Vacuum 110 (2014) 1e6

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Sharp folded graphene ribbons formed by CO2 laser ablation for

electron field emission studies
Vishakha Kaushik a, Himani Sharma a, b, A.K. Shukla a, V.D. Vankar a, *
a
Thin Film Laboratory, Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
b
Department of Electrical & Computer Engineering, University of Alberta, Edmonton, Alberta T6G 2V4, Canada

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

Article history: A facile approach is used to grow sharp folded and wrinkled graphene structures by laser ablation
Received 16 April 2014 process. The laser-graphite target interaction mechanism and effect of substrate temperature variation
Received in revised form (400
C and 700
C) on the growth structure of graphene is studied. The low solubility of carbon in Cu
30 July 2014
helps in the deposition of graphene flakes by self-limiting process. High resolution transmission electron
Accepted 31 July 2014
Available online 8 August 2014
microscopy and Raman spectroscopy are utilized to confirm the crystalline structure of graphene at
higher temperatures. These exotic structures are further studied for their electron field emission char-
acteristics after transferring over Si/SiO2 substrates. The sharp folded graphene structures (turn-on field
Keywords:
Laser ablation
1.4 V/mm) displayed enhanced electron field emission properties in comparison to wrinkled graphene
Graphene (turn-on field 2.0 V/mm). The obtained wrinkled graphene structure is extremely suitable for field
Microscopy emission applications. This work presents an efficient technique to grow different graphene structures
Electron field emission using laser ablation process that can act as potential candidates for future field emission devices.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction CO2 laser needs attention [13]. Graphene based nanostructures

Graphene, a single atomic sheet of graphite with ballistic
transport of charge carriers and metallic character possessing zero
band gap, is one of the potential materials for future electronic
applications [1]. Owing to marvellous properties to be explored for
plethora of applications such as nano-electronic devices, flash
memory devices, sensors and solar cells, synthesis of graphene is
still an important issue and is at nascent stage [2e5]. Graphene can
be synthesized by various means, such as, mechanical and chem-
ical exfoliation of graphite, epitaxial precipitation and chemical
vapour deposition (CVD) etc [6e8]. Out of various methods
mentioned, CVD has proven to be the most promising approach for
the growth of graphene films. Various groups have used carbon
dioxide (CO2) laser for the growth of carbon nanotubes and this
could also be exploited to synthesize graphene [9e12]. To the best
of our knowledge, very few studies mentioned the growth of
graphene based nanostructures by CO2 laser and thus, the growth
mechanism of graphene and other carbon nanostructures using
* Corresponding author. Tel.: þ91 11 26591329; fax: þ91 11 26581114.
E-mail addresses: vdvankar@gmail.com, vdvankar@physics.iitd.ernet.in
(V.D. Vankar).
and graphene nanocomposites synthesized by various different
techniques have been explored for field emission studies [4]. The
edges of graphene play an important role for emission of electrons.
Growth of unique graphene structures is also an important aspect
from field emission point of view, as structure defines and affects
the electron field enhancement properties of a material. Field
emission properties from single and few layer graphene flakes on
flat SiO2/Si substrate has been reported by Santedrea et al. [14].
They observed emission currents up to ~1 mA at applied field of few
hundred volt/mm for flat part of graphene. Guo and group showed
in their studies that increasing the wrinkle size and its top cur-
vature not only improves the field enhancement factor of the
wrinkled graphene but also decreases the electron affinities and
ionization potentials by first principles calculations [15]. The field
emission studies of graphene have been utilized by Lee et al. to be
explored for vacuum nano-electronics device studies [16]. All the
mentioned studies provide quite important information on the
field emission mechanism of graphene structures. But there is still
more room and interest for studying this unique structure for field
emission applications from graphene based nanostructures.
Keeping in view the above, the present paper dwells in to CO2 laser
ablated growth process of graphene nanostructures and its ap-
plications for field emission.

