REVIEW

Graphene Photonics, Plasmonics, and

Broadband Optoelectronic Devices
Qiaoliang Bao†,‡ and Kian Ping Loh†,‡,*
†
Graphene Research Centre, National University of Singapore, 6 Science Drive 2, Singapore 117546, and ‡Department of Chemistry, National University of Singapore,
3 Science Drive 3, Singapore 117543

S
ilicon photonics has been hailed as
the technology of promise which will ABSTRACT Graphene has been hailed
make super-high-speed Internet ac- as a wonderful material in electronics, and
cess a reality. In reality, progress toward a recently, it is the rising star in photonics, as
photonics-driven circuit is hampered by well. The wonderful optical properties of
problems in the downscaling and integra-
graphene afford multiple functions of
tion of optoelectronic hardware. The pre-
signal emitting, transmitting, modulating,
sent state of development in integrated
photonics is not unlike the integrated circuit and detection to be realized in one
revolution more than 50 years ago. Break- material. In this paper, the latest progress
throughs similar to what silicon transistors in graphene photonics, plasmonics, and
had achieved for integrated circuits are broadband optoelectronic devices is reviewed. Particular emphasis is placed on the ability to
critically needed for integrated photonics integrate graphene photonics onto the silicon platform to afford broadband operation in light
before it can take off in a big way.
routing and amplification, which involves components like polarizer, modulator, and photodetector.
It is good to remind ourselves why silicon,
which is prevalent in electronics, is also a Other functions like saturable absorber and optical limiter are also reviewed.
favorite choice in photonics. The main rea-
KEYWORDS: graphene . photonics . optoelectronics . broad band . ultrafast
son is its amenability to the monolithic laser . saturable absorber . polarizer . optical modulator . photodetector . optical
integration of optics and electronics.1 Silicon- limiter
based photonic components ranging from
passive devices to modulators, detec-
tors, and light amplifiers and sources have be realized in one material. Graphene shows
been developed.1
3 However, it is unlikely superior properties compared to silicon and
that all of the photonic components can be III
V semiconductors in terms of its high
silicon-based, especially when there is a thermal conductivity (∼36 times higher than
need to fulfill the stringent demands of Si and ∼100 times higher than GaAs), high
broadband data transferring. First of all, optical damage threshold12 (a few orders of
intrinsic silicon, which has an indirect band magnitude higher than Si13 and GaAs14),
gap, is not a broadband optical material even and high third-order optical nonlinearities
though its absorption edge can be tuned by (∼10
7 esu),15,16 as shown in Table 1.17
21
controlling the doping level.4 Other draw- These macroscale properties are important
backs inherent to silicon include low electro- for photonic devices. At present, the Holy
optic coefficient, low light emission efficiency, Grail for graphene growth is to deposit gra-
and high propagation losses due to scattering phene directly on insulators such as SiO2;22,23
off the side walls of the waveguide. To this this is an eagerly awaited breakthrough which
end, the fabrication of hybrid materials which will open up a route for monolithic integration
can marry the advantages of silicon and a of graphene and silicon photonics.24 The pro-
second broadband photonic material seems spect of integrating a graphene photodetec-
the most promising way forward. tor in CMOS (complementary metal
oxide
* Address correspondence to
chmlohkp@nus.edu.sg.
Graphene, a conjugated sp2 carbon sheet semiconductor) in the near future is particu-
arranged in a two-dimensional (2D) hexa- larly alluring. Recently, an IBM group demon- Received for review March 6, 2012
gonal lattice,5,6 is the new kid on the block strated the use of graphene as an optical and accepted April 18, 2012.
for electronics7,8 as well as photonics.9
11 receiver operating on a silicon-on-insulator
Published online April 18, 2012
The wonderful properties of graphene allow (SOI) substrate.25 A Berkeley photonics group 10.1021/nn300989g
multiple functions of signal emitting, has also successfully integrated graphene with
transmitting, modulating, and detection to a Si waveguide to fabricate a radio frequency C 2012 American Chemical Society

