Multilayered graphene efciently formed by mechanical exfoliation

for nonlinear saturable absorbers in ber mode-locked lasers

You Min Chang,
1
Hyungseok Kim,
2
Ju Han Lee,
1
and Yong-Won Song
2,a
1
School of Electrical and Computer Engineering, University of Seoul, Seoul 130-743, Republic of Korea
2
Optoelectronic Materials Center, Korea Institute of Science and Technology, Seoul 136-791,
Republic of Korea
Received 25 August 2010; accepted 6 November 2010; published online 22 November 2010
An efciently prepared graphene from a bulk graphite using mechanical exfoliation is
experimentally investigated for the rst practical application to ultrafast photonics. Overcoming the
limitations of the method in its size and atomic layer control, the multilayered graphene guarantees
a nonlinear intensity modulation. After conrming its excellent crystal quality and few-layered
nanostructure employing Raman analysis and atomic force microscopy the graphene layer is
introduced into a ber laser as an intracavity saturable absorber to realize the passive mode-locking
that produces picosecond pulses at the repetition rate of 10.9 MHz. Extinction ratio of the resultant
pulsed output is higher than 40 dB. 2010 American Institute of Physics. doi:10.1063/1.3521257
Graphene, a two-dimensional 2D atomic-scale honey-
comb lattice of carbon atoms, has attracted much scientic
attention as a high-potential material for the realization of
future smart devices, due to its outstanding electronic and
optical properties that originate from its semi-metal or zero-
bandgap energy band structure as well as its ultrafast intra-
and interband carrier excitation and relaxation.
1,2
The optical
nonlinear saturable absorption of graphene has especially
been intensively investigated in recent years to nd out if it
can replace traditional semiconductors
3
or carbon nanotubes
4
for photonic devices that highlight i ultrafast operation
recovery time of 200 fs, ii low saturable absorption
threshold, iii large modulation depth 60% for few-
layered graphene, and iv wavelength-independent
operation.
58
So far, graphene saturable absorbers have been
made with either a 2D at graphene thin lm closely at-
tached onto the end facet of an optical ber ferrule
6,8
or a
sprayed graphene layer on the polished surface of a
D-shaped ber for a high-power operating regime
7
providing
formation of high quality femotosecond pulses. Unfortu-
nately, however, the preparation processes of graphene and
graphene-based devices still rely on traditional and inef-
cient approaches, including chemical synthesis tools such as
chemical vapor deposition
9
and a solution method
10,11
that
cannot be free from the restrictions of additional transfer
process steps and the extremely low yield of graphene. A
dramatically simplied but elegant graphene preparation
method based on mechanical exfoliation of bulk graphite
with a strip of scotch tape was very recently reported.
12,13
For many years, practical applications of the method have
been limited by the size problem of the resulting graphene
akes as well as the difculty of controlling the monoatomic
layer.
In this study, a mechanically exfoliated multilayered
graphene was prepared, its optical properties were character-
ized, and the applicability of the graphene layers to ultrafast
photonics as saturable absorbers for passive mode-locking of
the ber lasers was experimentally investigated. After ensur-
ing the nanomorphologies of the prepared layers via atomic
force microscopy AFM and Raman analysis,
1315
the chro-
matic dispersion of the graphene samples was analyzed via
group delay measurement to nd that the nanoscaled thin
layers had negligible dispersion.
6
In a ber ring laser cavity,
the optical-intensity-dependent absorption modulation of the
multilayered graphene which ranged from subnanometer to
3 nm was demonstrated for the passive laser pulsation.
The multilayered graphene on the end facet of the opti-
cal ber ferrule was prepared by the efcient mechanical
exfoliation method. The starting material was commercially
available highly ordered pyrolytic graphite HOPG from
SPI Co. The HOPG sample, which had a dimension of 10
10 mm
2
, was prepared via mechanical cutting in a venti-
lated hood to avoid possible contamination. The HOPG
akes were peeled repeatedly to optimize the thickness of the
sample for pressing by the substrate. Considering the strong
interaction between the contacting surfaces of the graphite
and the optical ber amorphous SiO
2
that tended to form a
graphite/ SiO
2
interface with low interfacial energy, me-
chanical exfoliation can be applied to the graphene layer for-
a
Electronic mail: ysong@kist.re.kr.
Scotch
Tape
(a)
Graphene-
Deposited
Ferrule
(c)
Fiber
Ferrule
(ZrO
2
)
(b)
Fiber
Ferrule
(ZrO
2
)
Multilayered
Graphene
Optical
Fiber (SiO
2
)
(d)
FIG. 1. Color online Graphene preparation on a ber ferrule. a Initial
scotch tape exfoliation of the highly ordered pyrolytic graphite to adjust the
thickness. b Contact of a surface-cleaned ber ferrule with the graphite. c
Careful separation of the ferrule from the graphite. d Conceptual explana-
tion of the resultant graphene-deposited ber ferrule.
APPLIED PHYSICS LETTERS 97, 211102 2010
0003-6951/2010/9721/211102/3/$30.00 2010 American Institute of Physics 97, 211102-1
mation on the optical bers.
