Applied Surface Science 387 (2016) 822–827

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Low-energy electron irradiation of preheated and gas-exposed

single-wall carbon nanotubes
P.A. Ecton a , J. Beatty b , G. Verbeck b , W. Lakshantha a , B. Rout a , J.M. Perez a,∗
a
Department of Physics, University of North Texas, Denton, TX 76203, United States
b
Department of Chemistry, University of North Texas, Denton, TX 76203, United States

a r t i c l e i n f o a b s t r a c t

Article history: We investigate the conditions under which electron irradiation at 2 keV of single-wall carbon nanotube
Received 28 March 2016 (SWCNT) bundles produces an increase in the Raman D peak. We find that irradiation of SWCNTs that are
Received in revised form 10 June 2016 preheated in situ at 600 ◦ C for 1 h in ultrahigh vacuum before irradiation does not result in an increase in
Accepted 18 June 2016
the D peak. Irradiation of SWCNTs that are preheated in vacuum and then exposed to air or gases results
Available online 21 June 2016
in an increase in the D peak, suggesting that adsorbates play a role in the increase in the D peak. Small
diameter SWCNTs that are not preheated or preheated and then exposed to air show a significant increase
Keywords:
in the D and G bands after irradiation. X-ray photoelectron spectroscopy shows no chemical shifts in the
Carbon nanotubes
Defects
C 1s peak of SWCNTs that have been irradiated versus SWCNTs that have not been irradiated, suggesting
Electron irradiation that chemisorption of adsorbates is not responsible for the increase in the D peak.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction modified with low-energy electron irradiation to produce desired

Carbon nanotubes (CNTs) have been studied with great interest
due to their unique structural, chemical, and electrical proper-
ties. Of particular interest is the modification of the structural
and electrical properties of CNTs through chemical, plasma, and
low-energy electron irradiation processes. Numerous studies have
investigated the effects of low-energy electron irradiation on bun-
dled [1–4] and isolated [4–6] single-wall CNTs (SWCNT) at energies
of 20 eV to 20 keV and dosages of 1015 to 1018 e− /cm2 . These stud-
ies have found that the Raman spectrum of irradiated SWCNTs
shows an increase in the intensity of the D peak located at around
1350 cm−1 . The D peak’s intensity is observed to decrease after
annealing the sample at 300 ◦ C for 30 min. The increase in the D
peak was attributed to defects in the SWCNTs caused by dam-
age from the electron irradiation, and its reduction after annealing
was attributed to the healing of the SWCNTs. Studies of low-
energy electron irradiation of isolated SWCNTs have found that, in
addition to an increase in the D peak, irradiation induces a metal-
semiconductor or metal-insulator transition [4–8]. It has not been
conclusively shown if the transition is due to irradiation-induced
defects in the nanotubes [4–6] or substrate charging [7,8]. This find-
ing is particularly useful as it shows that isolated SWCNTs can be
∗ Corresponding author.
E-mail address: jperez@unt.edu (J.M. Perez).
electrical properties. The mechanism by which low-energy elec-
tron irradiation produces defects in bundled or isolated SWCNTs is
not well understood. Only at energies greater than about 86 keV do
electrons have sufficient momentum to cause knock-on collision
damage to SWCNTs [9]. Since the energy of electrons in the afore-
mentioned studies is well below this threshold, the defects cannot
be produced by knock-on collisions. It has also been reported that
the damage occurs as ever when SWCNTs are thoroughly degassed
in ultrahigh vacuum (UHV) before irradiation, with the report stat-
ing that the irradiation damage is caused by the irradiation itself
[4]. It would be of interest to know the conditions under which
low-energy electron irradiation of SWCNTs produces an increase in
the D peak. In this paper, we investigate the effects of pre-heating
SWCNT bundles in situ at temperatures of 400–700 ◦ C in UHV prior
to low-energy electron irradiation. In addition, we study the irra-
diation of SWCNT bundles that have been pre-heated in UHV and
then exposed to air and gases. The samples are characterized using
Raman spectroscopy and X-ray photoelectron spectroscopy (XPS).
2. Material and methods
The SWCNTs used in this study were manufactured by
Tubes@Rice using laser ablation and consist of nanotube bundles
with individual nanotubes having a distribution of diameters from
about 1.1 to 1.5 nm. We also studied purified SWCNTs manufac-
tured by Carbon Nanotechnologies, Inc. using the high-pressure

