Anal. Chem.

2006, 78, 7048-7053

Electrochemical Characterization of Recessed

Nanodisk-Array Electrodes Prepared from
Track-Etched Membranes
Takashi Ito,* Ahmad A. Audi, and Gregory P. Dible
Department of Chemistry, Kansas State University, 111 Willard Hall, Manhattan, Kansas 66506

Recessed nanodisk-array electrodes (RNEs) fabricated Scheme 1

from track-etched polycarbonate membranes (TEPCMs)
having cylindrical nanopores (50 nm in diameter) were
characterized using cyclic voltammetry (CV). Such elec-
trodes were prepared by depositing a gold thin film onto
a TEPCM via sputtering or thermal evaporation. CV of the
RNEs showed the transition from linear to radial diffusion
modes of redox-active molecules with decreasing scan
rate. The resulting change in maximum faradic current,
which is the peak current in a peak-shaped CV and the
plateau current in a sigmoidal CV, provides a simple
means for calculating the pore length and effective pore
density within a RNE. This method permits us to assess
the completeness of the seal between a TEPCM and gold
film as well as the extent to which air bubbles block the
nanopores.

A recessed nanodisk-array electrode (RNE) consists of an array

of recessed disk electrodes having nanometer-scale diameters
(Scheme 1). The recessed disks are formed from an insulator-
based membrane that contains cylindrical nanometer-scale pores
aligned parallel to each other, and an electrode blocks one end
of the pores. RNEs have been used to synthesize arrays of metal,
semiconductor, or conducting polymer nanowires via electro-
deposition.1-7 In addition, the recessed electrode structure was
used to study lateral diffusion of electroactive amphiphiles in
bilayer assemblies8-10 and to fabricate chemical sensors that are
* To whom correspondence should be addressed. Phone: 785-532-1451.
Fax: 785-532-6666. E-mail: ito@ksu.edu.
(1) Martin, C. R. Science 1994, 266, 1961-1966.
(2) Schönenberger, C.; van der Zande, B. M. I.; Fokkink, L. G. J.; Henny, M.;
Schmid, C.; Krüger, M.; Bachtold, A.; Huber, R.; Birk, H.; Staufer, U. J.
Phys. Chem. B 1997, 101, 5497-5505.
(3) Demoustier-Champagne, S.; Stavaux, P.-Y. Chem. Mater. 1999, 11, 829-
834.
(4) Nicewarner-Peña, S. R.; Freeman, R. G.; Reiss, B. D.; He, L.; Peña, D. J.;
Walton, I. D.; Cromer, R.; Keating, C. D.; Natan, M. J. Science 2001, 294,
137-141.
(5) Schuchert, I. U.; Toimil Molares, M. E.; Dobrev, D.; Vetter, J.; Neumann,
R.; Martin, M. J. Electrochem. Soc. 2003, 150, C189-C194.
(6) Thurn-Albrecht, T.; Schotter, J.; Kästle, G. A.; Emley, N.; Shibauchi, T.;
Krusin-Elbaum, L.; Guarini, K.; Black, C. T.; Tuominen, M. T.; Russell, T.
P. Science 2000, 290, 2126-2129.
(7) Cho, S. I.; Choi, D. H.; Kim, S.-H.; Lee, S. B. Chem. Mater. 2005, 17, 4564-
4566.
(8) Miller, C. J.; Majda, M. J. Am. Chem. Soc. 1986, 108, 3118-3120.
(9) Miller, C. J.; Widrig, C. A.; Charych, D. H.; Majda, M. J. Phys. Chem. 1988,
92, 1928-1936.
(10) Goss, C. A.; Miller, C. J.; Majda, M. J. Phys. Chem. 1988, 92, 1937-1942.
insensitive to convection.11-13 So far, RNEs have been prepared
by depositing metal onto one face of a track-etched polycarbonate
membrane (TEPCM)2,3,5,7 or onto an anodic alumina mem-
brane,4,14,15 or by using diblock copolymer films on conducting
substrates.6 For all applications of RNEs, the formation of a good
seal between a nanoporous membrane and metal film and the
complete removal of air bubbles from the nanopores are required
to obtain reproducible results. A bad seal (Scheme 1a) leads to
creeping of the electrolyte solution between the membrane and
the metal film,15 which forms a gap whose size often changes
during the measurements. The gap size also varies between RNEs.
