Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

DESYGN IT - Special Edition

Design, Synthesis and Growth of Nanotubes for
Industrial Technology

Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and

Vertically Aligned Nanofibers by Plasma Assisted Functionalization

Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou,
Manuel Ruether and Werner Blau
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This is an AZo Open Access Rewards System (AZo-OARS) article distributed under the terms of the AZo–OARS
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Submitted: 6th November 2007

Posted: 16th November 2007

DOI: 10.2240/azojono0126

Topics Covered
Abstract
Keywords
Introduction
Experimental
Production of Carbon Nanotubes
Production of Aligned Grown CNTs
Plasma Treatment
Analytical Methods
Results and Discussion
Bucky Paper Production
Plasma Treatment of Bucky Papers
Plasma Treatment of Aligned Grown CNTs
Conclusions
Acknowledgment
References
Contact Details

Abstract

Within the DESYGN-IT research project, funded by the European Commission, carbon
nanotubes (CNT) were investigated in the form of powder, vertically grown on a Si substrate
and as CNT sheets or mats, mostly referred as to "bucky paper". Due to their hydrophobic and
inert nature, functionalization or alteration of nanotubes can be necessary to optimize them for
desired applications. The low pressure glow discharge treatment was investigated in terms of
their ability to increase the wettability of bucky papers produced from multi walled carbon
nanotubes (MWNT) powders. Hydrophilized bucky papers are required for their use as

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 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

actuators in an electrolyte solution or a substrate for cell cultures. The opening of end caps of
aligned grown CNTs based on plasma treatment was a second aim. The as-produced carbon
nanotube materials (powder, bucky paper, aligned structures) as well as the plasma treated
samples were characterized by surface analytical techniques like SEM, ESCA, TGA, BET to find
optimized parameter sets. By using oxygen containing plasmas, the increase in wettability of
CNT mats could be successfully shown. Plasma polymerisation of a carbofluorine monomer
onto a bucky paper leads to superhydrophobic surfaces. We found that under gentle oxidation
parameters the vertical alignment of MWNTs remains unchanged whereas more harsh
conditions destroy the CNT shape without opening the end caps.

Keywords

Characterization, carbon nanotube, bucky paper, plasma treatment, functionalization, ESCA

Introduction

Ever since their discovery, carbon nanotubes have been heralded as the new wonder material
of the future. Their remarkable mechanical and electronic properties destine them to play a
major role in all kinds of nanotechnologies and molecular electronics [1, 2, 3]. At least two
major hurdles have to be overcome in order to fulfil this potential. First, manipulation of
individual tubes is at best difficult today, which prevents mass production of devices. Second,
the ability to fine-tune the various properties of the material to suit particular applications has
to be achieved. Thus there is a need to develop functionalization techniques for the post-
growth manipulation of the properties of the nanotubes [4, 5].
For example the application of nanotubes as reinforcements in polymer composites, substrates
for cell culture, sensors, actuators and field emitters with as-grown nanotubes is
technologically difficult due to the nonreactive and hydrophobic nature (limited solubility in
organic solvents), the relative noncleanliness of their surface (presence of an amorphous
carbon layer), and the natural agglomeration of the CNTs into bundles. To overcome these
problems, a modification of the carbon nanotubes by changing their surface chemical
composition has proven to be efficient.
Functionalizing the carbon nanotubes with a number of functional groups is known to increase
their chemical reactivity and can be used as a starting point for further chemical modification.
Several methods such as chemical [6, 7, 8, 9], electrochemical [10], polymer wrapping [11],
and plasma treatment have been applied to modify the CNT surface. Dai et al. describe the
opening of aligned grown nanotubes capped by Fe nanorods via H2O-plasma etching, as well as
acetaldehyd-plasma-activation and polymer-film deposition [12, 13]. In addition to that, other
films like PMMA [14] or pyrrole [15] have been deposited. The functionalization of CNTs has
been explored e.g. by using hydrogen [16], nitrogen [17], ammonia [18], O2/Ar [19], O2 [20],
CF4 [21, 22], or SF6 [23] plasmas. Crucially, for use of nanotube arrays in field emission and
sensor devices we have shown that plasma functionalization [24] can preserve the vertical
alignment of carbon nanotube arrays.
The ends of vertically aligned carbon nanotubes or nanofibers as synthesized are normally
capped by a carbon encapsulated catalyst particle. In order to enable the insertion of guest
molecules (DNA, hydrogen etch) the opening of the ends of nanotubes is desired. The various
methods used so far are based on three principles (i) wet chemical dissolution (ii) mechanichal
break up or (ii) high temperature oxygen assisted burning. However such methods are
accompanied by deleterious effects of destroying the vertical alignment and electronic
structure of the nanotubes.
In this paper we report a rapid and environmental friendly low pressure glow discharge (LPGD)
method to prepare carbon nanotube bucky papers with controllable wettability. We also report
on the effect of room temperature LPGD on the morphology and surface chemistry of vertically
aligned carbon nanofibers. Characterisation of the functionalized CNTs and nanofibers has been
carried out by surface analytical techniques like SEM, ESCA, TGA, BET to find optimized
parameter sets.