http://dx.doi.org/10.1016/j.apsusc.2016.06.111
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 P.A. Ecton et al. / Applied Surface Science 387 (2016) 822–827
carbon monoxide (HiPco) method that consist of nanotubes hav-
ing smaller diameters with a distribution from about 0.8 to 1.5 nm.
The nanotubes were mixed in a solution of dimethylformamide,
which was then ultra-sonicated. The mixture was then dropped on
a 0.5 × 1.5 cm2 conductive Si substrate and allowed to dry over a
24 h period.
Samples undergoing electron irradiation were first mounted
onto a quartz sample holder with two molybdenum clips attached
to allow for Ohmic heating and grounding of the substrates during
irradiation. The sample holder was then inserted into a preparation
chamber at a base pressure of 10−7 Torr. The preparation chamber
is connected via an all-metal through valve to a UHV system at
a base pressure of 10−10 Torr containing a heating stage used to
heat the samples and an electron gun used to irradiate the sam-
ples. The samples are transferred from the preparation chamber
to the UHV system using linear and rotary feedthroughs that can
transfer the sample onto the heating stage or lead the sample to
the electron gun. Samples undergoing pre-heating are heated to
temperatures from 400 to 700 ◦ C. The temperature of the sample
was measured using an external blackbody thermometer that had
line of sight access to the sample through a transparent viewport.
The data presented are for samples undergoing irradiation using a
beam of electrons with energy set to 2.0 keV and a beam current of
1.0 ␮A. The beam had a diameter of 1 mm and was rastered across
the sample area at a rate of 0.5 mm/s.
Samples prepared for gas exposure were returned after pre-
heating from the UHV system to the preparation chamber for
exposure to H2 O, H2 , O2 , N2 , or Ar gases. Before exposure, the
samples were pre-heated at a temperature of 675C for 1 h. The
preparation chamber was primed by filling the chamber with the
intended gas at up to 100 times the base pressure. The gas was then
pumped from the chamber until the chamber was brought back to
its base pressure. This procedure was repeated 10 times in order to
bring the initial residual gases down to 10−20 parts per million rel-
ative to the intended gas. Gasses, with the exception of H2 O, were
drawn from gas cylinders that tend to contain some water vapor.
Because of this, before using the gases drawn from such containers
the tubing connecting the gas cylinder to the preparation cham-
ber was passed through a water vapor trap containing a mixture
of acetone and dry ice, which condensed the water vapor in the
trap preventing further diffusion into the chamber. Once the prim-
ing was complete and after the sample had been pre-heated, the
sample was translated back to the preparation chamber and the
chamber filled with the selected gas. The pressure of the gas was
set to 1.00 Torr for 1 h. The gas was then removed from the prepa-
ration chamber to a pressure of 5 × 10−7 Torr, the through valve
opened and the sample translated back into the UHV chamber and
irradiated using the electron gun.
Electron irradiation was also carried out using electrons drawn
from a hydrogen plasma. This method was used to irradiate sam-
ples with electrons of lower energies (60–100 eV) that could not
be produced with the electron gun. Samples undergoing plasma
irradiation were inserted into a chamber at a base pressure of
3 × 10−7 Torr. The plasma system has been described in detail else-
where [10]. The plasma is generated by RF induction applied to a
quartz tube using a 50 W power supply at 20 MHz. Irradiation of the
