodes
Steady-state voltammetry is a straightforward and
reliable method to characterize these ultrasmall electrodes. Fig. 3 shows voltammograms of two carbon ber
electrodes fabricated using the inverted deposition procedure. The voltammograms were obtained in
0:5 mol dm 3 KCl containing 0:010 mol dm 3 K3 Fe
CN6 . It can be seen that the voltammograms have a
well-dened sigmoidal shape and that the forward and
reverse scans retrace each other exactly. As expected, the
current associated with charging/discharging of the
double layer is invisible. The sigmoidal shape of the CV
is maintained even at a potential scanning rate of
1 V s 1 . All these features indicate that the ber tip is
well sealed by the polymer insulation. Assuming that the
electrodes possess a hemispherical shape, the apparent
radii of these electrodes can be determined from the

Fig. 3. The steady-state voltammograms (both forward and reverse

scans) of reduction of 0:01 mol dm 3 K3 FeCN6 in 0:5 mol dm 3
KCl. Both electrodes were fabricated using three repeated EDP coating/heating cycles. The eective radii are calculated from the diusion
limited currents as 0.9 nm, (a); and 38 nm, (b). Scan rate of 10 mV s 1 .

83

limiting plateau currents (id ) according to the following

equation [13]:
id 2pnFDc1 r0 ;

where n is the number of electrons transferred during the

electrochemical process, F is Faraday's constant, D and
c1 are the diusion coecient and concentration of the
electroactive species, respectively, and r0 is the radius of
the electrode. By using the known value of the diusion
coecient of ferricyanide [14], 7:2  10 6 cm2 s 1 , the
eective radii of the electrodes in Fig. 3 are calculated as
0.9 and 38 nm, respectively. Usually, two or three deposition/heat cycles can produce electrodes of eective
radii less than 100 nm. For electrodes with eective radii
of less than 10 nm, at least three deposition cycles are
required. These reported radii are, of course, only approximate as deviation from the ideal hemispherical
shape will have some eect on the magnitude of the
limiting current. Furthermore, especially at the smaller
radius electrode we must question whether the standard
microelectrode theory holds. Several eects may potentially dominate the electrochemical response such as size
and geometry eects (especially when the size of the
electrode approaches the size of the electroactive species). Furthermore, the double layer surrounding the
EDP insulation on either side of the electrode may
overwhelm the local double layer over the carbon electrode, and we may see additional eects due to specic
and non-specic adsorption of ions on the surrounding
insulation.
For a totally reversible system the Tomes criterion
states that jE3=4 E1=4 j (i.e., the potential dierence
between the 1/4 and 3/4 along the current response)
should be 54:4=n mV for an n electrode reaction at
298 K. For the larger electrode of the two electrodes in
Fig. 2 this potential dierence is calculated as being 56
mV, close to the expected value. In contrast the value for
the smaller electrode is dicult to measure due to the
larger amount of electrical noise but appears to be larger
than expected in the range 8090 mV. We ascribe this
discrepancy to non-ideal eects for these extremely small
electrodes.
3.2.2. The eect of the absence of the supporting
electrolyte
The steady-state voltammetric response at microelectrodes in the absence of supporting electrolyte has
been theoretically predicted by incorporating the contribution of migration into the steady-state current [15].
This theoretical analysis was found applicable to the
voltammetric behaviors of most redox couples [15,16].
However, large deviation from the expected theory has
been reported on the reduction of ferricyanide on a
precious metal or carbon microelectrode [16]. According
to the theoretical predication, for ferricyanide there
should be a depression of about 10% in the steady-state

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S. Chen, A. Kucernak / Electrochemistry Communications 4 (2002) 8085