http://dx.doi.org/10.1016/j.vacuum.2014.07.032
0042-207X/© 2014 Elsevier Ltd. All rights reserved.
2 V. Kaushik et al. / Vacuum 110 (2014) 1e6
2. Experimental details
Graphene based samples were prepared using laser ablation
equipped with CO2 laser (l ¼ 10.6 mm) from a pyrolytic graphite
target (purity 99.99%) in a vacuum chamber. The chamber was
evacuated with a turbo-molecular pump to a base pressure of
~106 torr. The films were deposited on copper (Cu) substrates
placed ~ 50 mm apart from the graphite rotating target as shown in
Fig. 1. The substrate temperature was varied from RT to 700
C.
Details of the samples are provided in Table 1. Graphene was
transferred to Si/SiO2 substrate using FeCl3/PMMA recipe [17].
Laser evaporation process involves a high-power laser that ir-
radiates the surface of the graphitic target followed by absorption
of energy by graphite. The growth by laser ablation depends upon
the various parameters; laser energy, laser target interaction,
temperature of the substrate and the target etc. The continuous CO2
laser beam have sufficient energy to heat graphitic target, so no
auxiliary heater is needed. Further, the copper substrate kept at
higher temperature (700
C) facilitates the formation of nano-
structural graphene. On heating the copper to higher tempera-
ture, large polycrystalline grains are formed on its surface as shown
in the schematic (Fig. 2). When the continuous CO2 laser beam
impinges on the graphite target, ejected carbon atoms from the
target evaporate to deposit on the annealed copper grains. The low
solubility of carbon in Cu helps in the formation of graphene
nanostructures. Several reports on the growth of graphene also
mention the monolayer growth of graphene by CVD process [18]. In
our case, monolayer growth of graphene is not achieved but
nanostructures of graphene are formed. It is also observed that
nanostructures of the graphene are at substrate temperature as low
as 400
C.
3. Characterization
The graphene and other samples were characterized using
scanning electron microscopy (SEM: Zeiss EVO 50) operating at a
20 kV accelerating voltage and high resolution transmission elec-
tron microscopy (HRTEM:Technai G220S-Twin model) operating at
200 kV. Micro-Raman studies of the samples were carried out in
back scattering mode (T64000 JobinYvon triple monochromator
system). An excitation wavelength of 514.5 nm using an argon ion
laser was used to analyse the structure of the samples. The Raman
studies were carried out on the as deposited samples.
The electron emission characteristics of graphene samples were
studied using a diode setup in a vacuum chamber at a base pressure
of 2  106 torr. Graphene samples were used as a cathode and a
Fig. 1. A Schematic diagram showing growth of graphene structures using continuous
wave CO2 laser ablation set up.
Table 1
Parameters used for the growth of nanoclusters graphene samples by continuous
wave CO2 laser ablation technique.
Samples Structure formed Temperature Time of deposition
name (minutes)
G1 Amorphous carbon Room temperature 15
G2 Sharp folded graphene 400
C 15
G3 Wrinkled graphene 700
C 15
stainless steel plate was used as an anode. The distance between
the cathode and the anode was adjusted by using an ac stepper
motor and was kept at 200 mm. The measurements were carried out
using a high voltage dc power supply (H5KO2N) and a current
meter (Keithley 196 system DMM). Graphene samples were
transferred to the silicon substrate for carrying out field emission
studies.
4. Results and discussion
The SEM images of bare and deposited Cu foil are shown in
Fig. 3(a) and (b), respectively. The difference in both the micro-
structures can easily be marked out. The graphene grains are seen
in Fig. 3(b), indicated by dotted circles. These grains cover almost all
of the area of Cu foil. The low solubility of carbon in Cu helps in the
deposition of graphene flakes by self-limiting process [19].
Fig. 4 shows the HRTEM images of graphene based nano-
structures. Since the deposition was carried out at three different
temperatures, three different microstructures corresponding to
these temperatures are observed. These are named as G1, G2 and
G3. The sample G1 was deposited at room temperature and its TEM
micrograph is shown in Fig. 4(a). The micrograph shows the pres-
ence of non homogeneous amorphous carbon formation and is
non-crystalline as observed from the SAED pattern shown in
Fig. 4(b). A pattern of diffraction spots results from the electron
beam diffracted by a single crystal. The continuous rings are formed
in a sample consists of small randomly distributed grains; these
grains contribute to the formation of the diffraction pattern.
However, in the case of very small or the amorphous materials, the
feature of concentric rings disappears and only left a halo around
the bright spot in the centre, which indicates that the electrons are
diffracted randomly by the material of amorphous structure.
Fig. 2. A Schematic view presenting copper grains formed by heating copper to higher
temperature and growth of graphene structures on copper.
 V. Kaushik et al. / Vacuum 110 (2014) 1e6
Fig. 3. SEM micrographs showing (a) bare and (b) deposited Cu foil respectively and the graphene grains are indicated by dotted circles.
Amorphous carbon with short range order produces diffuse ring in
diffraction pattern.
Fig. 4(c) and (d) show the microstructure and SAED pattern of