sample is achieved by the presence of a positive potential difference
between the sample and the chamber that draws the electrons from
the plasma toward the sample and repels the positive ions.
Raman spectra were obtained using a Nicolet Almega XR dis-
persive Raman spectrometer with a 532 nm (2.33 eV) laser. XPS
measurements were made using a PHI 5000 Versaprobe Scanning
XPS Microprobe. Due to their one-dimensional structure, SWCNTs
have an electronic density of states that has sharp van Hove singu-
larities [11]. At a given laser energy, this results in resonant Raman
scattering for nanotubes that have energy spacing between van
823
Fig. 1. Raman spectra of laser ablation grown SWCNTs. Black curve (a) is a spec-
trum of pristine SWCNTs that have not been electron irradiated. Red curve (b) is
a spectrum of SWCNTs that have only been irradiated at 2.0 keV to a dosage of
3.2 × 1015 e− /cm2 . Blue curve (c) is a spectrum of SWCNTs that have been irradiated
at 2.0 keV to a dosage of 3.2 × 1015 e− /cm2 , exposed to air, and then post-annealed
in UHV at 450C for 1 h. Insets show the RBM region and the D band region. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
Hove singularities, Eii , equal to the laser energy. SWCNTs have 6
different Raman active symmetry modes associated with in-plane
vibrations: two A1g , and two doubly degenerate E1g and E2g modes
[11]. Due to different force constants perpendicular (TO) and par-
allel (LO) to the tube axis, the TO and LO modes produce Raman
peaks that are downshifted and upshifted, respectively, relative to
the graphene G peak at about 1580 cm−1 [12]. In metallic SWCNTs,
electron-phonon coupling results in a downshift and asymmetric
broadening of the G peak that is well fitted by a Breitt-Wigner-Fano
(BWF) curve [13,14]. In this paper, down-shifted and up-shifted G
peaks are referred to as G− and G+ peaks, respectively; and, super-
scripts “S” and “M” refer to semiconducting and metallic nanotubes,
respectively.
3. Results and discussion
Fig. 1 shows Raman spectra of pristine laser ablation grown
SWCNTs before and after processing. The spectra have been offset
for clarity. The insets show close-ups of the radial breathing mode
(RBM) and D peaks with no offsets. In this and other figures, the
plots in the insets are associated with the plots in the figure by color.
Henceforth, pristine will refer to as-received SWCNTs that have not
been pre-heated, irradiated or post-annealed. The amount of disor-
der in carbon is typically quantified by the ratio ID /IG , where ID is the
intensity of the D peak and IG is the intensity of the G peak. Since the
G band in SWCNTs consists of several peaks, we normalize the spec-
tra in Fig. 1 so that the maximum of the G band at around 1590 cm−1 ,
IM , has the same height. Fig. 1(a) shows a Raman spectrum of a pris-
tine sample without any processing. Fig. 1(b) shows a spectrum
of a pristine sample that has been irradiated using the electron
gun without in situ pre-heating or post-annealing. The D peak has
nearly twice the intensity as its original pristine state (ID /IM = 0.045
and ID /IM = 0.08 for pristine and irradiated, respectively). After the
Raman spectrum of the irradiated sample was taken, the sample
was post-annealed at 450C for 1 h. Fig. 1(c) shows a subsequently
acquired Raman spectrum revealing that the D peak was reduced to
just above the unprocessed level (ID /IM = 0.048), in agreement with
earlier studies [5,4]. Decomposition of the RBM curve reveals three
Lorentzian peaks at 177, 190 and 193 cm−1 for Fig. 1(a), 177, 191
824 P.A. Ecton et al. / Applied Surface Science 387 (2016) 822–827