13,16
After the surface of the op-
tical ber was cleaned using acetone, ethanol, and de-ionized
water to ensure an uncontaminated surface, the prepared
HOPG akes were pressed with the ber ferrule according to
the sequence described in Figs. 1a1c. As a result, thin
graphene layers were left on the targeted core area of the
optical ber, as conceptually illustrated in Fig. 1d.
The prepared graphene layers were analyzed with atomic
force microscopy AFM, XE-100, Park Systems, scan rate of
0.5 Hz. It was found that they had a multilayered morphol-
ogy with thicknesses that ranged from subnanometers 23
layers to several nanometers 78 layers; see Fig. 2. The
3D plot in Fig. 2 provides a visual insight for a morphologi-
cal understanding of the multilayered graphene formed using
the mechanical method. It was also revealed that the
graphene layers with heights of 12 nm 35 layers domi-
nated the scanned area. Although mechanical exfoliation
does not guarantee a uniform monolayered graphene, the av-
erage saturable absorption of the graphene layers can still be
applied to the laser mode-locking, sacricing the operation
window and the nonlinear intensity modulation depth that
are inversely proportional to the thickness of the graphene
layers.
5,7
The dimensions of the graphene layer were in the
micron scale and thus it can cover the large part of the
mode eld area of the optical ber, guaranteeing beam-
nanostructure interaction. Importantly, since the depth of the
nonlinear absorption depends mainly on the morphology and
dispersion of graphene, whereas the background absorption
level depends on the amount of the unwanted carbon mate-
rials such as the agglomerated graphene or the amorphous
carbon,
4,7
an attempt was made using the mechanical exfo-
liation to escape from the deleterious overlap, folding, dis-
tortion, deformation, and agglomeration of the graphene
layers, which are unavoidable in the conventional spray
methods. In Raman analysis, the D peak at 1350 cm
1
,
shown in Fig. 3a, was correlated with the disorder of the
graphene lattice, and the G peak at 1580 cm
1
corresponds
to the phonon excitation at the Brillouin zone center.
14,15
The
log scale plot in Fig. 3a emphasizes that the D peak has a
single and sharp shape as well as low intensity, which repre-
sent the high crystal quality of the mechanically exfoliated
graphene without signicant defects on it. With a 514 nm
excitation, the strong stronger than the G peak and narrow
shape of the 2D peak at 2700 cm
1
suggests that the pre-
pared graphene could have only a few-layered structure,
which has good correlation with the result described in Fig.
2.
15
The transmission electron microscope TEM image
shown in the inset of Fig. 3a also ensures the few-layered
structure of the mechanically prepared graphene. Normally,
it is known that the ratio of I
D
/ I
G
is inversely proportional to
the interdefect distance, and therefore proportional to the de-
fect density. Compared with the Raman peaks of the sprayed
graphene that was synthesized with the chemical method,
7
as
can be seen in the linear scale in Fig. 3b, the mechanically
exfoliated graphene has superior crystal quality that makes it
applicable to nonlinear photonic devices. It is thought that a
slight upshifting of the G peak of the chemically synthesized
graphene is related to the chemical contamination of the
graphene surface.
15
To characterize the dispersion property
of the graphene layers, the wavelength-dependent group de-
lay was measured. The group delay measurement resolution
was estimated to have been 300 fs, and the corresponding
group velocity dispersion GVD measurement resolution
was 30 fs/ nm. A 10 GHz sinusoidal signal from the net-
work analyzer was used as a driving signal for the LiNbO
3
modulator and an optical beam from a wavelength-tunable
external cavity laser was modulated by the driving signal.
The 10 GHz modulated beam was fed into a graphene
sample and then the transmitted beam from the sample was
converted back into an electrical signal and coupled into a
network analyzer. While the wavelength of the laser beam
was changed from 1540 to 1580 nm, the relative group delay
change of the transmitted beam was measured. Figure 4
shows the measured delays of the three graphene samples as
a function of the laser beam wavelength. It is clearly evident
from the curves that all the graphene samples had negligible
GVDs unlike the result of a recent study.
6
To apply the scotch tape-exfoliated graphene samples to
the ultrafast photonic device, a ring cavity of the ber laser
FIG. 2. Color online AFM analysis on the few-layered graphene. Its 3D
image left and height analysis on the selected parts right are presented.
1400 1600 1800 2000 2200 2400 2600 2800
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Raman Shift cm
-1
)
40 nm
Slep
Sleps
D
G
D
2D
(a)
1300 1400 1500 1600
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Raman Shift cm
-1
)
D
G
Mechanically
Exfoliated Graphene
Chemically
Synthesized
Graphene
(b)
FIG. 3. Color online a Raman characterization of the mechanically ex-
foliated graphene layer in a log scale. Inset shows a TEM image of the
terrace-structured graphene. b Comparison of the Raman peaks in a linear
scale between the mechanically exfoliated graphene and the chemically syn-
thesized one.