the sample G2, respectively. This sample was grown at 400
C. The
sharp folded graphene structure is seen in this Fig. 4(c). The crys-
tallinity of nano graphene structure is confirmed by the SAED
pattern. Fig. 4(e) and (f) show wrinkled graphene morphology and
corresponding SAED pattern of the sample G3 which was grown at
700
C. It is evident from HRTEM images that crystalline graphitic
morphology is observed in samples grown at higher temperatures
(G2 and G3) in comparison to the one grown at lower temperature
(G1). The d-values of samples G2 and G3 are found to match with
those corresponding to graphite (JCPDF no. 75-2078). The crystal-
linity of the samples G2 and G3 showing wrinkled nanostructure of
graphene is further confirmed by HRTEM images seen in Fig. 5(a)
and (b), respectively. The marked region in Fig. 5(b) show the
graphitic lattice planes with the despacing of 3.4 Å and the auto
correlated image of marked region is shown in Fig. 5(c). No lattice
planes were observed for G1 sample.
During the growth of wrinkled graphene, the direct interaction
between carbon and Cu plays an important role. In the present
study, it is mentioned that, sharp folded and wrinkled graphene are
formed at 400
C and 700
C temperatures, respectively. However
no graphene formation has taken place at room temperature. The
possible reason of no graphene formation is possibly due to the
presence of an oxide layer on Cu substrate at room temperature.
The formation of copper oxide is confirmed by Raman spectroscopy
(Fig. 6). Formation of copper oxide is also observed in samples held
at 400
C. No such oxide was observed on the substrate held at
700
C. This facilitated direct Cu/C interaction to form graphene
layers. The wrinkles are observed in the structure due to mismatch
of thermal expansion coefficient of Cu and carbon. Furthermore,
solubility of copper with carbon plays an important role in the
growth process of graphene. The solubility of carbon at room
temperature and 700
C is 1.5  104 ppm and 2.5 ppm, respec-
tively [19]. Thus, due to extremely low solubility at room temper-
ature, no growth of graphene is expected. However, as the
temperature is increased to 400
C, copper clusters are formed and
thus helps in the formation of graphitic structures. At 400
C mixed
phase of CueC is formed due to sintering and grain growth of
copper. As solubility of CueC is higher at 700
C temperature,
carbon segregates out to form graphene films on Cu surface. The
optimum temperature for growth of graphene is found to be 700
C
in the laser ablation process.
Our results are consistent with those of by Kidambi et al.,
wherein they reported the ease of oxygen intercalation between
3
graphene and Cu by in-situ X-ray photoelectron studies [20]. They
have mentioned that presence of oxygen easily decouples graphene
from metal. According to some reports, graphene formation will
commence by photo-thermal mechanism if the impinging laser
energy (2.3 eV) is lesser than the CeC bond energy (3.7 eV).
Otherwise, bonds between the carbon atoms break resulting into to
the formation of amorphous carbon [21]. However, graphene for-
mation is explained by photo electronic excitation using KrF laser
(5 eV), that involves the breakage of carbon bonds [22]. In present
study, CO2 laser has been used as an impinging laser with photon
energy of 1.16 eV, that is much smaller than CeC bond energy, thus
helps in the formation of nanostructure graphene by photo-
thermal mechanism.
4.1. Raman studies of graphene ribbons
Micro Raman spectroscopy, which is one of the powerful tech-
niques to probe structural and electronic characteristics of gra-
phene, has been utilized for structural analysis of graphene based
structures and other carbon based structures [23,24]. Various
important Raman modes are related to graphite based structures,
such as D, G band and 2D [25e27]. The presence of the mentioned
modes confirms the presence of graphene formation. Here, D mode
(1350 cm1) corresponds to presence of sp3 bonding present in the
formed; however in-plane vibration of sp2 carbon atoms is
confirmed by presence of G mode (~1580 cm1). Another mode (2D,
~2670 cm1) at higher wave number side is related to the charac-
teristic peak of graphene. Fig. 6(a) shows the Raman spectrum of
sample G1, which shows the presence of amorphous carbon. It is
seen that along with small intensity D and G modes, a more intense
appear at 1450 cm1. This shows characteristic features of amor-
phous carbon. Amorphous carbon show these minor modulations
around 1100e1200 and 1400e1500 cm1 [28]. An inset image
confirms the presence of an optical mode of copper oxide at
629 cm1. This Raman data supports our growth mechanism, ac-
cording to which at room temperature copper oxide formation
hinders Cu/C interaction and thus inhibits the formation of gra-
phene. A Raman spectra of samples G2 and G3, which are sharp
folded graphene and wrinkled graphene, are shown in Fig. 6(b) and
(c). Since the growth takes place at 400
C and 700
C for G2 and G3
sample, G and D modes are clearly visible confirming the presence
of crystalline graphite. The values of D and G modes are presented
in Table 2. However a very small intensity peak at 1162 cm1 sug-
gests the presence of amorphous carbon in these laser ablated
nanostructures. The inset image of Fig. 6(b) also confirms the for-
mation of copper oxide during growth of graphene nanostructures.
4 V. Kaushik et al. / Vacuum 110 (2014) 1e6