Fig. 3. Raman spectra of laser ablation grown SWCNTs. Black curve (a) is a spectrum
of a pristine unprocessed sample. Red curve (b) is a spectrum of a sample that was
pre-heated and irradiated in situ. Blue curve (c) is a spectrum of a sample that was
pre-heated, irradiated in situ, exposed to air and then re-irradiated. Insets show the
RBM region and the D peak region. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
Fig. 2. Deconvolution of the Raman curves in Fig. 1.

and 194 cm−1 for Fig. 1(b) and 173, 187 and 191 cm−1 for Fig. 1(c).
The RBM peaks correspond to the E33 S transition of semiconduct-

ing SWCNTs, as determined using a plot of Eii versus tube diameter,

dt , for a laser energy of 2.33 eV [11,15]. A small RBM component
due to metallic SWCNTs (E11 M transition) that is not observable at

the scale of Fig. 1 occurs at about 270 cm−1 . The inset also shows
the diameter of the nanotubes versus wavenumber calculated using
dt = 10 cm−1 + 234/ωRBM [16].
Fig. 2 shows an expanded view of the D and G bands in Fig. 1.
The D band is fitted with five Lorentzian peaks for each curve at
1301, 1330, 1343, 1372 and 1401 cm−1 for the pristine sample,
1310, 1332, 1344, 1373 and 1406 cm−1 for the irradiated sample,
and 1310, 1333, 1346, 1372 and 1413 cm−1 for the post-annealed
sample. In the literature, peaks at about 1310 and 1400 cm−1 have
been attributed to C H complexes [17] and asymmetric bend-
ing of CH3 [18], respectively. Peaks from 1330 to 1370 cm−1 have
been attributed to amorphous carbon, vacancies, open ends, and
chemisorbed species such as oxides [17,19]. As shown in Fig. 2 (b),
the most significant change after irradiation is the increase in the
peak at about 1333 cm−1 . The G band is fitted with four Lorentzian
curves at around 1549, 1567, 1590, and 1607 cm−1 . As discussed in
Ref. [12], these correspond to the E2g TO , (A1g + E1g )TO , (A1g + E1g )LO ,
and E2g LO resonance modes of semiconducting SWCNTs, respec-
tively. In addition, there is a small BWF peak at around 1521 cm−1
and Lorentzian at around 1585 cm−1 that are assigned to the LO and
TO modes of metallic SWCNTs, respectively [20].
Fig. 3 shows the effects of pre-heating samples in situ. Fig. 3(a)
shows a Raman spectrum of a pristine sample. Fig. 3(b) shows
the spectrum of a pristine sample that has been pre-heated at
675 ◦ C for 1 h before electron irradiation that exhibits no increase
in the D peak. However, as shown in Fig. 3(c), after exposing this
sample to air for 30 min, re-installment in the UHV chamber and re-
irradiation, the D peak increases (ID /IM = 0.033 and ID /IM = 0.065 for
the sample that was pre-heated and irradiated, and the sample that
was exposed to air and re-irradiated, respectively). As shown in the
inset, the RBM peaks do not significantly change after irradiation;
they shift by −3.7 cm−1 and increase in intensity by a factor of 0.15
after pre-heating. Decomposition of the RBM curve shows three
main peaks at 180, 190 and 195 cm−1 for Fig. 3(a), 170, 186 and
190 cm−1 for Fig. 3(b), and 171, 186 and 190 cm−1 for Fig. 3(c). Sim-
Fig. 4. Raman spectra of the D peaks of laser ablation grown SWCNTs exposed to
various gases after pre-heating at 675 ◦ C for 1 h. Samples include a) a pristine sample,
b) a sample undergoing pre-heating and irradiation only, samples exposed to c) O2 ,
d) Ar, e) H2 O, f) N2 , g) H2 , and h) irradiated only SWCNTS. The inset shows the same
peaks overlapping each other to illustrate changes in intensities.
ilar results were obtained with electrons having energies from 60 to
100 eV using the plasma system. That is, the D peak increased after
irradiation if the sample was exposed to air, but did not increase if
the sample was pre-heated in vacuum and then irradiated in situ.
Since air exposure is necessary to observe the phenomenon, we
investigated the effects of exposure to specific gases. Fig. 4 shows
the Raman spectra taken from laser-ablated SWCNTs undergoing
electron irradiation at 2 keV after pre-heating in the UHV chamber
and gas exposure in the preparation chamber. The spectra have
been normalized such that the maxima of the G band, IM , have
the same height. Curve (a) shows the D peak for pristine SWCNTs
that have not been irradiated. Curve (b) shows the D peak for a
sample that has been pre-heated at 675 ◦ C for 1 h and then irradi-
ated in situ at a dosage of 3.2 × 1015 e− /cm2 without gas exposure.
Curves (c)–(g) show D peaks for samples that have been pre-heated
at 675 ◦ C for 1 h, and then irradiated with 2 keV electrons at a dosage
of 3.2 × 1015 e− /cm2 after exposure to the following gases: (c) O2 ,
(d) Ar, (e) H2 O, (f) N2 and (g) H2 . Curve (h) shows the D peak of
 P.A. Ecton et al. / Applied Surface Science 387 (2016) 822–827 825