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 Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

Experimental

Production of Carbon Nanotubes

CNT raw materials were produced at University College Cork by chemical vapour deposition
(CVD) of methane over a MgO supported Co and Mo catalyst. MgO support was impregnated
from an aqueous solution of Co(NO3)2.6H2O and (NH4)Mo6O24.H2O, and the solution was
sonicated for 30 minutes and dried at 100 ºC overnight. The dried powder was sintered at 450
ºC for 8 hr to produce the catalyst. 0.5 g of the catalyst was placed in a quartz tube in a tube
furnace. The powder was reduced by heating to 800 ºC in 10% H2/Ar at a flow rate of 200 ml
min-1 for 30 min. Methane was then fed into the tube at a flow rate of 100 ml min-1. The
growth period for CNTs formation was set at 800 ºC at 60 min, after which the furnace was
cooled to room temperature. To purify CNTs the as-prepared catalyst/carbon mixture was
treated with 3 M HNO3 and was washed by water to remove the catalyst.

Production of Aligned Grown CNTs

Aligned MWCNT were produced via Plasma Enhanced Deposition at the University of Cambridge
[25]. MWCNT were grown in-situ on top of Si substrates with the aid of a thin catalyst (~5nm)
layer of Ni. Using a gas flow ratio of 1:4 of Acetylene (C2H2) to Ammonia (NH3) and growth
temperatures of 680°C these MWCNT were grown between 10 to 25mins to achieve the
desired heights of ~0.5-1.5 μm. During the growth process a DC plasma bias of 600V is
applied which maintains an electric field for aligning the MWCNT.

Plasma Treatment
During the project, two different plasma treatment systems were built up. First, a tube reactor
were used, schematically shown in Figure 1.

Figure 1. Schematic view of the tube reactor in horizontal design

The reactor is equipped with a high frequency generator (13,56 MHz), a gas inlet system with
flow controllers, a vacuum pump with an upstream liquid nitrogen trap and pressure
controllers. The generator enables an energy input between 10 and 600 W. The flow controller
can be set to a gas flow of up to 100 sccm with one monomer gas or gas mixtures. The gas
flow passes horizontally over the samples. The pumping system enables a base pressure prior
to the treatment of approx 0,001mbar. The found parameter sets were then transferred to a
more defined parallel plate plasma system depicted in figure 2 with a gas flow vertical to the
samples.

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 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

Figure 2. Parallel plate plasma treatment chamber to functionalize bucky papers and the
treatment of aligned grown structures with a size of 40x30 cm2 (DIN A3).

This symmetrical reactor consists of two plane parallel electrodes with a size of 40×30 cm2. In
the employed setup the plasma was capacitively coupled at 13,56 MHz frequency (RF) by the
use of an ENI® ACG-6B plasma generator and a suitable ENI® MWH-5 impedance matching
network (MKS Instruments Deutschland GmbH, Munich / Germany). The upper electrode was
connected to the RF while the lower one was grounded. More details on this reactor can be
found elsewhere [26].

Analytical Methods
Scanning electron microscopy (SEM; LEO 1530 VP) in combination with energy dispersive x-
ray spectroscopy (EDX) was used to assess the morphological structure of the raw materials
and the produced bucky papers. RAMAN-spectroscopy was carried out with the Ntegra Spectra
[NT-MDT] equipped with two lasers at 632,8 nm and 488 nm emission, respectively. A grating
of 1800 lines/mm yielding a resolution of 1,5 cm-1.
N2-adsorption isotherms were measured at 77 K by a gravimetric method (IGA system, Hiden
Analytical, Ltd.). The adsorption measurements were carried out after preevacuation of the
nanotube samples at 373 K and 1 mPa for 3h. The nanotube samples show a type II or type IV
behaviour which allows the calculation of the specific surface area via the BET-method in
accordance with DIN ISO 9277.
The surface analysis studies were performed by XPS/ESCA employing a Kratos Axis Ultra
System equipped with a DLD-detector and a monochromatic AlKα source. Details of this set-up
are described elsewhere [26, 27].