Since air bubbles remaining within nanopores are gradually
released, incomplete removal of air bubbles (Scheme 1b) results
in a gradual increase in effective pore density during experiments
as well as variation in effective pore density between RNEs.
Electrochemical methods provide a convenient means to
characterize recessed electrode structures. For example, capacitive
currents measured with cyclic voltammetry (CV) could be used
to qualitatively discuss the seal of an insulating membrane contain-
(11) Morita, K.; Shimizu, Y. Anal. Chem. 1989, 61, 159-162.
(12) Shimizu, Y.; Morita, K. Anal. Chem. 1990, 62, 1498-1501.
(13) Vlassiouk, I.; Takmakov, P.; Smirnov, S. Langmuir 2005, 21, 4776-4778.
(14) Miller, C. J.; Majda, M. J. Am. Chem. Soc. 1985, 107, 1419-1420.
(15) Brumlik, C. J.; Martin, C. R.; Tokuda, K. Anal. Chem. 1992, 64, 1201-
1203.

7048 Analytical Chemistry, Vol. 78, No. 19, October 1, 2006 10.1021/ac061043m CCC: $33.50 © 2006 American Chemical Society
Published on Web 08/23/2006
ing micrometer- to submicrometer-scale pores to a metal film.15-17
In addition, changes in faradic current at different scan rates as a
result of transition of diffusion modes were reported on a single
recessed microdisk electrode fabricated by photolithography,17 on
arrays of recessed micro- and submicrodisk electrodes,15,18 and
on a single truncated cone-shaped nanopore electrode.19,20
In this paper, RNEs having nanometer-scale pore diameters
were characterized using electrochemical methods. TEPCMs ∼10
µm thick and containing an array of cylindrical pores of 50-nm
diameter were used as nanoporous membranes. One face of each
membrane was coated with a gold thin film to construct the RNE
structure. Sputtering and thermal evaporation were used for
coating the TEPCMs. It is known that sputtering5,7 provides a good
seal between the TEPCM and the gold film, whereas a gold layer
coated via thermal evaporation3 often peels away from the polymer
membrane. This study demonstrates that a series of CV measure-
ments at different scan rates can be used to determine the pore
length and effective pore density in a TEPCM-based RNE. These
methods are also shown to provide valuable data on the quality
of the seal between a TEPCM and gold film, as well as the extent
to which air bubbles block the RNE nanopores.
EXPERIMENTAL SECTION
Chemicals and Materials. All solutions were prepared with
water having a resistivity of 18 MΩ cm or higher (Barnstead
Nanopure Systems). Potassium nitrate (Fisher Chemical), potas-
sium ferricyanide (K3Fe(CN)6) (Acros Organics), and 1,1′-fer-
rocenedimethanol (Fc(CH2OH)2; Aldrich Chemical) were of
reagent grade quality or better and used without further purifica-
tion. Track-etch polycarbonate membranes (50-nm pore diameter,
6 × 108 pores/cm2, ∼10 µm thick, 25 mm in membrane diameter)
and gold wire (99.99%) were obtained commercially (Whatman
and Surepure Chemicals, respectively). The pore density of the
TEPCMs was measured using contact-mode atomic force micros-
copy in air (AFM; Digital Instruments Multimode AFM) to be
6.6 × 108 pores/cm2, which was within its nominal precision
((15%) of the manufacturer’s specifications.