Fig. 5. Raman spectra of HiPco grown samples. Curve (a) is a spectrum of SWCNTs
that have not been processed. Curve (b) is a spectrum of SWCNTs that have been
irradiated and post-annealed in situ. Curve (c) is a spectrum of SWCNTs that have Fig. 6. RBM region of Raman spectra shown in Fig. 5 with corresponding labels
been irradiated, exposed to air, and post-annealed. Curve (d) is a spectrum of SWC- (a)–(g).
NTs that have only been pre-heated. Curve (e) is a spectrum of SWCNTs that have
been pre-heated and irradiated in situ. Curve (f) is a spectrum of SWCNTs that have
been pre-heated, irradiated in situ, exposed to air, and re-irradiated. Curve (g) is a
spectrum of SWCNTs that have only been irradiated. Inset (h) shows a magnification
of the RBM region.

a pristine sample that has been irradiated. For each of the gases,
hydrogen produces the highest D peak with ID /IM = 0.092, followed
by molecular nitrogen and water vapor at around ID /IM = 0.075 and
oxygen at 0.055, which is similar to pre-annealed/irradiated sam-
ples. The pristine sample has a D peak with around ID /IM = 0.065. A
slight increase in the D peak (ID /IM = 0.070) appears for Ar as well.
Because the profile of the D peak after oxygen exposure shows
no discernible difference from that of the sample that was pre-
heated and irradiated, this would suggest that oxygen does not
participate in the reaction producing the defect in the SWCNTs.
The D peak increases more after the sample has been pre-heated
and exposed to water vapor or molecular nitrogen suggesting that
water vapor and molecular nitrogen could be interacting agents. A
strong increase in the D peak after hydrogen exposure suggests
that hydrogen, a component of water, could be the main cata-
lyst. We note that in our previous experiments in which exfoliated
monolayer graphene was pre-heated, exposed to various gases and
Fig. 7. Decomposition of the D and G bands of the Raman curves in Fig. 5 with
irradiated in a similar manner, we found that molecular hydrogen corresponding labels (a)–(g).
and nitrogen exposure do not produce a D peak, but water vapor
exposure does [21]. The lack of appearance of a D peak in graphene
after molecular hydrogen and nitrogen exposure may be due to the irradiated. In these spectra, the G− band has significantly broadened
ease at which these gases desorb from graphene due to their weak and increased in intensity.
physisorption. SWCNTs tend to be more reactive due to their cur- Fig. 6 is a magnification of the RBM region of the curves
vature and nanotube bundles possess locations where molecular in Fig. 5 with corresponding labels (a)–(g). The region around
hydrogen and nitrogen can be trapped. 200–280 cm−1 shows six peaks for pre-heated samples that are
Fig. 5 shows Raman spectra of HiPco grown SWCNTs that have reduced or disappear for pristine samples or samples that have been
been processed under the same conditions as those of the laser abla- irradiated without heating. For SWCNTs exposed to a 532 nm laser
(2.33 eV), these peaks correspond to E11 M transitions for metallic
tion grown SWCNTs. Fig. 5(a) shows a spectrum of pristine SWCNTs
that have not been irradiated. The G− band is noticeably broadened SWCNTs. There also appears two peaks at around 175 and 185 cm−1
that would correspond to E33 S transitions for semiconducting nano-
and shifted to lower wave numbers in comparison to that of the
laser ablation grown semiconducting SWCNTs, consistent with it tubes. There are also peaks at around 290 cm−1 corresponding to
S transitions for semiconducting SWCNTs. Pristine SWCNTs show
E22
being due to metallic SWCNTs. Figs. 5(b)–(e) show spectra for SWC-
a slight increase in the E33S peaks and a decrease in the E M peaks
NTs that have been preheated and/or post-annealed as follows: (b) 11
irradiated and post-annealed in situ; (c) irradiated, exposed to air, with respect to heated samples and no change in the E22 S peaks.