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 Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

Results and Discussion

Bucky Paper Production

During the production process, carbon nanotubes form typically large agglomerates of
entangled CNTs, often mixed with remaining little catalyst nanoparticles encapsulated in
carbon nanotubes and amorphous carbon. Figure 3 represents SEM figures of MWNT and
SWNT raw material produced via the CVD method. To obtain a good and stable bucky paper,
those agglomerates have to be broken up, ideally to single CNTs or CNT bundles.

Figure 3. SEM figures of MWNT and SWNT raw material. The as-produced material consists
of large, up to 100-500µm large agglomerates of entangled CNTs. The highest magnification
also indicates the different shape of MWNT compared to SWNT.

The process parameter can also influence the specific surface area of the obtained CNT-
material. From N2-adsorption measurements the following values were obtained:
Table 1. Specific surface area measured at SWNT- and MWNT-powders.

Material specific surface area [m2/g]

UCC SWNT No. 1 444.1 ± 2.5
UCC SWNT No. 2 581.3 ± 13.4
UCC MWNT No. 1 368.2 ± 2.6
UCC MWNT No. 2 555.2 ± 7.2
The production of carbon nanotube sheets (bucky papers) was first described by Rinzler et al.
[28] as one step during the purification of SWNT raw material. A systematic optimization of the
parameters influencing the bucky paper production was done along the production steps shown
in the schematic view in figure 4.

Figure 4. Schematic view of the steps to produce bucky papers

Depending on the size and thickness of the finally produced bucky paper (papers up to a
diameter of 150 mm can be produced) 40 mg up to 500 mg of CNT powder were dispersed in a

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 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

tensides like Triton X can be used but SDS seem to be more effective. Ultrasonic assistance is
indispensable to break up the agglomerates. It could be shown that an ultrasonic tip is more
effective then an ultrasonic bath. With a bath up to 16 hours treatment is necessary for a good
dispersion but the treatment is gentler. With an ultrasonic tip (diameter 7 mm) typical
treatment times are 30min. Longer treatment times lead to a shortening of the CNTs as
assessed via photon correlation spectroscopy. To remove large and undispersed particles,
consecutive centrifugation for 15 min 5000 rpm is recommended. The obtained CNT-
suspension is then filtered using 0,45 µm polycarbonate filter membrane. Also other
membrane materials like PVDF, PTFE, PES or Nylon are suitable. But our observation is that
from the PC membrane peeling off of the freshly prepared bucky paper is easier. The filtration
can be done by vacuum or high pressure filtration. Figure 5 shows photographs of both
filtration techniques.

Figure 5. Photographs of the vacuum (left) and high pressure (right) filtration technique to
produce bucky papers. Depending on the equipment size, bucky papers up to 150mm in
diameter can be produced.

In figure 6 two SEM pictures together with the photographs of the obtained bucky papers are
shown. The left part shows a picture of a BP produced with a bad parameter set. The ultrasonic
treatment was to shorten the tubes, however the dispersion wasn't centrifuged thoroughly
prior to the filtration. It could be clearly seen that large CNT agglomerates dominates the
bucky paper leading to a brittle sheet. With optimized parameters a good entanglement of the
CNTs and CNT-bundles and a stable bucky paper could be obtained.

Figure 6. SEM-figures and photographs of bucky papers produced under non and optimized
parameters.

Most of the produced bucky papers were used to analyse their electromechanical properties
(actuation performance) [29, 30]. For this application but also for the use of the bucky paper
as substrate for cell cultivation [31], remaining SDS has to be removed. TGA-measurements,
carried out at TCD, clearly indicate that the bucky paper have to be rinsed 5 times with 150 ml
hot water to remove the excess SDS whereas cold water is less effective.

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 Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

Plasma Treatment of Bucky Papers

To measure the actuation performance of bucky papers or to increase the ability of cells to
settle and proliferate at it, a hydrophilization of the paper surface is required. As produced
bucky papers typically have non-wetting properties with contact angles of 90° up to 130°. This
can be traced back to the hydrophobic nature of the CNTs. To measure the electromechanical
properties, an electrolyte is required [32]. A hydrophilization of the bucky papers due to a
plasma treatment should lead to an instant wetting and better penetration of the electrolyte
into the CNT mesh.
To optimize the plasma process several parameters have to be considered due to their
influence on the kind and amount of active species in the plasma zone. Figure 7 summarizes
the most important ones.

Figure 7. Parameters influencing the plasma treatment

We have investigated the influence of the monomer gas, the power, the gas flux, and the
treatment time. The assessment of the plasma functionalization was mainly done by X-ray
photoelectron spectroscopy (XPS/ESCA). In figure 8 typical C1s spectra of SWNT, MWNT and
plasma treated MWNT are shown. The SWNT bucky paper in this case was made from an arc
discharge raw material. The additional peak at approximately 287 eV, attributed to the
enhancement of oxygen functionalities is more pronounced for the SWNT material.