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optical modulator.26 These successes are the first mile- VOCABULARY: photonics
the science and applied
stones toward hybrid silicon
graphene photonic circuits. technology involves the generation, emission, transmis-
The Optics Vision. Due to the unique electronic struc- sion, modulation, signal processing, switching, amplifica-
ture in which conical-shaped conduction and valence tion, detection, and sensing of light · polarizer
a device
bands meet at the Dirac point, the optical conductance that converts a beam of light with undefined or mixed
of pristine monolayer graphene is frequency-indepen- polarization into a beam with well-defined polarization ·
dent in a broad range of photon energies: G1(ω) = optical modulator
a device that is used to vary the
G0 t e2, where ω is the radian frequency, e is electron fundamental characteristics (amplitude, phase, or
charge, and p is reduced Planck's constant.27
30 As a polarization) of a light beam propagating either in free
direct consequence of this universal optical conductance, space or in an optical waveguide upon external electric
the optical transmittance of pristine graphene is also field · photodetector
a device that measures photon
frequency-independent and solely determined by the flux or optical power by converting the energy of the
fine structure constant R = e2/pc (c is the speed of light): absorbed photons into a measurable form. It has two
T  (1þ2πG=c)
2  1
πR  0:977 (1) principal classes: photoelectric detector and thermal de-
When scaled to its atomic thickness, graphene tector · saturable absorption
a property of materials
actually shows strong broadband absorption per where the absorption of light is decreased to a steady level
unit mass of the material (πR = 2.3%, Figure 1a), at sufficiently high incident light intensity · saturable
which is ∼50 times higher than GaAs of the same absorber
an optical material that is used in laser cavities
thickness.29,31,32 The reflectance under normal light in- to reshape laser pulses due to saturable absorption. The
cidence is relatively weak and written as R = 0.25π2R2T = key parameters for a saturable absorber are its working
1.3  10
4, which is much smaller than the trans- wavelength, dynamic response, modulation depth, and
mittance.28 The absorption of few-layer graphene can saturation intensity · optical limiter
a kind of nonlinear
be roughly estimated by scaling the number of layers optical device that strongly attenuates intense optical
(T = 1
NπR). In principle, a low sheet resistance can be beams while exhibiting high transmittance for low-inten-
attained without sacrificing the properties of transparency sity ambient light ·
too much (i.e., tens of Ω/0 for T > 90%). As such, graphene
enthusiasts are hopeful that few-layer graphene can According to above equations, both interband and
potentially replace ITO (indium tin oxide) as transparent intraband conductivities are closely correlated with the
conductors for applications in solar cells33
35 and touch chemical potential of graphene and the frequency of
screens9,36,37 in cases when it is sufficiently doped. incident light. The chemical potential of doped gra-
The property of graphene is largely controlled by phene is determined by the carrier concentration
the chemical potential (μ, also Fermi level EF). The n0 = (μ/pν)2/π, which can be controlled via chemical
transition from dielectric to metallic behavior in terms doping or electrical gating. There is no intraband
of optical transition32,38 can be tuned by chemical contribution for pristine graphene which has μ = 0.
doping or electrical gating, as schematically illustrated Due to the occurrence of zero band gap, the intraband
in Figure 1b,c. Within the random-phase approxima- and interband contributions compete and the inter-
tion, the dynamic optical response of graphene can be band transition only occurs above the threshold of |μ|=
derived from Kubo formula in a complex form consist- pω/2, as shown in Figure 1d. Generally, for slightly
ing of interband and intraband contributions27,30,39 doped graphene (|μ| < pω/2), the high-frequency
σ ¼ σintra þ σinter 0 þ iσinter 00 (2) dynamic conductivity is dominated by interband con-
tribution for Dirac fermions extending across a wide
where the intraband conductivity σintra has the
bandwidth from visible to infrared (IR), which covers
Drude-like form
the telecommunication bands and also the mid-IR
4μ 1
σintra ¼ σ0 (3) regions. The intraband contribution will only be rele-
π pτ1
ipω
vant in the terahertz range when |μ| > pω/2 (Figure 1d);
where σ0 = πe2/(2h), τ1 is the relaxation rate associated this condition allows for plasmon momentum enhance-
with intraband transitions, and μ > 0 is the chemical ment, and thus propagation of surface plasmon in
potential. The interband contribution has the form graphene is possible.40
42 As a result, the relative con-