1540 1550 1560 1570 1580
-1
0
1
2
Port S1
Device
Under
Test
10GHzRFNetworkAnalyzer
LiNbO
3
Electro-optic
Modulator
Highspeed
Photo-detector
Port S2
Wavelength
TunableLaser
Sample 1
Sample 2
Sample 3
R
e
l
a
t
i
v
e
G
r
o
u
p
D
e
l
a
y
(
p
s
)
Wavelength (nm)
FIG. 4. Color online Chromatic dispersion characteristics of the three
graphene samples, which reveal that the dispersion values were negligible.
The inset presents the dispersion measurement setup based on the phase
shift method.
211102-2 Chang et al. Appl. Phys. Lett. 97, 211102 2010
was constructed, as depicted in Fig. 5a. Here, the graphene
layer acts as a passive mode-locker based on the nonlinear
saturable absorption effect. The cavity was composed of a
5 m long erbium-doped ber EDF, a 980/1550 nm wave-
length division multiplexer WDM, an isolator-incorporated
1480/1550 nm WDM, a 90:10 coupler, and a polarization
controller. The graphene layer on the ber ferrule was sand-
wiched and protected in a rigid case. The EDF was pumped
bidirectionally. Along with the state of polarization that is
one of the critical factors of the phase matching condition,
the pumps power level was also adjusted to provide enough
gain and intracavity nonlinearities. The pulsation due to the
saturable absorption of the graphene layer was initiated in
the high-pumping regime pump power of 300 mW. At
this power level, unlike other weak modes that are absorbed
by the graphene layer, only a limited mode with enough in-
tensity can pass through the graphenes saturable absorber to
stimulate other modes with phase-locking, which will result
in the passive formation of periodic short pulses. Here, the
pulse duration is inversely proportional to the number of
modes that are phase-locked. Once the laser pulsation is
achieved, the pump power can be decreased while maintain-
ing the pulsation operation to optimize the clean pulse for-
mation without the nonlinear pulse breaking that originated
from the extra power and the unwanted multiple lasing. The
reproducibility of the graphene layer was conrmed by re-
peating the same mode-locking experiments with three
samples to nd that the tape-exfoliated graphene can be
readily applied to ultrafast photonic devices. Figure 5b
shows the measured oscilloscope waveform traces of the out-
put pulse trains. The pulse period was 91.7 ns, which indi-
cates a repetition rate of 10.9 MHz that is coincident with the
fundamental frequency of the implemented ring cavity, the
length of which is estimated to 19 m. In Fig. 5c, the
optical spectra of the mode-locked lasers, which were mea-
sured in a resolution bandwidth of 0.02 nm, are shown to-
gether with theoretical sech
2
tting curves. The 3 dB spectral
bandwidth of all the three cases was 0.8 nm. Assuming that
the pulses were in transform-limited soliton forms, the esti-
mated output pulse width for the cases was 3.2 ps. The out-
put power of the mode-locked laser was 4.8 dB m irrespec-
tive of the graphene samples used. The corresponding rf
spectra of the output pulses, which were measured under a
resolution bandwidth of 300 Hz, are shown in Fig. 5d. The
fundamental repetition rate and the peak-to-background ratio
were 10.92 MHz and 40 dB, respectively, for all three
cases, which veries that the graphene saturable absorbers in
this work operated as reliable laser pulse formers for future
ultrafast photonic devices.
This work was partly supported by Institutional Re-
search Program of Korea Institute of Science and Technol-
ogy KIST funded from Korean Ministry of Education, Sci-
ence and Technology MEST. Also supported by the Basic
Science Research Program through the National Research
Foundation of Korea NRF funded by the Ministry of Edu-
cation, Science, and Technology MEST, Republic of Korea
Grant No. 2009-0064477.
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Graphene
Mode-Locker
Polarization
Controller
Single-Mode
Fiber
Er-Doped
Fiber Amplifier
90/10
Fiber Coupler
Isolator
Output
(a)
1574
1576
1578
Sample 1
Sample 2
Sample 3
O
p
t
i
c
a
l
P
o
w
e
r
(
1
0
d
B
/
d
i
v
)
W
a
v
e
le
n
g
th
(n
m
)
(c)
-500
-250
0
250
500
0.0
0.5
1.0
Sample 1
Sample 2
Sample 3
N
o
r
m
a
l i
z
e
d
A
m
p
l
i
t
u
d
e
T
im
e
(
p
s
)
(b)
-8
-6
-4
-2
0
2
4
6
8
-110
-100
-90
-80
-70
-60
-50
Sample 1
Sample 2
Sample 3 E
l
e
c
t
r
i
c
a
l
P
o
w
e
r
(
d
B
m
)
F
re
q
u
e
n
c
y
(k
H
z
)
(d)
FIG. 5. Color online a Experimental setup for a passively pulsed ber
ring laser. b Measured oscilloscope waveform traces, c optical spectra,
and d rf spectra of the output pulse trains of samples 1, 2, and 3, which
verify the case-insensitive operation of the graphene saturable absorbers that
were prepared via mechanical exfoliation.
211102-3 Chang et al. Appl. Phys. Lett. 97, 211102 2010