Figure 8. C1s spectras of SWNT, MWNT and an Ar/O2-plasma treated bucky paper.

In the literature different approaches have been discussed concerning the deconvolution of the
C1s peak of carbon nanotubes. Some use a graphite peak shape for the large peak at 284,6 eV
with the tail at the high energy binding site[33, 34, 35], others distinguish between sp2- and
sp3-carbon at 284,6 eV (C1) and at 285,1 eV (C2), respectively[36, 37]. The peaks with
binding energies higher than 290 eV have been interpreted as π-π* transitions (shake
ups)[38], as O=C-O-C=O / carbonate [39] or have been neglected [40]. The three main peaks
centered at 286,7 eV (C3), 287,9 eV (C4), and 289,2 eV (C5) that emerge after plasma
oxidation are generally attributed to C-O (alcohol/ether), C=O (keton/aldehyd), and O-C=O

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 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

(carboxyl/ester) groups, respectively. All components were fitted by using a

Gaussian/Lorentzian (70/30) line shape after a linear background substraction and constant
peak positions and FWHMs.
To investigate the role of hexagonal layers on the plasma induced modification we have
compared MWNT and SWNT material treated with nitrogen, N2/O2 (50:50), and oxygen
plasma, respectively. The plasma power was set to 10 W and the applied treatment times were
10 sec or 10 min, respectively. The obtained elemental compositions are given in table 2.
Table 2. Comparison of the elemental composition of SWNT and MWNT material after different
plasma treatments with increased oxidation potential and 2 different treatment times.

As expected, longer treatment times and higher oxidation potential of the plasma lead to
higher oxygen content. Taking a closer look at the oxygen content it can furthermore be
concluded that in all cases the degree of oxygen functionalization is higher for the SWNT
material than for the MWNT material. This can be explained by the information depth of XPS.
The functionalization of the MWNT-material occurs only at the outermost 1-3 CNT-layers. The
information depth of XPS (approx. 5-10nm) includes the unmodified inner shells too, resulting
in a reduced O/C-ratio for the MWNTs.
The oxygen functionalities were substantially improved after plasma treatment in N2 (for
SWNTS increased from 5.1 to 15.7 at%; for MWNTs increased from 2.5 to 13.2 at%), whereas
the incorporation of nitrogen was moderate ( 0.5 to 2.5 at%). This significant uptake of
oxygen can be explained by considering the large number of defects generated during the
plasma treatment. The introduction of defects in the hexagonal lattice leaves the surface with
very highly reactive sites capable of adsorbing oxygen.
High plasma power and treatment times were efficient not only to introduce oxygen
functionalities on the first few surface layers of the CNTs, but also to remove amorphous
carbon and even destroy the nanotubes up to a full burning (see also next section). This is in
agreement with the decrease in specific surface area measured at MWNTs bucky paper before
and after treatment in Ar/O2 plasma. Whereas the raw material has a specific surface area of
368 ± 3 m2/g the pristine and plasma treated bucky paper shows values of 203 ± 2 m2/g and
188 ± 2 m2/g respectively. Therefore plasma treatment under optimized conditions can serve
as a purification process able to etch non crystalline carbon related impurities.
A gentler but also effective hydrophilization can be achieved by using nitrogen plasma followed
by a deliberate post-treatment oxidation with oxygen. Here, the nanotubes are activated by
the nitrogen plasma leading to a significant amount of radicals, as assessed by electron spin
resonance (ESR). The consecutive flooding of the plasma reactor with oxygen enables the
reaction of the biradical oxygen with the radicals formed at the nanotube surface. The bucky
papers treated with this method show also an instant wetting and contact angles below 10°.

Plasma Treatment of Aligned Grown CNTs

Initially plasma treatments were carried out on entangled CNTs deposited by drop dry
technique on gold coated silicon wafers. The left hand side of figure 9 shows optical

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 Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

micrographs of the entangled samples after oxygen plasma treatment at various conditions
The table at the right side summarizes the elemental composition obtained by electron
spectroscopy chemical analysis (ESCA). All the experiments were carried out in the horizontal
tube reactor. It is clear, that within this reactor a strong oxidation occurs by using oxygen as
process gas and a power of 50 W. After 5 minutes treatment at 50 W the CNT coating was
burned off.

Figure 9. Optical micrographs of entangled CNTs deposited on Ag/Si by drop dry technique
after different oxygen plasma treatments, together with their elemental compositions.