1 pω
2μ 1 pω þ 2μ tributions from optical interband transition and intraband
σ inter 0 ¼ σ 0 1 þ arctan
arctan (4)
π pτ2 π pτ2 transition can be varied, leading to tunable optical
and response32,38 as well as polarization-selective coupling.26,43
1 (2μþpω)2 þ p2 τ22 Nonlinear Effects in Graphene. The optical nonlinearities
σinter 00 ¼
σ0 ln (5) originate from the interactions of the optical field with
2π (2μ
pω)2 þ p2 τ22
electrons and phonons. Specifically, the electric field of
where τ2 is the relaxation rate associated with inter- the optical signal resonates with the electrons in the outer
band transitions. shells of carbon atoms and displaces the electron cloud

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TABLE 1. Materials Properties of Graphene, Si, GaAs, Si, and Hexagonal-BN (h-BN)

optical damage threshold nonlinear Kerr

thermal conductivity energy gap refractive (peak intensity of single shot, third-order optical coefficient
(W m
1 k
1) Eg (300 K) eV index n MW/cm2) nonlinearities (esu) (m2 W
1)

graphene12,15
17 5300 0 2.6 3  106 ∼10
7 10
11 at 1.55 μm

Si13 149 1.11 3.44 500 2.5
5  10
11 (4.5 ( 1.5)  10
18 at 1.55 μm
GaAs14,18,19 55 1.43 3.4 45 ∼4  10
8 3.3  10
17
h-BN20,21 ∼500 1.36  10
14
)

20 ( ), 27 (^) 4.0
5.8 2.2

Figure 1. Schematic diagrams showing possible optical transitions in graphene. (a) In intrinsic graphene, single-photon absorption
in terms of symmetric interband transition can take place over a broad wavelength range from visible to infrared. (b) In n-doped
graphene, an optical photon (pω2) with energy less than 2EF cannot be absorbed because the electron states in resonance in the
conduction band are occupied. (c) In p-doped graphene, an optical photon (pω2) with energy less than 2EF cannot be absorbed
because there are no electrons available for the interband transition. (d) Interband plasmon absorption (pω2) and intraband
plasmon (pω3) absorption with momentum enhancement. (e) Electromagnetic wave (E) passing through the graphene lattice and
inducing dipole moments (P). The displaced electron cloud is shown only for one atom. (f) One-photon and two-photon absorption
(TPA) process. (g) Under an intense optical field, the electron states in the conduction band are filled and prevent further optical
transition due to Pauli blocking, producing the condition of saturable absorption (SA). (h) Carrier dynamics after photoexcitation
showing the processes by which the non-equilibrium electron and hole distributions approach equilibrium. Reproduced from ref 60.
Copyright 2008 American Chemical Society.

with respect to the nucleus, resulting in a net dipole such as two-photon absorption (TPA) (Figure 1f), self-
moment (polarization), as shown in Figure 1e. In the focusing, self-phase modulation, saturable absorption
simplest case of linear optics regime, the induced dis- (SA) (Figure 1g), optical bistability, etc.
placement (x) manifests as electronic polarization (P), Dipole excitations with bound and free electrons
obeying a linear relationship with the applied field (E): induced by a single photon are described by the
P = ε0χ(1)E, where ε0 is the permittivity of free space and first-order susceptibility χ(1), where the real part is corre-
χ(1) is the first-order (linear) susceptibility. In the case of lated to the real part of the refractive index and
large displacement caused by strong optical field, elec- the imaginary part is related to optical loss or gain. The
tronic polarization is significantly nonlinear with respect to effective linear susceptibility to optical fields at a fre-
quency ω can be modulated by applying a dc field across
displacement as well as applied electric field, which could
graphene, which changes the refractive index. This linear
be described by a Taylor expansion:44
electro-optic effect is manifested readily in graphene,32
P ¼ ε0 (χ(1) E þ χ(2) E 2 þ χ(3) E 3 ) þ ::: (6) which forms the basis of a broadband optical modulator
recently demonstrated.26 Due to the inversion symmetry
where χ(2) and χ(3) are the second- and third-order non- of the graphene unit cell, the second-order susceptibility
linear susceptibilities, associated with nonlinear phenomena χ(2) is generally absent as a result of the cancellation of the

