Journal of Alloys and Compounds 618 (2015) 33–36

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Journal of Alloys and Compounds

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

A simple route for fabrication of graphene nanoribbons by pulsed laser

irradiation in ethanol
Sin Young Bang a, Jeong Ho Ryu b, Bong Geun Choi a, Kwang Bo Shim a,⇑
a
Division of Materials Science and Engineering, Hanyang University, Seoul 133-791, Republic of Korea
b
Department of Materials Science and Engineering, Korea National University of Transportation, 50 Daehak-ro, Chungju, Chungbuk 380-702, Republic of Korea

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

Article history: Graphene nanoribbons (GNRs) are fabricated from multi-walls carbon nanotubes (MWCNTs) via an
Received 25 May 2014 unzipping process by using pulsed laser irradiation in ethanol. We confirm the successful transformation
Received in revised form 20 July 2014 from MWCNTs to GNRs by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman
Accepted 2 August 2014
spectroscopy. Related transformation mechanism is presented based on the pyrolithic and the photolithic
Available online 10 August 2014
interaction of MWCNTs with laser light.
Ó 2014 Published by Elsevier B.V.
Keywords:
Graphene nanoribbon
Pulsed laser irradiation
Unzipping process
Raman spectroscopy

1. Introduction
Graphene is a planar structure of carbon atoms at one atom of
thickness. It has attracted much attention due to its excellent char-
acteristics such as unique structure, electronics, chemical, mechan-
ical and physical properties which are useful for various
applications [1]. The graphene can be divided into different types
based on their structural characteristics such as graphene nanorib-
bons (GNRs) [2], graphene oxide [3], graphene sheet [4], graphene
film [5] and reduced graphene oxide [6,7]. GNR shave smooth
edges and a narrow width distribution (10–20 nm), and their elec-
tric properties show a semi-metal of zero-gap semiconductor
depending on the aspect ratio, the structure (zigzag and armchair),
the number of layers and edge states [8]. They have been utilized
for various applications such as electronic device [9] and compos-
ite materials owing to unique electronic property [10], flexibility,
high strength, high thermal property and gas barrier ability [11].
GNRs have been synthesized by lithographic [12], chemical [13],
plasma methods [14], chemical vapor deposition [15] and solution
based oxidative processes [16]. Nevertheless these methods have
some disadvantages such as the complex step processes, long exper-
iment time, and the use of toxic chemicals such as strong acids. Rao
et al. reported a new synthesis method for GNRs by a pulse laser
irradiation technique through longitudinal unzipping of MWCNTs
coated on glass substrate [17]. This method is fast and simple
⇑ Corresponding author. Tel.: +82 2220 0501; fax: +82 2 2291 7395.
E-mail address: kbshim@hanyang.ac.kr (K.B. Shim).
without using strong acid or oxidizing agent. Also, the final GNR
products are quite clean without impurities. However, it has low
productivity and difficult to collect the synthesized GNRs after pro-
cessing due to limited laser scanning area and processing scale-up.
Another novel technique using laser irradiation is a pulsed laser
irradiation (PLI) in liquid medium. The PLI process in liquid has
been a one of the promising techniques for several advantages such
as comparatively simple and easy processing of complex nanopar-
ticles. [18,19] However, there is little report on the preparation of
GNRs by PLI in liquid medium. In this study, we report a novel and
simple transformation route for fabrication of GNRs using PLI in
liquid medium. The MWCNTs (multi-wall carbon nanotubes)
successfully transformed to GNRs through unzipping process. Also,
transformation mechanisms of the synthesized GNRs are investi-
gated using transmission electron microscopy (TEM), X-ray diffrac-
tometer (XRD) and Raman spectroscopy.
2. Experimental
The MWCNTs as starting materials were prepared by catalyst chemical vapor
deposition (CCVD) method [20]. The diameter and purity of the MWCNTs were
10–20 nm and 99.0%, respectively. The 0.005 g of as-prepared MWCNTs was
dispersed in 2 L ethanol by ultrasonic for 10 h. Subsequently, the solution of the
MWCNTs (100 ml) was irradiated by pulsed laser (Nd:YAG 355 nm, Quanta
Ray-LAB190) with 100 mJ/pulse for 1 h as shown in Fig. 1. The repetition rate and
pulse width were 30 Hz and 10 ns, respectively. Nanostructure and morphology of
the fabricated GNRs were investigated by a high resolution TEM (HR-TEM, Jeol
3010, Japan). Crystallinity was investigated by XRD (Rigaku D/MAX 2C, Japan) using
Cu Ka radiation (1.5406 Å). The chemical structure of the fabricated GNRs was
measured by Raman spectroscopy (LabRam HR, Ar-ion laser excitation 514.5 nm,
Japan).