and post-annealed; (d) only pre-heated; (e) pre-heated and irra-
diated in situ. In these spectra, the D peak is reduced from that of
the pristine sample shown in Fig. 5(a), but the G− peaks are about
the same. Fig. 5(f) shows the spectrum of a pristine sample that
was pre-heated, irradiated in situ, exposed to air, and re-irradiated,
and Fig. 5(g) shows the spectrum of a pristine sample that was only
Samples that have been irradiated without pre-heating show a
M region
large increase in the 175 cm−1 peak and a reduction in the E11
with respect to heated samples.
In Fig. 7, the curves in Fig. 5 were fitted with eight sub-curves;
three Lorentzian curves at around 1310, 1325 and 1372 cm−1 for
the D band, and four Lorentzian curves centered at around 1517,
826 P.A. Ecton et al. / Applied Surface Science 387 (2016) 822–827
Fig. 8. XPS of laser ablation grown SWCNTs. No difference is indicated between the
as-prepared pristine and irradiated samples. Annealing shows a decrease in the C O
peak as well as a reduction in the FWHM of the C1s peak.
1542, 1572, and 1585 cm−1 , and a Breit-Wigner-Fano (BWF) curve
centered at 1518 cm−1 for the G band. Peak assignments and sym-
metries are extrapolated from previous studies [16]. The BWF curve
is attributed to phonon modes of A1g symmetry in metallic nano-
tubes and is asymmetric due to electron phonon coupling [20]. The
most likely source of this curve in the samples comes from the
metallic nanotubes with E11 M transition. The 1517 cm−1 curve can
be attributed to a G−S peak from the small diameter E22 S semicon-
ducting nanotubes of E2g symmetry overlapped with a G−M peak
from mid diameter nanotubes with E11 M transitions and A symme-
1g
try. The 1542 cm−1 curve can be attributed to the G−M peak from
upper mid diameter metallic nanotubes with E11 M transitions and
A1g symmetry in which inter-tube electron-phonon coupling does
not appear to occur [22,23]. The 1572 cm−1 curve can be attributed
to the G−S peak of the large diameter semiconducting nanotubes
with E33S transitions and E −1 curve
1g symmetry, and the 1585 cm
+
can be attributed to the G peak for both metallic and semiconduct-
ing nanotubes. The lower three curves (BWF and two Lorentzians)
that contain metallic components tend to significantly increase
after irradiation without heating but decrease when heated. These
curves correspond to nanotubes that have smaller diameters than
those grown using laser ablation. Their greater curvature may make
them more susceptible to damage from irradiation.
Since gas exposure is required for the phenomenon to occur,
we carried out XPS measurements to determine if physisorbed
gases chemisorbed on the nanotubes as a result of the irradiation.
Fig. 8 shows the XPS spectra of the C 1s region of four laser abla-
tion grown SWCNT samples; a pristine sample, a pristine sample
that was irradiated without pre-heating, a pristine sample that was
irradiated and then post-annealed in situ (600C for 30 min), and a
pre-heated sample (600 ◦ C for 30 min) that was irradiated in situ.
No noticeable change between the spectra of a pristine sample
and an irradiated pristine sample is observed. Both spectra show
peaks due to C O bonds and no peaks due to hydrogen or nitrogen
species. The XPS spectra of the two samples that underwent pre-
heating and post-annealing are similar and show that the oxygen
species that were originally chemisorbed on the pristine samples
have desorbed. Fig. 9 shows XPS spectra of HiPco grown SWCNTs
that were similarly processed showing again no noticeable change
between the spectra of a pristine sample and an irradiated pris-
tine sample. Since the XPS data show no change in the chemical
composition of the CNTs, this indicates that although the adsorbed
gases mediate the defect formation, they do not strongly chemisorb.
Therefore, the adsorbed gases may facilitate the production of a
structural defect in the C lattice and remain physisorbed, or pro-
duce a charge-transfer complex that distorts the lattice but does
not strongly chemisorb.
Fig. 9. XPS of HiPco grown SWCNTs. Similar to the laser ablation grown SWCNTs,
no difference is found between the pristine and irradiated samples. A slight shift