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optically excited second-order electrical current at oppo- of optical nonlinear effects in graphene, which includes
site momenta with respect to the Dirac point. However, saturable absorption,53
56 self-focusing and nonlinear
χ(2) may be operative in strained,45 disordered, or functio- refractive index change (i.e., Kerr effect16), optical bist-
nalized graphene46
48 in which the bilayer symmetry is ability and switching, and soliton propagation.57
59
broken, thus allowing many possibilities to be exploited in In practice, the total sheet current in graphene
χ(2) nonlinear electro-optic active material. For example, in fluctuates with time as well as the pumping conditions
graphene derivatives that do not possess inversion sym- (duration of ultrashort intense optical field). The use of
metry, the application of an optical field at frequency ω ultrashort terahertz laser pulse allows the carrier dy-
may generate its second harmonic at 2ω, which may find namics in graphene to be investigated,60 as shown in
important uses for laser frequency doubling as well as high- Figure 1h. The interband optical excitation produces a
resolution optical microscopy. More interesting effects may non-equilibrium carrier population in the valence and
arise by applying the incident field with two frequencies conduction bands of graphene. Shortly after photoexci-
(ω1 and ω2), for example, to generate the sum and tation (within 10
150 fs), the hot electrons thermalize to
form a hot Fermi
Dirac distribution, which will be
difference frequencies (ω1 ( ω2). Recently, Wu et al.49
further cooled by intraband phonon scattering in the
demonstrated that a giant and tunable second-order non-
following 150 fs to 1 ps. Electron
hole recombination
linear susceptibility can be observed in bilayer graphene
will dominate in the process beyond ∼1 ps, which affects
when an in-plane electrical current between source and
the interband conductivity. In view of the nonlinearities
drain electrodes is introduced to suppress the cancellation
in time domain, the interplay between intraband and
of optically induced electric current.
interband dynamics should be considered to completely
In principle, third-order nonlinear processes are al-
describe the nonlinear optical response in graphene.52
lowed in all materials, whether they process inversion
Plasmons in Graphene. Surface plasmons are collective
symmetry or not. Most of the optical nonlinearities in
oscillations of electrons at the surface of a conductor,
graphene are associated with the third-order susceptibility
and it can be excited by photon or electron. Noble
χ(3). However, χ(3) is correlated to the polarization per unit
metals (e.g., Au and Ag) are widely regarded as the best
volume to the third power of the electric field E and
available plasmonic materials, but devices fabricated
graphene is an infinitesimally thin and isotropic conduc-
from these suffer from large Ohmic losses and non-
tivity surface. The classical model fails to fully interpret the
tunability once the geometry of the structure is fixed.
optical nonlinearities in graphene, and it is more appro-
Graphene has been recently proposed as a new
priate to describe the nonlinear response in terms of the
platform for plasmon waveguiding at infrared
nth order total integrated sheet current:15,45,46,50
52
frequencies40
42,61,62 and can be considered as tera-
Z
1 hertz metamaterials.63 Photons in the infrared or ter-
Jνn ¼ dpjνn N(ε) (7)
4π2 ahertz domain can be readily coupled to surface
plasmons in graphene and form a surface plasmon
where the thermal factor N(ε) = nF(
ε)
nF(ε) =
polariton (SPP) surface wave with many appealing
tanh(ε/2kBT), and jνn = ψ†kvvψ, where the current operator
properties,42,64 such as extreme confinement, tunabil-
k
v v = (∂H)/(∂pv) with v = x, y.
ity via electrical gating or chemical doping, and low
The first-order total current, that is, linear optical
losses resulting from long lifetime with hundreds of
response, J1 = e2E/(4p), after converting into real units,
optical cycles. These features make graphene plas-
coincides with the universal conductance deduced
monics an attractive alternative to traditional metal
from above-mentioned Kubo formula (eq 2). For a
plasmonics. Graphene plasmonics have been demon-
symmetric crystal, ^v(x) = ^v(
x), which implies the
strated in photonic metamaterials,63 light harvesting,65
second order total sheet current J2 = 0. The third-order
optical biosensing,66 and transformation optics.67
current can be written as51
The tunability of SPP surface waves in graphene
J3 ¼ J3 (ω) þ J3 (3ω) originates from its complex dynamic conductivity de-
termined from the Kubo formula (eq 2), which largely
σ1 e2 ν2F E02
¼ [N1 (ω)eiωt þ N3 (ω)e3iωt ] (8) depends on the radian frequency (ω), relaxation time
p2 ω4 (τ1) of excited carriers, and chemical potential (μ).39,68
where vF ≈ c/300, σ1 = e2/4p, the thermal factors The imaginary part of dynamic conductivity, which
N1(ω) = N(ω) and N3(ω) = 13N(ω/2)/48
N(ω)/3 þ may have a negative or positive signature at different
45N(3ω/2)/48. According to eq 8, the third-order frequency ranges depending on the chemical poten-
current is a superposition of two third-order terms tial, plays an important role in supporting different
correlated to three-photon processes, that is, a single types of surface waves. Pristine graphene or graphene
frequency term J3(ω) and a third-harmonic generation with very low chemical potential has a negative σ00 over
term J3(3ω). Both of these two terms are inversely a large frequency range, leading to a semiconductor-
proportional to ω4 and proportional to E20 which is the like behavior, capable of guiding a transverse-electric
power of the field. They are responsible for a wide variety (TE) electromagnetic SPP surface wave, as illustrated in