http://dx.doi.org/10.1016/j.jallcom.2014.08.004
0925-8388/Ó 2014 Published by Elsevier B.V.
34 S.Y. Bang et al. / Journal of Alloys and Compounds 618 (2015) 33–36
Fig. 1. A schematic diagram for pulsed laser irradiation process for fabrication of
GNRs.
3. Result & discussion
The microstructures of the raw MWCNTs and PLI-processed
sample are shown in Fig. 2(a) and (b). The MWCNTs have diameter
of 10–20 nm with tubular structure as shown in inset of Fig. 2(a).
The black arrows of Fig. 2(b) reveals that the MWCNTs successfully
transformed to GNRs by the PLI process, however, the broken
MWCNTs were observed as marked in white arrows. The trans-
formed GNRs had a good edge roughness, and the width of these
GNRs is around 30 nm as shown in inset of Fig. 2(b).
The possible mechanism of transformation from MWCNTs to
GNRs by PLI process is distinctly illustrated in schematic diagram
Fig. 2. (a) TEM picture of the MWCNTs raw sample. The inset shows the diameter of
the MWCNT is 20 nm. (b) TEM picture of PLI processed sample for 1 h. The
transformed GNRs and broken MWCNTs are marked with black and white arrows,
respectively. The inset shows that the transformed GNR has a good edge roughness
and width of 30 nm.
of Fig 3. The laser irradiation is based on the interaction of laser
light with matter. The interaction of material with photon can be
recognized as two different phenomena: pyrolithic and photolithic
processes [21]. Pyrolithic process is based on breaking of the chem-
ical bonds by photon energy. Pyrolithic method can be applied to
polymers by using ultraviolet lasers with wavelengths from 157
to 351 nm. Photon energy is converted directly in breaking chem-
ical bonds and there is very little thermal interaction with the
material. On the other hand, photolithic processes are based on a
rapid thermal cycle heating, melting, and partly evaporation of
the heated volume [21]. Therefore, the PLI process can be consid-
ered as a combined interactive process with the pyrolithic and
the photolithic mechanism.
The pulse laser with 355 nm wavelength is absorbed mostly by
MWCNTs based on the photolithic mechanism [21]. Higher energy
in laser can be applied to MWCNTs compared to the breaking
energy of C–C bond (248.5 eV) of walls, which attaches oxygen-
containing functional groups such as carbonyls, carboxyls, epox-
ides or hydroxyls to the edges and surface (Fig. 3(a)) [2–6,16]. This
process is analogous to the longitudinal unzipping of carbon nano-
tubes [22]. Once the carbon bonds with oxygen-containing func-
tional group by laser irradiation, unzipping proceeds further
along the strain induced by the carbon–carbon bond angle [23]
as shown in Fig. 3 (b) and (c). Under PLI process, the pyrolithic
and the photolithic process accelerate the unzipping process. Sub-
sequently, the PLI breaks C–C bonds and generates considerable
thermal vibration simultaneously, which leads to the transforma-
tion from MWCNTs to GNRs.
The transformed GNRs via unzipping process from MWCNTs are
obviously observed in Fig. 4. The transformed GNRs (black arrow)
and broken walls of MWCNTs (white arrow) after PLI process are
shown in Fig. 4(a). Fig. 4(b) shows the unzipping process at the
mid-section of the MWCNTs under PLI process [22]. The width of
inner side of unzipped area is larger than that of the tip, which cor-
responds to the unzipping mechanism of Fig. 3(b). Fig. 4(c) pre-
sents the magnified figure of the unzipping tip showing
exfoliated inner, middle and outer layer as shown in Fig 3(c).
Fig. 4(d) shows the transformed GNR layer with 61.6 nm width.
The inset of Fig. 4(d) is the selected area electron diffraction (SAED)
patterns of GNRs transformed from MWCNTs, it is similar to simu-
lated SAED pattern of highly ordered pyrolytic graphite (HOPG)
indexed as the (0 0 1) zone axis. The conventional SAED patterns
of MWCNTs show the ring pattern or spot pattern in line to
(0 0 2) direction due to poorly ordered carbon atoms among the
curling layers in the multitubular structure. However, the SAED
patterns of transformed GNRs are similar to HOPG due to the
improved ordering of carbon atoms among the layers by curved
multilayers when the tubular structure change to the planar layers
structure of 2D by unzipping of MWCNTs by PLI [24] (see Fig. 5).
The carbon characteristic peaks of MWCNTs in XRD patterns are
shown at 25.76° [d(0 0 2) = 3.44 Å] and GNRs at 25.86°
[d(0 0 2) = 3.41 Å]. The hexagonal carbon sheets of MWCNTs have
tubular structure, while the GNRs have planar structure. Thus,
the interplane d(0 0 2) space of MWCNTs is larger than GNRs
[25,26]. It is concluded that MWCNTs is transformed to 2D struc-
ture of GNRs throughout the sample.
Fig. 6 shows the Raman spectra of the MWCNT and transformed
GNRs after PLI process. The spectra show three Raman bends at
1342 cm 1 (D band), 1579 cm 1 (G band) and 2706 cm 1 (2D
band). The G band indicates the original graphite feature due to
the in-plane vibration of sp2 carbon atoms. Also, the D band can
be explained since amorphous carbon contains a certain fraction
of sp3 carbons, and disordered carbon atoms in the graphite struc-
ture [27]. The intensity ratio of the D band to the G (I(D)/I(G)) and
the ratio of their sizes were employed to determine the fraction
of in-plane crystallite in the graphite structure. The value of
 S.Y. Bang et al. / Journal of Alloys and Compounds 618 (2015) 33–36 35

