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Thin Solid Films 516 (2008) 3474 3477

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Physical properties of carbon nanotubes radiated by proton beams:

Gas adsorption and electron microscopy studies
Byung-wook Kim a , Euikwoun Kim a , Jungjil Lee a , Kyoohyun Han b , Jae-yong Kim a,
a

BK21 Program Division of Advanced Research and Education in Physics, Hanyang University, Seoul 133-791, South Korea
b
Department of Physics, Ume University, Ume, S-90187, Sweden
Available online 23 August 2007

Abstract
Single walled carbon nanotues (SWCNTs) of high purity and multi walled carbon nanotubes (MWCNTs) were radiated by high energies of
proton and electron beams. The surface physical properties were examined by XRD and TEM for both irradiated and non-radiated samples to
compare the effect of radiation. The possible changes of surface characteristics were investigated by isotherm gas adsorption technique using Ar
which can probe the local structure in an order of atomic scale. A series of Ar gas adsorption results measured below 77 K revealed significant
changes in surface properties of carbon nanotubes by the bombardment of proton beams, which may induce the local surface defects. It is
speculated that reactions on carbon nanotubes radiated by beams were led by kinetic energy transfer of the bombardments.
2007 Elsevier B.V. All rights reserved.
Keywords: Nanotubes; Proton radiation; Ar adsorption; AFM

1. Introduction
Since the discovery of the two-dimensional condensation of
a solid van der Waals atomic layer on highly homogeneous
substrates [13], adsorption isotherm techniques have been
extensively used to probe the physical/chemical properties of
surfaces such as porosities, surface area of powders, and
interaction of molecules on surfaces. These studies include
characterizing the thermodynamic and structural properties of
noble gases, such as Xe, Ar, Kr, CH4 on exfoliated graphite, on
pure or doped metal oxides [4] or on carbon nanotubes (CNTs).
CNTs are the interesting adsorbates that draw much attention for
future technological applications such as various sensors,
advanced electronic devices due to their unusual physical,
electrical, and mechanical properties. These properties are
mainly originated from their molecular structures, which consist
of graphene sheets rolled to form hollow cylinders with
extremely high aspect ratio [5].
Recently, many researches have focused on the direct
modification of CNT surfaces using intense radiations.
Particularly, proton radiation on CNTs is known to induce the
Corresponding author. Tel.: +82 2 2220 0917.
E-mail address: kimjy@hanyang.ac.kr (J. Kim).
0040-6090/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.08.080

chemical and structural modification of polymer-CNT composite [6,7]. The proton irradiated graphite also showed the
inducement of magnetic ordering [8]. Proton irradiation on
CNTs mostly resulted in morphological damage, such as
welding, curve and fraction of small pieces, and chemical
modification forming CH bonding [6,9,10]. Electron beam
radiation is also known to induce the radiation defects, when
electron beam hits the target CNTs. Considerable studies of
electron beam irradiation effects in carbon nanotubes were
concentrated on the interactions of energized electron particles
with CNTs [11]. Interestingly, CNTs under a variable-pressure
or low-vacuum scanning electron microscopy were cut or were
bent into the desired lengths at the room temperature, which can
be used as a novel method for processing of CNTs [12]. The
synthesis and/or design of the structure and properties of CNTs
as well as inducing self-repair were presented by generating the
carbon ad-atoms from electron irradiated CNTs [13]. CNT
fillers in polymer composites under electron beam radiation
showed the excellent property to defense polymer degradation.
The electric/magnetic and thermal properties, surface structure
including defects, and CC bonds are also expected to be
modified by radiation [14,15]. Once the high-energy of proton
beams impact on CNTs (or met on the condition for the Bragg
peak), one may predict that the surface morphology will be

B. Kim et al. / Thin Solid Films 516 (2008) 34743477

Fig. 1. Ar adsorption isotherms of SWCNTs measured at 66.9 K before

(solid squares) and at 67.4 K after radiating the proton beam of 35.7 MeV
(solid circles). Irregular isotherm steps are indicated by arrows.

changed by inducing the defects on the outer shell of the CNTs.