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Figure 2a.40,61 At a large chemical potential (|μ|>pω/2), real-space images of plasmonic field profiles, and they
it will give a positive σ00 and graphene will behave like experimentally measured the confinement factor to be
metal thin film capable of supporting a transverse- 40
60.70,71 We should take note that these works
magnetic (TM) electromagnetic SPP surface wave were carried out on a graphene-oxide-semiconductor
(Figure 2b), which shows similar behavior to that in (Si) device; the feasibility of optical nanoimaging of
noble metals.47,53
55 Such TM SPP is a type of p-polar- graphene plasmons will definitely pave the way
ized surface plasmon propagating along the sheet with for advanced graphene
Si
metal hybrid plasmonic
a dispersion relation described by42 circuits.

 Photonic Applications. Motivated by the interesting
p2 i
ksp  2 (ε þ 1)ω ω þ (9) optical properties of graphene, many graphene-based
4e EF τ1
photonic and optoelectronic applications have been
The dispersion curves can be obtained by solving developed recently.9,10 Here we will provide a brief
the above equation using a semiclassical approach, as review of the latest development in graphene photo-
shown in Figure 2c, in which the results from random- nics, which include a graphene waveguide, broadband
phase approximation (RPA) are also shown for polarizer,43 graphene modulator,26 graphene photo-
comparison.41,69 The quadratic dependence of ksp on detector,72
77 surface plasmon enhanced photo-
ω is a typical characteristic of 2D electron gases. The detector,78,79 saturable absorber for mode-locked80
83
field profiles of plasmon in graphene look quite similar and Q-switched pulse lasers,84
86 broadband optical
to those of surface plasmons in metals except for limiter,87 etc. We found that most of these photonic
qualitative differences in electronic dispersions (linear devices exhibit broadband performance, which is directly
Dirac cones versus usual parabolic). The degree of or indirectly correlated with the unique electronic struc-
confinement of SPP surface wave in graphene can be ture in graphene. The broadband operation of these
written as devices ranges from visible to near-infrared (NIR) wave-
length and is summarized in Figure 3.
4R EF
λsp =λ0  (10) Broadband Polarizer. The semimetal nature of gra-
ε þ 1 pω
phene inspires researchers to explore its optical wave-
where λ0 is free-space-light wavelength and λsp = guide phenomenon. The local dynamic response of
2π/Re{ksp} is the wavelength of the SPP surface wave. ultrathin metal film to electromagnetic wave is de-
Assuming λ0 =10 μm, the chemical potential of scribed by the Drude model, in which the concentra-
graphene μ = EF = 0.15 eV and τ ≈ 10
13 s, thus it tion, effective mass, and scattering rate of electrons are
gives λsp = 144 nm and the confinement factor (also the key parameters. The spectra of electromagnetic
the effective SPP index, nspp) is calculated to be 69.34. modes are sensitive to the electron mass in conven-
The in-plane propagation distance of such TM SPP, tional 2D electrons systems with parabolic dispersion.
given by 1/Im{ksp}, reaches a value of 2.25 μm, which is However, as discussed above, the massless Dirac fer-
15.6 times the surface plasmon wavelength.67 This can mions in graphene modify the plasmon and plasmon
be experimentally achieved by fabricating ribbon-like polariton spectra and introduce some radically new
sections of graphene with different chemical poten- features.39,40,61,88 The consequence is that graphene
tials, which is analogous to a conventional metal
can selectively support either the TM or TE electro-
insulator
metal (MIM) waveguide, as shown in magnetic modes depending on its Fermi level and