Fig. 4. HRTEM micrographs showing graphene based nanostructures grown at three different temperatures (a) nano-cluster is deposited at room temperature and (b) (b) these
nanoclusters are not crystalline as observed from the SAED pattern (c, d) show the microstructure and SAED pattern of nano-cluster deposited at 400
C (e, f) show the micro-
structure and SAED pattern of nano-cluster deposited at 700
C respectively.

Fig. 5. HRTEM images showing the crystallinity of the samples G2 and G3 (a) and (b), respectively, (c) show the auto correlated image of planes shown in the yellow circle in (b). The
marked regions show the graphitic lattice planes with the d-spacing of 3.4 Å. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
 V. Kaushik et al. / Vacuum 110 (2014) 1e6
Fig. 6. First order and second order micro Raman spectra of nanostructured graphene samples (a) sample G1 deposited at room temperature and (b) sample G2 deposited at 400
C
(c) sample G3 deposited at 700
C respectively (d) shows comparison of 2D spectra of G1, G2 and G3 samples.
However, no such peak is seen in Fig. 6(c). Thus, the growth tem-
perature ~700
C is the optimum temperature for growth of gra-
phene structures by laser ablation. The ID/IG ratio explains about the
crystallinity of carbon based structures shows that G2 and G3
samples are crystalline. However, no such crystalline behaviour is
seen in sample G1. Fig. 6(d) shows the 2D mode of samples G1, G2
and G3, respectively. The peak positions of all Raman modes are
mentioned in Table 2. It is seen that G3 shows more characteristic
features of graphene. However, the 2D mode of samples is quite
broad in comparison to G3 sample. The growth of graphene shows
sharp features of 2D mode. In case of laser ablation process, the
presence of amorphous carbon may modify the Raman mode.
4.2. Electron field emission studies of graphene ribbons
The field emission of amorphous carbon (G1) sharp folded
graphene nanostructures (G2), wrinkled graphene nanostructures
(G3) are well related with the HRTEM studies. The electron emis-
sion characteristics of CNs are given by Fowler-Nordheim (FeN)
theory [29e32]. The current density (J) versus electric field (E) and
their corresponding FeN plots are shown in Fig. 7.
The turn on field (Eon) is taken as (10 mA/cm2). No threshold field
values are obtained due to very low current. The Eon values are
found as 1.4 V/mm and 2.0 V/mm for G2 and G3 samples, respec-
tively. The Eon value for G1 samples is found to be 3.5 V/mm, which
is very high in comparison to other samples. It is found that sharp
folded graphene nanostructure shows better field emission prop-
erties than wrinkled graphene nanostructures. The field emission
property of amorphous carbon is lower in comparison to both the
other nanostructures. The better emission from sharp folded
Table 2
Raman parameters presenting the D, G and 2D mode for samples G1, G2 and G3.
Samples name D mode G mode 2D mode
G1 1335 1589
G2 1355 1584.5 2872
G3 1354.5 1585.1
5
graphene nanostructure is appears to be due to presence of more
emission cites in the structure in comparison to wrinkled graphene
nanostructure. As seen in HRTEM images, the sharp folded nano-
structures have more sharp edges in comparison to the wrinkled
structure; these sharp structures act as more prominent cites for
electron emission. The electrons will be emitted from sharp wrin-
kled tops on application of high field.
According to theoretical studies carried out by Guo et al.,
wrinkles act as protrusions formed on graphene sheets [15].
Increasing the wrinkle size improves their field emission proper-
ties. In our case, more wrinkled and sharp folded graphene nano-
structures show better emission. On the application of bias, more
local density of states (LDOS) is available, providing more electrons
for emission in case of sharp folded graphene structures in com-
parison to the other structures. Thus, helps in better emission
properties.
5. Conclusions
In conclusion, we have demonstrated a simple way to grow
wrinkled and sharp folded graphene structures. It is found that
growth of graphene on copper foil substrates occurs at an optimum
ID/IG
Fig. 7. The macroscopic emission current density (J) as a function of applied macro-
e
scopic field (E) from nanostructured graphene samples G1, G2 and G3 prepared at
0.6
different substrate temperature respectively. The inset shows the FeN plots for the
0.4
same samples.
6 V. Kaushik et al. / Vacuum 110 (2014) 1e6
temperature after limited dissolution and hence segregation.
Furthermore, it is observed that the resulting structures exhibit
enhanced electron field emission properties. Sharp folded nano-
structures have more sharp edges in comparison to the wrinkled
structure; these sharp structures act as more prominent cites for
electron emission. The electrons will be emitted from sharp wrin-
kled tops on application of high field. Our study has shown sig-
nificant progress of graphene in the fabrication of appealing
structures for field emission applications.
Acknowledgements
One of the authors (V.K.) is thankful to director IIT Delhi for
providing a research scholarship. Authors are also thankful to Dr. D.
C. Sharma for using SEM facility. The financial support of the
Ministry of Information Technology (MIT), Government of India, is
gratefully acknowledged.
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