of about 0.2 eV is apparent between the annealed samples and the non-annealed
samples.
We characterize the defects produced in SWCNT bundles by
their effect on the BWF peak. The BWF peak in bundles has been
reported to increase as a result of tube–tube interactions that are
thought to produce a plasmon band that increases the plasmon-
phonon coupling [24]. For example, when bundles are reduced in
size [24], or the nanotubes within a bundle are isolated by oxi-
dation [25] or wrapping with DNA molecules [22,23], the BWF
peak decreases. The BWF peak increases again when the oxide or
DNA molecules are removed. In addition, defects such as vacan-
cies, oxides and cut edges produced by high power pulsed laser
irradiation decrease the BWF peak [17,26]. Since the BWF peak
increases as a result of an increase in tube–tube interactions, we
propose that the defects formed by low-energy electron irradia-
tion are such that they increase tube–tube interactions. This would
exclude oxides, vacancies and cut edges since they decrease the
BWF peak. A defect that may increase tube–tube interactions is
inter-tube linking in which adjacent tubes form bridges. Inter-tube
linking has been reported to form in SWCNT bundles as a result of
electron irradiation at an energy of 80 keV [27,28]. Although this
energy is about an order of magnitude higher than those used in
our experiments, it is below the theoretical knock-on threshold of
86 keV. We note that cross-linking has been reported in C60 films
irradiated with electrons at energies comparable to those used in
our experiments. Adjacent C60 molecules in such films have been
observed to form cross-linked peanut-shaped structures as a result
of irradiation at 3 keV [29]. Post-annealing at 200 ◦ C for 2 h reverts
the peanut-shaped structures back to C60 [30].
4. Conclusions
Our work shows that low-energy electron irradiation of SWCNT
bundles itself does not cause damage; we find that, for damage to
occur, there must also be adsorbates present on the nanotubes. To
our knowledge, this has not been reported to date. This conclu-
sion is based on our observation that the D peak does not increase
after adsorbates have been removed from the sample through the
process of preheating in UHV at 600 ◦ C before electron irradiation
is performed, but does increase after the sample is preheated and
exposed to air or gases before irradiation. We find that the influence
of gas adsorbates is more significant on the HiPco-grown samples
than the laser-ablation grown samples. The laser-ablation grown
samples consisted mainly of large-diameter E33 S semiconducting
SWCNTs, while the HiPco-grown samples consisted of E11 M metallic
SWCNTs that have smaller diameters than the laser-ablation grown
S semiconducting SWCNTs that have smaller
samples, as well as E22
M
diameters than the E11 metallic SWCNTs. It is known that the Fermi
level electrons in metallic SWCNTs can participate in chemical reac-
 P.A. Ecton et al. / Applied Surface Science 387 (2016) 822–827
tions. Such electrons are absent in semiconducting SWCNTs. It is
also known that as the diameter of a SWCNT decreases, the reac-
tivity increases due to the increase in curvature and resulting bond
strain [31]. We attribute the greater influence of adsorbates on
the HiPco-grown samples to the Fermi level electrons and smaller
M metallic SWCNTs, and the smaller diameters
diameters of the E11
S semiconducting SWCNTs. Both laser-ablation and HiPco
of the E22
grown samples recover after post-annealing at 450 ◦ C. XPS spectra
shows no evidence for irradiation-induced chemisorption as the
cause for the increase in the D peak. Since the BWF peak in metallic
SWCNTs increases after irradiation, we propose that the increase in
D peak for such nanotubes is due to defects that increase tube–tube
interactions, such as inter-tube linking. Since isolated SWCNTs have
been reported to show an increase in the D peak after low-energy
electron irradiation, it would be interesting to investigate if pre-
heating isolated SWCNTs in UHV before irradiation prevents an
increase in the D peak and occurrence of a metal-semiconductor
transition.
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