Electrode Fabrication. RNEs were prepared by coating the
rougher face of a TEPCM with gold via thermal evaporation
(model DV-502, Denton Vacuum) or sputtering (EFFA Coater,
Ernest F. Fullam). The thickness of the gold layer was >100 nm,
as was confirmed using a surface profiler. The gold-coated TEPCM
was mounted on a glass slide (1 × 1 cm2) that had been previously
spin-coated with PDMS (Sylgard 184, Dow Corning). Electrical
contact to the gold surface was made using conducting copper
tape (Electron Microscopy Sciences). The gold-coated TEPCMs
were used as the working electrode.
Electrochemical Measurements. Electrochemical data were
obtained using a CH Instruments model 618B electrochemical
analyzer. Electrochemical experiments were carried out in a three-
electrode cell (Scheme 2) containing a Ag/AgCl (3 M KCl)
reference electrode and a Pt counter electrode. The RNE (serving
as the working electrode) was immobilized at the bottom of the
cell using an O-ring. The diameter of the membrane area in
(16) Penner, R. M.; Martin, C. R. Anal. Chem. 1987, 59, 2625-2630.
(17) Henry, C. S.; Fritsch, I. Anal. Chem. 1999, 71, 550-556.
(18) Tokuda, K.; Morita, K.; Shimizu, Y. Anal. Chem. 1989, 61, 1763-1768.
(19) Zhang, B.; Zhang, Y.; White, H. S. Anal. Chem. 2004, 76, 6229-6238.
(20) Zhang, B.; Zhang, Y.; White, H. S. Anal. Chem. 2006, 78, 477-483.
Scheme 2
contact with the solution was 6.6 mm, as defined by the inner
diameter of the O-ring. Prior to electrochemical measurements,
0.1 M KNO3 was added to the chamber, and air bubbles within
the nanopores were removed under reduced pressure.21,22 CV
measurements were performed at sweep rates ranging from 2
mV/s to 10 V/s, but the CVs obtained appeared irreversible at
scan rates higher than 5 V/s. CVs obtained at the second potential
cycle are discussed. The maximum faradic current, which is the
peak current in a peak-shaped CV and the plateau current in a
sigmoidal CV, was measured by subtracting the extrapolated
charging current. Chronoamperometry was performed by applying
a potential step from 0 to +0.5 V (vs Ag/AgCl) for Fc(CH2OH)2
and from +0.5 to 0 V (vs Ag/AgCl) for Fe(CN)63-. Data fitting
was performed using the Goal Seek tool in MS-Excel.
Characterization of Electrode Structure. The TEPCM of a
RNE prepared via sputtering was dissolved in CH2Cl2. A horizon-
tally oriented metal substrate was lifted through the CH2Cl2
solution, leading to collection of the remaining gold film on the
metal substrate. The surface structure of the gold film was
measured by tapping-mode AFM. AFM tips used (75 kHz resonant
frequency) were obtained from Budget Sensors.
RESULTS AND DISCUSSION
Diffusion Models for a RNE at Different Scan Rates. The
diffusional flux of molecules to a recessed microdisk-array
electrode is known to change according to the scan rate, spacing
between pores, and pore geometry.15,18 The same model can also
be applied to RNEs containing 50-nm diameter pores. Scheme 3
summarizes the diffusional flux of molecules at a recessed disk-
array electrode (a, pore radius (cm); L, pore length (cm); N, the
number of pores involving the redox reaction) at different time
scales, that is, scan rate, v (V/s), in CV.
For fast scans, only redox-active molecules within nanopores
diffuse linearly to the electrode surface and react (Scheme 3a),
and thus, a peak-shaped voltammogram is obtained. The peak
current (ip (A)) is the sum of faradic currents from individual
recessed electrodes and, thus, is given by the following equation,18
ip ) 0.446nF(Nπa2)C
xnFDv
RT
(1)
where n is the number of electrons (n ) 1 for the redox-active
(21) Monahan, J.; Gewirth, A. A.; Nuzzo, R. G. Anal. Chem. 2001, 73, 3193-
3197.
(22) Dai, J.; Ito, T.; Sun, L.; Crooks, R. M. J. Am. Chem. Soc. 2003, 125, 13026-
13027.