Figure 2d.67 The chemical potential in a different incident energy. This provides the basis for the
section of graphene is controlled by different thickness development of graphene/silica hybrid waveguide,
of the dielectric layer. Alternatively, dielectric film with which supports either a TM or TE surface wave
the same thickness but different dielectric constant can selectively, thus transforming unpolarized incident
be used as a spacer. Clever design in growth and light into polarized light. Such polarization is vital to
fabrication methods can be applied to tailor the shape reducing signal fading and error in coherent optical
of graphene. Some proposed structures of graphene communications.
SPP waveguiding structures which mimick the metal/Si In order to fabricate a polarizer which relies on the
waveguides are shown in Figure 2e
g.64,67 waveguiding property of graphene, coupling and
We should remark that many of the considera- phase-matching issues have to be considered. Using
tions above are still theoretical due to the practical conventional prism or gratings is possible but lacks
difficulties in exciting and detecting the SPP surface high efficiency and is not easy to operate with gra-
wave in graphene. This is because of the large wave phene. Due to the atomic thickness of graphene,
vector mismatch between graphene plasmons and it is challenging to realize highly efficient coupling
free-space photons. Recently, researchers discovered and high-confinement guiding. Recently, researchers
gate-tunable graphene plasmons by scattering-type successfully coupled wide-band light into graphene
scanning near-field optical microscope (s-SNOM) using film by fabricating a graphene-to-fiber coupler in
infrared excitation light (Figure 2h), which provided which graphene grown by chemical vapor deposition

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Figure 2. Graphene plasmons and SPP surface wave. (a) Schematic illustration of interband transition (left) which supports
the TE wave propagation (right). (b) Schematic illustration of intraband transition which supports the TM wave propagation
(right). (c) Dispersion curves of plasmon in graphene by semiclassic and RPA approaches. For black solid and black dot-dashed
lines, graphene is suspended in a vacuum. For blue dashed and blue dotted lines, graphene is on top of dielectric material with
ε = 4. Reprinted with permission from ref 41. Copyright 2009 The American Physical Society. (d) Electric field profile (Ey) of the
TM surface wave at a frequency of 30 THz propagating along the ribbon-like section of graphene with the chemical potential
of 0.15 eV (L = 560 nm, w1 = w2 = 200 nm). (e) Similar to (d), but the TM surface wave is split into two paths along the Y shape
graphene junction (L1 = 1077 nm, L2 = 560 nm, w1 =600 nm, w2 = 200 nm). (f) Similar to (d), but the TM surface wave
propagates along a bent ribbon-like section of graphene (L = 370 nm, w1 =120 nm, w2 = w4 = 30 nm, w3 = 60 nm, w5 = 120 nm).
Panels d-f reprinted with permission from ref 67. Copyright 2011 The American Association for the Advancement of Science.
(g) Schematic illustration of two parallel graphene ribbons embedded in silica (top) with a distance of 5 nm and electric near-
field of plasmon modes for two ribbons separated by a distance of 5 nm with energies of 0.15 (middle) and 0.21 eV (bottom).
Reproduced from ref 64. Copyright 2012 American Chemical Society. (h) Schematics of s-SNOM on top of graphene/SiO2
interface which is designed to probe Dirac plasmons by IR excitation light. IR near-field nanoscopy images displayed at two
different frequencies are shown on the right. Reproduced from ref 71. Copyright 2011 American Chemical Society.

