Received 3 August 2006; received in revised form 28 February 2007; accepted 14 March 2007
Available online 25 April 2007
Abstract
Electrically conductive polymers, such as polypyrrole (PPy), show promise for modifying the dimensions and properties of micro- and nanoscale
structures. Mechanisms for controlling the formation of PPy films of nanoscale thickness were evaluated by electrochemically synthesizing and
examining PPy films on planar gold electrodes under a variety of growth conditions. Tunable PPy coatings were then deposited by electropoly-
merization on the sidewalls of individual, electrically addressable carbon nanofibers (CNFs). The ability to modify the physical size of specific
nanofibers in controllable fashion is demonstrated. The biocompatibility, potential for chemical functionalization, and ability to effect volume
changes of this nanocomposite can lead to advanced functionality, such as specific, nanoscale valving of materials and morphological control at
the nanoscale.
© 2007 Elsevier B.V. All rights reserved.
0379-6779/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2007.03.004
B.L. Fletcher et al. / Synthetic Metals 157 (2007) 282–289 283
can be electrochemically deposited at room temperature and pore spacings on the order of 500 nm. Reducing the spacing by
under aqueous conditions. Typically, this is accomplished by increasing the diameter of the CNFs can lead to molecular-scale
anodic oxidation of the pyrrole monomer in an ionic solution, sieving. The electropolymerization of PPy is an attractive route
an environment compatible with biomolecules. A number of to realizing this goal. Further, the biocompatibility, potential for
biochemical immobilization methods exploit pyrrole polymer- chemical functionalization, and ability to effect volume changes
ization [15,16]. To initiate polymerization, an electrically active in PPy can lead to advanced designs that allow for the specific
scaffolding material is required and serves as a backbone for for- gating of materials. Here we demonstrate that electropolymer-
mation of the PPy film. This can enable an alternate approach to ization of PPy can modify the physical size of specific nanofibers
selective patterning of thin films. That is, addressable electrodes in a controllable fashion.
can be used in place of the photolithography-dependent tech-
niques that are required in conventional patterning processes. 2. Experimental
The thickness of the resulting polymer film can be tailored by
controlling the amount of electric charge that passes through 2.1. Materials
the circuit during electropolymerization [17]. The controllabil-
ity, addressability, and biocompatibility of pyrrole films can have Pyrrole monomer was obtained from Acros Organics. Silicon
significant advantages when complex fabrication schemes or the wafers with and without 1 m of thermal oxide were obtained
synthesis of tunable nanocomposite materials are required. from Silicon Quest International (Santa Clara, CA). Potassium
Here we investigate the use of PPy films for controllably chloride and 1 M sulfuric acid of reagent grade were obtained
modifying vertically aligned carbon nanofibers (CNFs) with from Sigma–Aldrich.
high spatial precision. CNFs can be deterministically grown,
allowing for command of their length, shape, orientation, and 2.2. Wafer preparation
chemical composition [18–20]. CNFs are nanoscale materi-
als, with diameters on the order of 500 nm, or less, and with For PPy film characterization, planar electrodes were pre-
length up to several tens of microns [21]. Patterned catalyst par- pared on SiO2 wafers. Metal layers were deposited on these
ticles determine the placement of individual fibers or forests wafers using the electron beam evaporation (EBE) technique
of CNFs, which are grown by a plasma enhanced chemical (100 Å Ti, 2000 Å Au). The wafers were then diced using a
vapor deposition (PECVD) process. CNFs are compatible with DiscoDad-2H6T wet dicing saw into strips 0.5 cm wide and 4 cm
a variety of MEMs-based processing techniques, can be con- long.