Analytical Chemistry, Vol. 78, No. 19, October 1, 2006 7049
Scheme 3
molecules used in this study), F is Faraday’s constant (96485
C/mol), R is the gas constant (8.31 J/Kmol), T is temperature
(298 K for 25 °C), D is the diffusion coefficient of the redox-active
species (7.6 × 10-6 cm2/s for Fe(CN)63- and 6.4 × 10-6 cm2/s
for Fc(CH2OH)2),23,24 and C (mol/cm3) is its concentration.
Importantly, the peak current is also dependent on N, the number
of nanopores participating, but not on L, the length of the channels.
Thus, assuming the C and D within the pores are the same as
those in solution bulk and there is no creeping of the solution
between the TEPCM and gold, N can be determined from the
slope in the relationship between of ip and v1/2. From N, the density
of open nanopores (d (pores/cm2)) can be determined from
N ) πr2d (2)
where r is the radius of the O-ring in Scheme 2. On the other
hand, if the seal between the TEPCM and gold film is not
complete, a larger ip will be observed because of the larger
electroactive surface area formed by the creeping of the solution
between the TEPCM and gold film.
At slower scan rates, the redox-active molecules will radially
diffuse from outside the pores (Scheme 3b), and thus, a sigmoidal
voltammogram is observed. The limiting current of such voltam-
mograms (ilim) can be written as follows:25
4πnFCDa2N
ilim ) (3)
4L + πa
This limiting current is observed only when the spacing between
pores is large;26 otherwise, the radial diffusion regimes from
(23) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, Fundamentals and
Applications, 2nd ed.; Wiley: New York, 2001.
(24) Fan, F.-R. F. J. Phys. Chem. B 1998, 102, 9777-9782.
(25) Bond, A. M.; Luscombe, D.; Oldham, K. B.; Zoski, C. G. J. Electroanal.
Chem. 1988, 249, 1-14.
7050 Analytical Chemistry, Vol. 78, No. 19, October 1, 2006
Figure 1. Tapping-mode AFM image (700 × 700 nm2) of the gold
film surface exposed after the removal of the TEPCM of a TEPCM-
based RNE prepared via sputtering. The line profile from the AFM
image is shown below.
multiple pores will overlap (Scheme 3c), again giving a peak-
shaped voltammogram.15 In the absence of the overlap of
individual radial diffusion layers, the limiting current in the
sigmoidal CV at low scan rate will be very similar, regardless of
scan rate, and should be also similar to that obtained using
chronoamperometry. In such a case, the limiting current ilim can
be used to determine L (see eq 3) if the pore number N (or the
effective pore density d) is independently determined from the
CVs at faster scan rates (see eq 1).
The bottom gold electrodes of RNEs used here do not have a
perfect disk shape. Figure 1 shows an AFM image of the surface
structure of a bottom gold film after dissolving a gold-coated
TEPCM in CH2Cl2. Bumps formed by gold deposited within
TEPCM nanopores were observed. The diameter of the bumps
was ∼70 nm, which is a little larger than the nanopore diameter
(∼50 nm), probably because of the convolution of the AFM tip.
The top of the bump is not flat, and instead, there is a hole at the
center of each bump, which was formed by preferential gold
deposition near the pore surface.7 However, the resulting rough-
ness of the electrode surface is expected to be smaller than the
height of the bumps (<40 nm) and, thus, is much smaller than
the thickness of the diffusion layer (2 µm for v ) 10 V/s, according
to eqs 4 and 5; see below). This indicates that the faradic current
of RNEs used here will be determined by the cross-sectional area
of the diffusion field rather than the actual electrode surface area.23
Under the experimental conditions used in this study, i.e., CV at
v ∼ 2 mV/s to 10 V/s and chronoamperometry, the effect of
electrode surface roughness on the faradic current is, thus,
negligible, and the above equations can be applied to TEPCM-
based RNEs used in this study.