Compared to the irradiation by Ar ions, however, the effects of
proton and electron beams on CNTs have not been much
discussed. Therefore, our studies on radiation effects on CNTs
were motivated by analyzing the adsorption isotherm data
measured by using adsorbed gas molecules, which is a method
to probing the structural changes and surface modification of the
CNTs.
2. Experimental procedure
High quality of CNTs, prepared by an arc-discharge method,
were purchased from the commercial products at the ILJIN
Nanotech Co. LTD. The electron microscopy studies including
TEM and SEM have shown that the diameters of SWCNTs were
11.2 and MWCNTs were 1015 nm, and both CNTs have a
purity of higher than 90 vol.%.
Proton radiation was carried out by using the MC-50
Cyclotron, the first cyclotron facility installed in Korea, at the
Korea Institute of Radiological And Medical Sciences (KIRAMS)

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[16]. The proton energy of the MC-50 was tuned to 38 MeV by a

cyclotron adjustment and Al energy degrader was placed in front
of the target [17]. The degrader can control the exit beam energy
and the scatterer also tunes the beam fluency and flux on the target
area. Detailed conditions, such as radiation energy, dose, and
beam fluency will be listed on the separate paper. In this experiment, accelerated protons with energies of 10, 20 and 35.7 MeV
were used.
Electron beam for our experiment was generated from the
high-average-current 2-MeV electron accelerator at the Korea
Atomic Energy Research Institute (KAERI). The sample stage
was located in the middle between a dump and a kicker magnet.
To examine the radiation effects of electron, the experiments
were performed using the accelerated electron of 2 MeV energy.
The radiation doses were each 0, 60, 120, 180, 240 kGy.
The adsorption isotherm data were collected using a
computer-controlled apparatus. The temperature of the sample
cell was controlled and monitored by using a temperature
controller (LakeShore 331S) with less than 5 mK accuracy.
The pressure measurements were performed using two different
capacitance manometers (MKS Baraton) with a scale from 0 to
100 Torr for pressures lower than 100 Torr, and with a scale
from 0 to 1000 Torr for pressures higher than 100 Torr. Vapor
pressures lower than 100 Torr were assumed to be in
equilibrium when they changed by less than 1 mTorr over
1 min, while the vapor pressures higher than 100 Torr were
assumed to be in equilibrium when they changed by less than
5 mTorr over 1 min. Volume of the dead space of the cell
(a few cm3) was subtracted from the carefully calibrated dosing
volume (37.43 cm3) using successive helium gas expansions.
Magnetic force gradient images and topography were
simultaneously obtained at room temperature with a Nanoscope
IV scanning probe microscope from Digital Instruments. The
magnetic images were taken with a standard magnetic-etchedsilicon probe (MESP) with tip coercivity (Hc) of 300 Oe.
Magnetic force gradient images and topography were simultaneously obtained at room temperature with a Nanoscope IV
scanning probe microscope from Digital Instruments. The
magnetic images were taken with a standard magnetic-etched-

Fig. 2. TEM pictures of before (left) and after (right) radiating the proton beam of 35.7 MeV.

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B. Kim et al. / Thin Solid Films 516 (2008) 34743477

Fig. 3. Ar adsorption isotherms of MWCNTs measured before (a) and after

(b) radiating the electron beam with energy of 10 MeV.

silicon probe (MESP) with tip coercively (Hc) of 300 Oe. The
magnetic force microscopy (MFM) measurements were performed in the tapping/lift TM scanning mode with the phase
detection system. The first scan of the surface is made in the
intermittent contact mode to determine the topography (Tapping
mode). During the second scan the tip follows a constant height
pathway determined from the topography scan and senses the
magnetic forces (Interleave mode). This method is used for the
separation of the magnetic and the topographic signals; however
one needs to note that tapping the surface with a magnetic tip
during the initial scan may modify the magnetic structure of the
sample.
3. Results and discussions
Fig. 1 shows the isotherm data of Ar adsorbed on SWNTs
measured below the triple point (83.7 K) as a function of its
normalized saturation vapor pressure before and after radiating
with a 35.7 MeV proton beam at the Bragg-peak position for
15 min. Interesting observations are the following; first, very
steep step height during the formation of the first layer was