Subsequently, the plasma treatment of vertically aligned CNTs grown on a Si substrate was
carried out with the aim of opening their end. Due to the top growth mechanism the nickel
catalyst is located at the tip of the CNTs seen as white dots in the SEM-pictures The
experiments were performed in the parallel-plate reactor. Due to the larger plasma zone, the
effective power per cm2 is smaller compared to that of the tube reactor. Different monomer
gases were assessed including oxygen, nitrogen, hydrogen, water as well as argon/oxygen-
and hydrogen/oxygen-mixtures. The roles of power (10 W, 50 W), gas flux, pressure and
treatment time (between 10 sec and 10 min) were also investigated. We found that the harsh
treatments necessary for opening the CNTs were severely disrupting the shape and vertical
alignment of the CNTs. Figure 10 presents typical SEM images.

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 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

Figure 10. SEM-pictures of aligned CNTs before and after plasma treatment. After short
treatment times (10sec) at 10 W power no disruption is visible whereas longer treatment
times or higher power destroy the shape of the tubes without opening of the end caps.

We found that oxygen plasma treatment leads to a significant disruption of the vertical
alignment configuration even after short treatment times of 60 sec. Ar/O2- and H2/O2-mixtures
can be applied up to approx 60 sec without strong alteration of the tube shape whereas longer
times show the same deleterious effects. Plasma treatments employing reduced oxidation
potentials like those produced by molecular nitrogen resulted on an unaltered vertical CNT
configuration even after 10 min.
Acid solutions such as hydrochloric acid have been shown to assist the opening of plasma
treated SWNTs [41]. The plasma treatment leads to a destruction of nanotube wall, enabling
the HCl to react with the iron catalyst particles and burn away the tube caps. In our study,
employing plasma treated MWNTs (150 nm in diameter) a consecutive wet chemical treatment
after mild plasma conditions lead to a "tipi-building" of the CNTs due to capillary forces without
opening the ends. The 3D network structure is illustrated on the SEM-pictures of figure 11. We
envisage that more harsh conditions (longer treatment times) are needed to expose the
catalyst particles; such studies are underway.

Figure 11. "Tipi-building" of aligned grown CNTs after a wet chemical treatment.

Conclusions

Bucky papers were successfully produced after optimization of the production steps. SDS was
identified as appropriate Tenside together with an ultrasonic tip treatment to obtain good CNT
suspensions. The ultrasonic treatment was set to 30 min to avoid significant shortening of the
CNTs. Remaining CNT agglomerates were removed by centrifugation prior to the filtration over
a 0,45 µm pore size polycarbonate membrane. PC-membranes were assessed as best to peel
of the bucky papers. The effects of plasma treatment on the surface wettability of carbon
nanotube bucky papers and aligned nanotubes have been systematically investigated A
hydrophilization of the produced bucky papers was successfully demonstrated by plasma

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 Tailoring the Wettability of Carbon Nanotube Powders, Bucky Papers and Vertically Aligned Nanofibers by Plasma Assisted Functionalization

treatment using oxygen containing process gases or post treatment reaction with oxygen after
plasma activation. As a result, an instant wetting and contact angles <10° was obtained. We
also found that under gentle oxidation parameters the vertical alignment of MWNTs remains
unchanged whereas stronger conditions destroy the CNT shape without opening the end caps.

Acknowledgment

The authors acknowledge the European Union for funding this project within the EU Specific
Targeted Research Project DESYGN-IT (No NMP4-CT-2004-505626)

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Volume 3 | November 2007 Page 11 of 12 DOI: 10.2240/azojono0126

 Uwe Vohrer, Justin Holmes, Zhonglai Li, AunShih Teh, Pagona Papakonstantinou, Manuel Ruether and Werner Blau

Contact Details

Uwe Vohrer Justin D. Holmes, Zhonglai Li

Fraunhofer Institute Interfacial Engineering Department of Chemistry, Materials Section
and Biotechnology and Supercritical Fluid Centre,
Nobelstrasse 12 University College Cork,
70569 Stuttgart Cork
Germany Ireland
[email protected] [email protected]
[email protected]

Pagona Papakonstantinou AunShih Teh

Northern Ireland Bioengineering Research University of Cambridge
Centre School of Electrical and Mechanical Cambridge
Engineering Newtownabbey, UK
Co. Antrim BT37 0QB
[email protected]
N. Ireland
[email protected]

Manuel Ruether, Werner J. Blau

Trinity College
NMR Unit
School of Chemistry
Dublin 2
Ireland
[email protected]
[email protected]

Volume 3 | November 2007 Page 12 of 12 DOI: 10.2240/azojono0126