jugated with biomolecules, and are electrically addressable For PPy-CNF nanocomposite characterization, 100 Å Ti,
[22–25]. This combination of features enables the incorpora- 2000 Å W, 100 Å Ti, 50 Å Si metal stacks were deposited on
tion of nanoscale elements within larger (wafer) scale structures, SiO2 wafers using EBE. The wafers were then vapor primed
thereby enabling a wide range of applications, including elec- with hexamethyldisilazane (HMDS) priming agent and photore-
tron emission devices, gene delivery structures, and synthetic sist was spin coated. Nickel catalyst sites for CNF growth were
membranes [25–28]. then defined using UV-optical projection lithography (GCA
Carbon nanofibers can be used as microelectrodes, as demon- AutoStep 200). Resulting catalyst sites were 500 nm in diameter
strated in such applications as electrochemical probes [23] and and were patterned at a 5 m pitch. After a post-exposure bake
sensors [24]. The ability to electrically address individual car- and development, residual photoresist was removed in an oxygen
bon nanofibers also presents a route to selectively controlling plasma. Catalyst metal, 500 Å Ni, was deposited by EBE on the
their shape through electropolymerization. Examples of car- wafers and the excess metal was removed using an acetone liftoff
bon nanotube (CNT) surface modification by polymerization of process. CNF growth was then performed using a previously
polypyrrole exist in the literature. In these studies, thin polypyr- described PECVD process [19–21]. Resulting CNFs were, on
role coatings (10–93 nm) are used to modify the electrical average, 10 m tall and 500 nm thick halfway between the base
properties or surface chemistry of bulk addressed, stochastically and the tip (where measurements were made). After growth, an
grown forests of CNTs [29,30]. This suggests the possibility of additional layer of photoresist was spin coated on these wafers to
depositing polypyrrole films on individually addressable carbon pattern leads for addressing the CNFs. The interconnect pattern
nanofiber electrodes as a means of selectively modifying their was defined using a contact aligner. After development, resid-
geometry and other properties. ual photoresist was removed by an oxygen plasma treatment.
CNF arrays are promising, three-dimensional scaffolds for The metal stack in the exposed areas of the wafer was then
the synthesis of PPy nanocomposites. A tunable PPy film on the etched away using an SF6 /O2 /CF3 based plasma for 7 min. This
surface of arrays of carbon nanofibers would be useful for inte- provided arrays of electrically addressable nanofibers, as well
gration with MEMs and biomimetic devices. Specific to current as unaddressed “control” nanofibers in adjacent regions where
interests, a greater understanding of this nanocomposite would metal was removed. The wafer was stripped of remaining pho-
be essential for designing membrane structures with defined pore toresist with acetone and the defined leads were wire bonded to a
sizes. Previous efforts have demonstrated the utility of CNFs to custom printed circuit board. A circle of epoxy (FDA2T, Tracon,
create membranes within microfluidic structures [27,28,31]. In Bedford, MA) was painted around the perimeter of the device,
this application, the physical spacing between nanofibers deter- forming a fluidic well to confine subsequent electrochemical
mines the pore size. CNF growth typically leads to average deposition/analysis.
284 B.L. Fletcher et al. / Synthetic Metals 157 (2007) 282–289
2.3. Characterization tools positioned above the 100 L droplet of monomer so that its
tip was immersed in monomer but not touching the structure.
The electropolymerization of PPy was controlled using a The platinum counter electrode was similarly positioned from
Model 660A CH Instruments Electrochemical Analyzer. PPy above. A constant potential of 0.75 V was applied for a range
film thicknesses were quantified in solution using the acous- of polymerization times from 15 to 105 s. The structure was
tic ac mode of a Molecular Imaging PicoPlus AFM system. then washed in deionized water, dried, and examined in the
Data analysis software was written in Matlab 6.5.0 (Mathworks, SEM.
Inc.). Film roughness and thickness data were obtained from
cross-sections through 2D captured, AFM images. PPy-CNF 3. Results and discussion
nanocomposites were also investigated using a Hitachi S4700
high-resolution cold cathode field emission scanning electron For synthesis of PPy films of submicron thickness, we eval-
microscope (SEM). uated the effect of polymerization reaction time, monomer
concentration, and applied bias on film formation to deter-
2.4. Polypyrrole film growth on planar electrodes mine the relative degree of control afforded by these easily
manipulated variables. The best variable to use for controlling
Control of the formation of PPy films was investigated polymerization was then selected by determining which vari-
by studying the effects of three electropolymerization growth able produced a reproducible and linear response in growth
parameters. These were polymerization time, monomer concen- rate and quality. Variables such as pH and temperature also
tration, and applied voltage. Monomer solutions were prepared have an effect on electropolymerization but, outside of a
in 300 mM KCl and 0.01 M H2 SO4 and were handled in 1.5 mL narrow range, can have deleterious effects on biomolecules
centrifuge tubes. and were not considered for controlling film thickness. After
A platinum coil was used as the counter electrode and evaluating the reaction parameters and selecting the best vari-
a Ag/AgCl (3 M KCl) electrode with a glass frit mem- able, tunable PPy coatings were deposited on the sidewalls of
brane was used as the reference. The counter, reference, and CNFs.