Cyclic Voltammograms on RNEs Prepared via Gold Sput-
tering. Figure 2a shows typical cyclic voltammograms in 1.0 mM
(26) Beriet, C.; Ferrigno, R.; Girault, H. H. J. Electroanal. Chem. 2000, 486,
56-64.

Figure 2. (a) Cyclic voltammograms for a TEPCM-based RNE in
1.0 mM K3Fe(CN)6 and 0.1 M KNO3 at five different scan rates (5,
20 mV/s; 0.1, 0.4, and 1 V/s). Gold was deposited via sputtering,
and almost all nanopores are filled with the solution. (b) Cyclic
voltammograms for a TEPCM-based RNE having blocked nanopores
in 1.0 mM K3Fe(CN)6 and 0.1 M KNO3 at the five different scan rates.
Gold was deposited via sputtering. (c) Relationship between the
square root of scan rate and voltammetric maximum reduction current
of 1.0 mM Fe(CN)63-. Filled circles: taken on the RNE whose pores
are not blocked (data from Figure 2a, but not all CVs are shown in
Figure 2a). Open circles: taken on the RNE in which some of the
pores are blocked (data from Figure 2b, but not all CVs are shown in
Figure 2b). The solid and dashed lines were obtained by least-squares
fitting of the data shown as filled circles using eqs 1-2 and 3,
respectively, which gave d ) 7.1 × 108 pores/cm2 and L ) 13.6 µm.
In panels a and b, “+” indicates zero current.
K3Fe(CN)6 for a TEPCM-based RNE prepared via gold sputtering.
CVs remain very similar for >24 h once the air bubbles are
removed, whereas the faradic current in a CV gradually increases
when air bubbles are present in the nanopores. Sigmoidal
voltammograms were observed at lower scan rates, and then redox
peaks were observed at g0.4 V/s. This indicates that, as discussed
above, radial diffusion is dominant at slower scan rates, and the
contributions of linear diffusion become more significant with
increasing scan rate. On the TEPCM-based RNEs, transition from
sigmoidal (Scheme 3b) to peak-shaped CVs (Scheme 3c) at very
slow scan rates was not observed because of the relatively large
spacing between pores: the spacing between pores is 0.4 µm on
average, calculated from the pore density (6 × 108 pores/cm2;
provided by the manufacturer), which is 8 times larger than the
pore diameter (50 nm). This is a big contrast to recessed
microdisk-array electrodes formed by anodic alumina membranes
having much higher pore density (∼65% porous), which did not
give sigmoidal CVs at any scan rates in the absence of convec-
tion.15 On the other hand, the peak potential difference (∼100 mV)
in the peak-shaped CVs is larger than the theoretical value for
the reversible CV (60 mV), which is probably due to uncompen-
sated resistance in the system.17
Figure 2c (filled circles) shows the relationship between v1/2
and the maximum reduction current, which is the peak current
in a peak-shaped CV and the plateau current in sigmoidal CV.
The maximum reduction current was similar at scan rates slower
than 0.3 V/s and gradually increased at faster scan rates. The
plateau current in Figure 2c (2.6 µA) is close to the limiting current
measured with chronoamperometry (2.8 µA), which supports the
negligible overlap of radial diffusion layers due to the relatively
large spacing between pores (vide supra). The scan rate where
the maximum reduction current starts to increase is close to the
transition scan rate (0.3 V/s for L ) 11 µm) estimated from
equations on the transition time, τ, converted from the scan rate
and the thickness of a diffuse layer, which corresponds to the
pore length (L) when the transition of the diffusion modes
occurs.15
RT
τ) (4)
Fv
L ) x2Dτ (5)
The break in maximum current due to the transition of the
diffusion modes is, however, subtle compared with that observed
using a RNE based on an anodic alumina membrane in stirred
solution.15 The subtle break in maximum current can be explained
by the nonuniform pore length in a TEPCM due to variation in
track tilt angle.2 This difference in pore length gives a different
transition scan rate at each pore according to eqs 4 and 5, resulting
in the subtle break in the maximum current.