found which is a significantly different behavior compared to

the one measured from the metal oxide powders [18], and
secondly, the total amount of adsorbed Ar gas to complete the
monolayer did not change after the radiation. These results
reflect that the molecular structure of the SWCNTs remains the
same even after radiating the proton beam, as confirmed by
TEM (see Fig. 2). Noticeable changes in the adsorption
isotherms were observed during the formation of the second
Ar atomic layer. Before irradiation, the adsorption isotherms
showed a hint of irregular step (as indicated by an arrow in
Fig. 1). However, this peculiar isotherm step disappeared in the
samples after radiating the proton beam. Furthermore, a
complete wetting did not take place from the radiated sample.
Instead, an abrupt change of saturation vapor pressure was
noted. These results strongly suggest the modification of the
surface characteristics including alteration of textures, variation
of CC atom distances, and inducement of defects occured.
To compare the effects of electron bombardments on CNTs
with the ones of proton radiation, MWCNTs were radiated by
10 MeV electron beams, and the gas adsorption isotherms using
Ar were measured for both e-beam radiated and unradiated
samples near 67 K (see Fig. 3). Contrary to the results from the
proton radiated samples, it is evident that MWCNTs exhibit the
existence of the second layer formation although the reasons are
not clear if the difference is due to the intrinsic properties of
MWCNTs and SWCNTs. Another interesting result is that there
was no clear difference in isotherm data between e-beam
radiated and unradiated samples in terms of slop of the steps and
amount of gas covering the monolayer. These results may
suggest that the electron beam did not effectively modify the
surface of the CNTs due to the low incident energy (2 MeV)
compared to proton beams (35.7 MeV at the Bragg peak
position).
Magnetic force images were also taken and the results were
examined. Normally, magnetic response of the samples is
represented as a two-dimensional field with dark and bright
areas. In the phase detection mode, the repulsive interaction
shifts the resonance frequency towards higher frequencies
which leads to a bright contrast in the phase detection. Similarly,
shift to lower frequencies reveals an attractive tipsample

Fig. 4. MFM images of unradiated MWNTs with scan height of 10 nm (a), and electron beam radiated MWCNTs with scan heights of 30 nm (b), and 100 nm (c).

B. Kim et al. / Thin Solid Films 516 (2008) 34743477

interaction, and the regions with attractive interaction are

represented by dark contrast. In order to study the origin of the
MFM contrast in detail, measurements for the opposite tip
magnetizations have been carried out. Prior to acquiring an
image, the scanning probe was magnetized to the positive z
direction (perpendicular to the basal plane of the sample),
making the MFM sensitive to the second derivative of the zcomponent of the sample stray field. The tip was magnetized
by placing it in close vicinity to a rare-earth permanent
magnet. At the surface, the employed magnet exhibits a field
of 3000 Oe. After obtaining the images, the tip was taken
away, magnetized in the opposite ( z) direction and returned
to the same position. Therefore, the magnetic contrast in these
experiments was achieved due to the interaction between the
features on sample and the MFM tip. In general, it was
difficult to find variation of topography and magnetic images
after the proton irradiation. As shown in Fig. 4, however, we
measured still clear MFM images from the proton radiated
samples even the scan heights were higher than 100 nm,
although no images were obtained from the un-radiated
samples when the distance of the tip to the sample was larger
than 10 nm. This may be due to the exhibits of the induced
magnetism by the proton radiation as suggested by Lee and
Lee [19].
4. Conclusions
High energy of electron and proton beams were radiated
on carbon nanotubes, and the possible physical changes in
surface were investigated by using XRD, TEM and electron
microscopy. Analysis of the Ar adsorption isotherm data measured below the triple point revealed different behaviors in
adsorption steps for the electron and proton radiated CNTs.
It is not clear, however, that this unusual isotherm curve
reflects the intrinsic structural difference between SWCNTs
and MWCNTs or was due to the different incident energies of
electron and proton beams. It is believed that more detailed
studies are necessary to address the questions raised by our
study.

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Acknowledgements
This work was supported by R01-2006-000-11227-0 from
the Basic Research Program of the Korea Science &
Engineering Foundation (KOSEF), and by the User Support
Program of the Proton Engineering Frontier Project.
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