gold planar electrode structure were immersed in monomer To facilitate the evaluation of these reaction parameters, PPy
solution, with care being taken to avoid contact between elec- films were synthesized on gold planar electrodes. This enabled
trically active surfaces. Constant potential was applied using accurate film thickness measurements using an atomic force
the electrochemical workstation over a given polymerization microscope. While PPy films nucleate on the surface of gold
time. electrodes differently than on carbon-based electrodes [32,33],
For assessing polypyrrole coatings on gold electrodes, an the resulting effects are typically limited to physical proper-
area of polypyrrole in the center of the electrode was typically ties such as surface morphology and crystal structure. In some
scraped clean with forceps after polymerization to provide the cases, the electrode material may also have an effect on the
abrupt change in height necessary for accurate thickness mea- polymerization reaction rate. If the electrode does not con-
surements. Polypyrrole film thicknesses were determined from duct current uniformly, PPy will nucleate and propagate more
the lateral cross-sections of resulting AFM scans, with the gold quickly on the less resistive areas of the electrode. The forma-
substrate providing the baseline from which measurements were tion of oxides on the surface of the electrode can also slow
made. or inhibit the polymerization reaction. Further, some electrode
For variable polymerization time experiments, the monomer materials are subject to dissolution during electropolymeriza-
concentration was held constant at 20 mM pyrrole. A constant tion. In these cases, anodic polarization leads to dissolution
potential of 0.65 V was applied for polymerization times that of the electrode material and passivation of the substrate [33].
ranged from 15 to 180 s. For variable monomer concentration However, if the electrode material is inert (Au, Pt, glassy car-
experiments, a constant potential of 0.65 V was applied for 15 s bon) and conducts current uniformly, its participation in the
using monomer solutions with concentrations of 10–500 mM. polymerization reaction is negligible [33,34]. Even when the
For variable potential experiments, a 20 mM monomer solution electrode material is subject to dissolution, the effects on the
was prepared. Potentials covering a range of 0.7–1.0 V were polymerization rate are relatively small [35]. Thus, it is possible
applied for 15 s. to evaluate the effect of reaction parameters on films synthe-
sized on gold and apply these observations as a first order
2.5. Polypyrrole film growth on carbon nanofiber electrodes approximation of what will occur with activated carbon-based
electrodes.
Conditions for polypyrrole film growth on CNF electrodes Studying films in aqueous solution prevents the use of many
were based on results from polypyrrole film characterizations commonly available characterization instruments, such as con-
on planar gold electrodes. For these experiments, a wire bonded ventional electron microscopy tools. The sub-micron features of
microelectrode structure was secured in place on top of a metal the sample add further limitations and make tools such as the
stand. Pyrrole monomer was prepared at a 20 mM concentration profilometer less practical. A readily accessible characterization
and ∼100 L was pipetted into a fluidic well formed from epoxy. tool was the atomic force microscope (AFM). The AFM is capa-
A single nanofibered lead of the electrode array was connected ble of examining samples in aqueous media and is sufficiently
as the working electrode. The Ag/AgCl reference electrode was sensitive for measuring nanoscale features.
B.L. Fletcher et al. / Synthetic Metals 157 (2007) 282–289 285
3.2. Control of pyrrole coating thickness on carbon needed for a faithful response from the AFM’s z-piezo dur-
nanofibers ing scannings, making this approach inefficient for routine data
collection.