The effective pore density (d) was estimated from the change
in peak current at the faster scan rates by using eqs 1 and 2. The
average and standard deviation of the effective pore density of
three different electrodes were (6.5 ( 0.6) × 108 pores/cm2, which
is close to the pore density provided by the manufacturer (6 ×
108 pores/cm2; nominal precision, ( 15%) and one measured by
AFM (6.6 × 108 pores/cm2). In addition, the pore length calculated
from the plateau current using eq 3 was (14 ( 2) µm, which is
similar to the thickness of TEPCM measured by surface profilo-
metry (11 µm).
Similar trends were also observed for different redox-active
molecules. Figure 3a shows typical cyclic voltammograms for 3.0
mM Fc(CH2OH)2 using a TEPCM-based RNE prepared via gold
sputtering. The transition from sigmoidal to peak-shaped CVs was
similarly observed with increasing scan rate. Figure 3c (filled
circles) shows the relationship between v1/2 and the maximum
oxidation current. The maximum oxidation current was similar
at scan rates slower than 0.2 V/s and gradually increased at faster
scan rates. Again, the plateau current (7.3 µA) is close to the
limiting current measured with chronoamperometry (7.5 µA). The
effective pore density and the pore length , calculated using data
from three different electrodes, were (7.4 ( 0.6) × 108 pores/
cm2 and (12 ( 1) µm, respectively. These values are similar to
those obtained in 1 mM Fe(CN)63-. These results indicate that
Analytical Chemistry, Vol. 78, No. 19, October 1, 2006 7051

Figure 3. (a) Cyclic voltammograms for a TEPCM-based RNE in
3.0 mM Fc(CH2OH)2 and 0.1 M KNO3 at five different scan rates (5,
20 mV/s; 0.1, 0.4, and 1 V/s). Gold was deposited via sputtering,
and almost all nanopores are filled with the solution. (b) Cyclic
voltammograms for a TEPCM-based RNE in 2.9 mM Fc(CH2OH)2
and 0.1 M KNO3 at the five different scan rates. Gold was deposited
via thermal evaporation. (c) Relationship between the square root of
scan rate and voltammetric maximum current of 3 mM Fc(CH2OH)2.
Filled circles: taken on the RNE prepared via gold sputtering (data
from Figure 3a, but not all CVs are shown in Figure 3a). Open
circles: taken on the RNE prepared via gold thermal evaporation (data
from Figure 3b, but not all CVs are shown in Figure 3b). The solid
and dashed lines were obtained by least-squares fitting of the data
shown as filled circles using the theoretical equations, which gave d
) 7.0 × 108 pores/cm2 and L ) 11.2 µm. In panels a and b, “+”
indicates zero current.
the CV measurements at different scan rates provide a simple,
reproducible means for estimating the effective pore density and
length of a RNE.
Effect of Blocking of RNE Nanopores. When removal of
air bubbles from the RNEs was not complete (e.g., due to
insufficient time under reduced pressure), the faradic currents
observed were smaller than those of a RNE having open pores.
Figure 2b depicts representative CVs of 1.0 mM K3Fe(CN)6
obtained under these conditions for a TEPCM-based RNE
prepared via gold sputtering. The transition from sigmoidal to
peak-shaped CVs was similarly observed, as was the expected
increase in maximum reduction current at higher scan rates
(Figure 2c (open circles)). However, the slope of the increase in
peak current (at higher scan rates) and the limiting current (at
slower scan rates) are smaller in the presence of air-bubbles. The
smaller slope and limiting current are expected from eqs 1 and 3,
respectively. For this specific RNE, the effective pore density and
7052 Analytical Chemistry, Vol. 78, No. 19, October 1, 2006
the pore length were 3.0 × 108 pores/cm2 and 12 µm, respectively.
When these values are compared among different RNEs having
nanopores blocked by air bubbles, the observed effective pore
density varied in relation to the length of time the sample was
exposed to vacuum; however, the pore length observed was always
close to the film thickness (11 µm). This result indicates that the
electrochemical measurements are suitable to determine the
density of open pores in a RNE in the case of a good seal between
the TEPCM and gold thin film.