limiting current in the absence of supporting electrolyte

compared to the result obtained in its presence. In reality, the actual depression observed is much larger. In
addition, it was found that such a depression depends on
the electrode size and the concentration of the electroactive species [17,18]. For example, almost no reduction
current can be observed at microelectrodes having a
radius of 5 lm in 1 mM FeCN36 solution [16],
whereas about 30% depression occurred in 5 mM
FeCN36 solution at an electrode of 6 lm radius
[17,18].
We investigated the eect of the absence of supporting electrolyte on the voltammetric behavior of ferricyanide reduction at our small carbon electrodes in 10 mM
FeCN36 solution. Similar to the results obtained on
metallic microelectrodes [16,17], we see excessive inhibition far beyond the theoretical prediction expected in
the absence of supporting electrolyte. Furthermore, the
extent of this inhibition is strongly correlated with
electrode size. Very small electrodes showed a signicant
reduction in current compared to larger electrodes. This
eect is illustrated in Fig. 4. These plots are obtained by
scaling the voltammetric response in the absence of
supporting electrolyte by the limiting current found in
the presence of supporting electrolyte thus were there
no variations in limiting current we would expect to see
a response similar to that shown in Fig. 4(a). It can be
seen that a decrease of more than 30% of the limiting
plateau current occurs upon removal of the supporting
electrolyte even on electrodes with electroactive radius
of around 3 lm. At electrodes having radii of 100 nm or
less, a greater than 95% decrease in the reduction current was seen. Moreover, the steady-state voltammograms in the absence of the supporting electrolyte

Fig. 4. Normalised response of the eect of the absence of supporting

electrolyte as a function of electrode size. The response for each electrode is normalised to the limiting current for that electrode in
0:01 mol dm 3 K3 FeCN6 0:5 mol dm 3 KCl. Response for
3:5 lm radius electrode in presence of supporting electrolyte, (a); relative response in 0:01 mol dm 3 K3 FeCN6 and the absence of supporting electrolyte when the eective radius of the electrode is 3:5 lm,
(b); 0:46 lm, (c); 0:14 lm, (d). Potential scan rate of 10 mV s 1 .

become rather ill-dened as the electroactive radius of

the electrodes decreases.
The exact mechanism of such strong inhibition is still
not very clear. Lee and Anson [16] suggested that the
diuse double layer eect on the electrode reaction in the
dilute solution is the major reason for the inhibition of
ferricyanide reduction in the absence of the electrolyte.
However it must be recognized that the Debye length,
j 1 , in these solutions is only of the order of 1 nm, with
the diuse double layer being about 5j 1 , and so such
an eect might be expected to only become signicant at
electrode sizes in the 10's nm regime. Alternatively, a
possible surface blockage eect due to adsorption of
reactant decomposition products has been suggested as
the cause for the observed inhibition of ferricyanide
reduction in the absence of supporting electrolyte [17].
Furthermore, the electroneutrality assumption used in
developing the voltammetric theory may be no longer
valid at such small electrodes [19].
To understand which of these eects might be dominating, we looked at the reduction of hexaammineruthenium(III) in the absence of the supporting electrolyte
as this is a non-adsorbing redox couple with a high rate
of electron transfer [1,6]. All of the voltammetric curves
in the presence of supporting electrolyte showed close to
ideal electrochemical behavior with forward and reverse
branches overlapping. The results for the ratio of limiting currents in the presence and absence of supporting
electrolyte are shown in Fig. 5. On electrodes with
electroactive radii larger than 50 nm, the reduction
current increases by approximately 10% upon removal
of the supporting electrolyte. This is consistent with the
theoretical prediction under combined migration/diusion transport of the electroactive species to the electrode [15]. In contrast when the electrode size becomes
less than 50 nm, obvious diminishment in the limiting

Fig. 5. The dependence of the ratio between the limiting plateau current (I) in 0:01 mol dm 3 RuNH3 6 Cl3 and the limiting plateau current (Id ) in 0:01 mol dm 3 RuNH3 6 Cl3 0:5 mol dm 3 KCl on the
eective radius of the carbon microelectrode electrode.