A remarkable degree of control over the shape, location, An alternate approach that facilitated the use of conventional
and chemical composition of carbon nanofibers can be exerted tips was considered. The nanofibers were buried in a photoresist
by adjusting the plasma growth parameters during synthesis layer such that ∼500 nm of their tips were exposed [40], reduc-
[17–20]. However, selective modification of the geometry of ing the necessary deflection of the AFM tip and, subsequently,
individual or groups of nanofibers within an array is not feasible improving the quality of images collected using conventional
through alteration of plasma process parameters. Post-synthesis AFM tips. However, variations in nanofiber height, and thus the
modification of carbon nanofibers, as described in this work, can amount of exposed nanofiber tip, made it necessary to examine
however be used to alter the geometry of individual or groups the same individual nanofibers before and after polymerization
of fibers. for accurate film analysis. Additionally, photoresist was found
PPy was deposited on the surfaces of CNFs by controlled to be problematic when used in the presence of PPy. Typical sol-
electrodeposition. Initial analyses of PPy-coated CNFs were vents for dissolving photoresists, such as methanol and acetone,
pursued by direct analysis using AFM in buffered solutions. had a detrimental effect on the PPy films. During polymeriza-
However, this method of characterization presented unique chal- tion, the presence of photoresist also appeared to reduce the
lenges. Although the probe tip of an AFM allows sensitive amount of polymerized pyrrole on the exposed portions of the
nanoscale measurements in vertical and lateral dimensions, its carbon nanofibers and decreased the observed oxidation cur-
aspect ratio prevents accurate measurements of tall, high aspect rents; possibly due to loss of monomer from solution due to
ratio structures. High aspect ratio AFM tips are commercially partitioning of pyrrole into the photoresist matrix. These obser-
available and yield improved results. However, these probes are vations have ramifications for multistep fabrication protocols
significantly more expensive and proved to be more fragile than that involve photoresist patterning and electropolymerization of
conventional probes. Further, slow scan speeds of 0.1 lines/s pyrrole. Even after burial within photoresist, the aspect ratio
(∼10 times slower than scanning with conventional tips) were of the carbon nanostructures remained too high for accurate
Fig. 2. SEM images of CNFs selectively modified by electropolymerization of PPy. (A) The electrical lead labeled 1 has not been polymerized. Leads 2–5 are
progressively darker due to the presence of increasingly thick PPy coatings. (B) A close up of CNFs modified by PPy. The surrounding SiO2 substrate and CNFs are
unpolymerized. (C) CNFs on an electrical lead, prior to polymerization and (D) after polymerization. The surrounding SiO2 substrate and CNFs are unmodified by
the PPy deposition.
B.L. Fletcher et al. / Synthetic Metals 157 (2007) 282–289 287
Fig. 3. SEM images of electrically addressed CNF electrodes before polymerization of pyrrole (A and B) and after (C and D). A deposition of 75 s was performed
on the nanofibers depicted in (A) before collecting the image shown in (C). A deposition of 115 s was performed on the nanofibers depicted in (B) to yield the result
shown in (D).
collection of film characteristics in the lateral direction. Addi- Resulting PPy films were analyzed by comparing electron
tionally, the growth of the polymer would sometimes extend out micrographs of individual nanofibers before and after polymer-
from the carbon nanofibers and over the photoresist, resulting ization. Fig. 3 shows electron micrographs of groups of CNFs
in a blurring of the interface between the nanofibers and the prior to polymerization (A and B) and after polymerization of
photoresist. Thus, accurate AFM measurements of the polypyr- PPy (C and D). As learned from the studies on planar gold elec-
role coating on carbon nanofibers are complicated by multiple trodes, polymerization time proved to be an effective way to
factors. control the formation of polypyrrole films. Visual inspection of
Due to the described challenges, electropolymerization on the electron micrographs reveals that the roughness of the poly-
individual CNFs was characterized by SEM. This approach is mer coating increases as the polymerization time and thickness
reasonable considering that only small, predictable ∼7% PPy increase. This might be partially attributed to the relatively high-
film volume reductions are induced by dehydration of planar applied bias during polymerization. CNF surface defects may
PPy films [9 and data not shown]. Voltage and monomer con- also be physically accentuated as the PPy film increases in thick-
centration were constant for these experiments while a range ness. In addition, the sputtering of the substrate onto the CNFs
of polymerization times were studied. PPy films were synthe- during fiber growth can lead to the passivation of some areas of
sized on specific groups of CNFs by applying potential to the the nanofiber surface. PPy would initially polymerize at a higher
metal leads addressing them. This restricted PPy synthesis to the rate on the more electrochemically active areas, contributing to
addressed CNFs while leaving surrounding CNFs unchanged. the increasing roughness of the polymer coating.
The ability to selectively pattern the CNFs can be assessed in Fig. 4 shows the relationship between polymerization time
the SEM micrographs presented in Fig. 2. In Fig. 2A, electri- and PPy film thickness on the CNF electrodes. A linear relation-
cal leads with CNFs modified by PPy coating appear as the ship is observed with PPy film formation occurring at a rate of
lines labeled 2–5. The progressive darkening in color, from 9 nm/s. This rate differs from rates determined on gold planar
leads 2 to 5, corresponds to an increase in polymer coating electrodes under comparable reaction conditions. Size effects
thickness due to increasing polymerization times. Surround- appear to play a role in the rate of film formation that may require
ing CNFs grown on the SiO2 substrate and on other electrical further study. However, as with the planar gold electrodes, the
leads (labeled 1) were not addressed and have not been modified growth rate appears to become linear with time after initially
(see Fig. 2B–D). forming relatively slowly.
288 B.L. Fletcher et al. / Synthetic Metals 157 (2007) 282–289
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