Fig. 3. Representation of the transformation process via gradual unzipping of MWCNTs during pulsed laser irradiation.

c 100 010
110
110

010 100

Fig. 4. TEM pictures confirming unzipping process by pulsed laser irradiation. (a) Transformed GNRs (black arrows) and broken MWCNTs (white arrows), (b) the unzipping
process occurred at the mid-section of MWCNT, (c) picture of exfoliated layers and (d) transformed GNR layer with 61.6 nm width.

2D band
G band
1579 cm -1
2703 cm -1
D band
Intensity ( a.u.)

1579 cm -1
2706 cm-1

Raman Shift cm-1

Fig. 5. XRD patterns of fabricated GNRs and MWCNTs as the starting materials. Fig. 6. Raman spectra of the MWCNTs and transformed GNRs at 514.5 nm.
36 S.Y. Bang et al. / Journal of Alloys and Compounds 618 (2015) 33–36
I(D)/I(G) for the starting material is 0.75. It reveals that our starting
material was conventional MWCNTs. The intensity ratio, I(D)/I(G)-
value of the transformed GNR was equal (0.75) to that of MWCNTs.
This indicates no change in crystallinity during transformation
from MWCNTs to GNRs [28]. The increase of 2D band peak indi-
cates transformation of tubular structure into planer structure
[29]. The value of I(G)/I(2D) was decreased from 1.20 to 0.91 and
2D band peak was shifted from 2706 to 2703 cm 1 by transforma-
tion from MWCNTs to graphene layers. The FWHM of the 2D peak
for the transformed GNRs was 51 cm 1s, which is smaller than that
of the MWCNTs, 84 cm 1. These indicate a reduction of the Raman
laser penetration depth, but the thickness of graphene layers was
almost same with the thickness of walls in MWCNTs.
4. Conclusions
A novel transformation route for graphene nanoribbons (GNRs)
using pulsed laser irradiation (PLI) in liquid medium is proposed.
The multi-wall carbon nanotubes (MWCNTs) are successfully
transformed to GNRs through unzipping process by PLI in ethanol.
The mechanism of transformation and nanostructures are
explained based on the unzipping process, which originated from
the pyrolithic and the photolithic reaction with carbon–carbon
bonds. It is noted that the PLI process in liquid medium is simple
and green experimental process. Therefore, the PLI technique is a
one of the promising methods for fabrication of GNRs compared
to the known chemical routes.
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