Cyclic Voltammograms on RNEs Prepared via Thermal
Gold Evaporation. Figure 3b shows cyclic voltammograms in
3.0 mM Fc(CH2OH)2 for a TEPCM-based RNE prepared via
thermal gold evaporation. At all scan rates, the capacitive current
is much larger than those observed at RNEs prepared via gold
sputtering. This large capacitive current originates from the
creeping of the solution between the TEPCM and gold thin film
due to weak adhesion between them.15 Indeed, gold films
deposited via thermal evaporation can be easily peeled from the
TEPCMs. The faradic current is also very large (Figure 3c, open
circles), especially at higher scan rates. Increased faradic currents
result from redox reactions occurring in the resulting gap. At
slower scan rates (e5 mV/s), the CV approaches sigmoidal shape,
and the current is close to the plateau current observed with RNEs
prepared via gold sputtering. This is probably because the current
at slow scan rates is mainly determined by mass transport of
redox-active molecules through the TEPCM nanopores, which
involves radial diffusion of redox-active molecules from the
solution bulk into the nanopores. This is supported by the
observation that the limiting current measured with chronoamper-
ometry (7.9 µA) on the RNE prepared via the thermal evaporation
method is close to the value observed with the RNE prepared via
gold sputtering (7.5 µA, vide supra). Similar results (i.e., larger
peak currents in CVs and similar limiting currents in chrono-
amperograms, compared to the theoretical predictions) have also
been reported for electrodes modified with a track-etched poly-
ester membrane mechanically contacted to the electrode surface.27
The distance between the membrane and electrode cannot be
controlled accurately in these systems.
For RNEs prepared via thermal gold evaporation, the larger
capacitive and faradic currents in CVs have been observed for all
RNEs prepared to date. In addition, the absolute value of these
currents was different for individual electrodes, because the
distance between a TEPCM and gold film is not controllable. In
contrast, the limiting current in chronoamperometry was very
similar among the different electrodes. This result indicates that
the density of open pores (or pore length) in RNEs can be
determined from the limiting current measured by chronoamper-
ometry using eq 3, even in the presence of the gap due to the
incomplete seal between a TEPCM and gold film, as reported
previously.27
SUMMARY AND CONCLUSIONS
This paper has demonstrated that CV measurements at
different scan rates (0.002-10 V/s) provide a rapid, reproducible
means for determining the effective pore density and pore lengths
within RNEs. This method is applicable to characterizing RNEs
(27) Kralj, B.; Dryfe, R. A. W. Phys. Chem. Chem. Phys. 2001, 3, 3156-3164.
having relatively low pore density, because such RNEs show the
transition between linear and radial diffusion modes. In contrast,
NREs having high pore densities cannot be characterized using
the proposed method, because the overlap of radial diffusion layers
prevents observation of this transition.15 Although the analysis
methods used in this paper are not based on detailed computer
simulation19,20 and although the distribution of the pores is random,
the results are fairly reasonable, probably because the current
measured is the sum of currents from a large number of recessed
nanodisk electrodes. The electrochemical characterization method
demonstrated here will provide those developing RNEs with a
simple, rapid, and reproducible means to assess the quality of
the devices being prepared.
ACKNOWLEDGMENT
The authors thank Dr. Daniel A. Higgins (Department of
Chemistry, Kansas State University) for access to the thermal
evaporation system, Drs. Hongxing Jiang and Zhaoyang Fan
(Department of Physics, Kansas State University) for providing
the sputter coater used in early experiments, and Dr. Christopher
T. Culbertson (Department of Chemistry, Kansas State University)
for access to the surface profiler. They also thank Dr. Daniel A.
Buttry (Department of Chemistry, University of Wyoming) for his
suggestions. The authors gratefully acknowledge financial support
from Kansas State University.
Received for review June 7, 2006. Accepted July 26, 2006.
AC061043M
Analytical Chemistry, Vol. 78, No. 19, October 1, 2006 7053