S. Chen, A. Kucernak / Electrochemistry Communications 4 (2002) 8085

plateau current occurs in the absence of supporting

electrolyte. This indicates that for electrodes of 50 nm or
larger, mass transport of hexaammineruthenium(III)/
hexaammineruthenium(II) species is adequately described by the diusion-migration theory previously
mentioned. However in the absence of supporting electrolyte, when the electroactive radius of the electrode
becomes 20 nm or less, there is signicant deviation
from theory.
Thus, it may be concluded that ferricyanide reduction
in the absence of the supporting electrolyte is almost
completely suppressed at electrodes having electroactive
radii of about 100 nm, which is far greater than the
characteristic thickness of the diuse layer at these
concentrations. The inhibition of ferricyanide reduction
could possibly be due to a surface blockage and inhibition eect. In the presence of supporting electrolyte,
the excess KCl in the solution may not only eliminate
the diuse double-layer eect, but also decrease the
possibility of decomposition of ferricyanide since the
excess potassium cations can stabilize the ferricyanide
through ion association [17]. The decomposition process
therefore becomes pronounced upon removal of the
supporting electrolyte. The comparison with the hexaammineruthenium(III)/(II) couple is interesting. Again
we nd an inhibition of the electrochemical process, but
now it occurs for electrodes which are signicantly
smaller, and which approach a size at which diuse
double-layer eects might become important. Nonetheless, it must be admitted that there is no clear-cut case
for any specic mechanism, with the precise geometry of
the microelectrodes potentially having the greatest eect
on the electrochemical response. A detailed investigation
of the eect of the absence of supporting electrolyte on
our nanometer-sized microelectrodes is currently underway.
4. Conclusion
We have shown that voltammetrically well-behaved
carbon microelectrodes with down to nanometer eective radii can be readily fabricated by combining electrochemical etching and EDP insulation utilizing a new
inverted deposition procedure. The investigation of
these small electrodes indicates that the absence of
supporting electrolyte aects ferricyanide reduction
more severely than for hexaamineruthenium(III) reduction. In the absence of supporting electrolyte, signicant deviation from theory is seen in ferricyanide at
electrodes 3 lm or less in size whereas in hexaamine-

85

ruthenium(III) such deviations are only seen for electrodes with eective radii of 20 nm or less. A possible
diuse double layer eect may arise when the active
radius of electrodes becomes less than 20 nm, which is
comparable to the size of the double layer in the dilute
solution without supporting electrolyte. For ferricyanide
reduction, the absence of supporting electrolyte potentially favors the reactant decomposition reaction which
produces adsorbed species which block the electrode
surface, thus resulting in a signicant inhibition of the
reduction current.

Acknowledgements
We thank the Leverhulme trust for the nancial
support, Mr. Peter Hope from LVH Ltd. for providing
the electrophoretic paint solution and suggestions on its
use, and Mr. Simon Turner for his workshop skills.

References
[1] R.M. Penner, M.J. Heben, T.L. Longin, N.S. Lewis, Science 250
(1990) 1118.
[2] Y. Shao, M.V. Mirkin, G. Fish, S. Kokotov, D. Palanker, A.
Lewis, Anal. Chem. 69 (1997) 1627.
[3] B. Giros, M. Jaber, S.R. Jones, R.M. Wightman, Nature 379
(1996) 606.
[4] F-R.F. Fan, A.J. Bard, Science 267 (1995) 871.
[5] C.J. Slevin, N.J. Gray, J.V. Macpherson, M.A. Webb, P.R.
Unwin, Electrochem. Commun. 1 (1999) 282.
[6] J.L. Conyers, H.S. White, Anal. Chem. 72 (2000) 4441.
[7] A. Schulte, R.H. Chow, Anal. Chem. 70 (1998) 985.
[8] X. Zhang, W. Zhang, X. Zhou, B. Ogorevc, Anal. Chem. 68
(1996) 3338.
[9] T.G. Strein, A.G. Ewing, Anal. Chem. 64 (1992) 1368.
[10] C.E. Bach, R.J. Nichols, H. Meyer, J.O. Besenhard, Surf. Coat.
Technol. 67 (1994) 139.
[11] J. Wang, A. Brennsteiner, A.P. Sylwester, C.L. Renschler,
Electroanalysis 3 (1991) 505.
[12] X. Zhang, J. Wang, B. Ogorevc, U.E. Spichiger, Electroanalysis
11 (1999) 945.
[13] M.I. Montenegro, M.A. Queiros, J.L. Daschbach (Eds.), Microelectrodes: Theory and Applications, Kluwer Academic Press,
Dordrecht, 1991.
[14] K.T. Kawagoe, J.A. Jankowski, R.M. Wightman, Anal. Chem. 63
(1991) 1589.
[15] C. Amatore, B. Fosset, J. Bartelt, M.R. Deakin, R.M. Wightman,
J. Electroanal. Chem. 256 (1988) 255.
[16] C. Lee, F.C. Anson, J. Electroanal. Chem. 323 (1992) 381.
[17] C. Beriet, D. Pletcher, J. Electroanal. Chem. 361 (1993) 93.
[18] M.B. Rooney, D.C. Coomber, A.M. Bond, Anal. Chem. 72 (2000)
3486.
[19] K.B. Oldham, A.M. Bond, J. Electroanal. Chem. 508 (2001) 28.