(CVD) was transferred onto the side-polished optical pristine graphene is used (with slight substrate-induced
fiber, as schematically illustrated in Figure 4a.43 As doping), the TE surface wave is supported whereas the TM

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materials. When shifting the electronic Fermi level by
chemical doping or electric gating, the optical transi-
tions in graphene can be controllably tuned over a
wide bandwidth.32,93
By integrating graphene with a Si optical wave-
guide, graphene had been used as the active medium
in an optical electro-absorption modulator,26 as shown
in Figure 5a. The coupling strength between the
evanescent waves and graphene can be controlled
by changing the Fermi level (EF) using an external gate
field, which produces changes in the transmission of
Figure 3. Broadband operation of graphene-based photo- the optical modulator, as illustrated in Figure 5b.26
nic devices including polarizer, optical modulator, photo- Changing the bias voltage shifts the Fermi level above
detector, pulse laser, and optical limiter.
or below the threshold value (pω/2), and hence optical
wave is scattered via leaky modes. The TE-pass polariza- interband transitions can be switched “on” or “off”. This
tion effect works over a wide wavelength range from forms the basis of an electrically controlled optical switch.
visible to NIR with a large polarization extinction ratio The optical modulation effect can be observed in optical
(∼27 dB at 1.55 μm), as shown in Figure 4c. This polariza- bandwidth from 1.35 to 1.6 μm and a very large radio
tion effect is distinct from that in a metal-clad fiber frequency bandwidth up to 1.2 GHz.26 By constructing an
polarizer with a similar configuration (shown in Figure 4b), optical modulator with two graphene layers separated by
in which only the TM wave is supported due to SPP an oxide layer, the modulation depth can be further
propagation in the metal strip.89,90 increased to ∼0.16 dB/μm.94 The proven modulation
In principle, the TE-pass polarizer can be switched to efficiency is already comparable to traditional optical
TM-pass polarizer once the graphene film is sufficiently modulators made of Si,95 GeSi,96 and InGaAs.
Apart from the modulation based on optical inter-
doped to shift the chemical potential to a
band transition, the modulation of optical intraband
value larger than half excitation energy (pω/2). For in-
transition (or so-called plasmon absorption) is also
stance, ferroelectric polymers such as polyvinylidene fluor-
possible. Andersen et al.97 proposed a TM surface
ide (PVDF), which has strong dipole moments, can be
plasmon modulator at long-wavelength IR range
coated on top of the graphene film and applied as a top
(λ = 10 μm), in which an electric back gate is used to
gate, as shown in Figure 4d. A small external bias can cause
change Fermi level in graphene, as shown in Figure 5c.
a strong dipole field in PVDF,91,92 which can further dope
The modulation principle is based on the plasmon
graphene and shift the Fermi energy to a level which can losses versus carrier density, that is, high or low losses
support TM SPP at telecommunication wavelength (e.g., for different carrier densities when the interband ab-
1.55 μm). Alternatively, a change in the sign of external sorption of the plasmon energy is allowed or blocked
field can also cause a switchable polarization effect be- (Figure 5d). The theoretical on/off ratio can reach ∼62
tween a TM and TE wave in such an electro-optical device. dB. In principle, such a modulator should have a much
Broadband Optical Modulator. An optical modulator is a faster switching speed than the modulator based on
device that is used to vary the fundamental character- optical interband transition because the intraband
istics of a light beam propagating either in free space or carrier relaxation time (τ1 < 1 ps) is intrinsically much
in an optical waveguide upon external voltage control. faster than the interband carrier (τ2 > 1 ps) relaxation
These devices can be amplitude, phase, or polarization time (see Figure 1h).
modulators. As discussed above, the effective linear The complementary role of graphene to silicon
susceptibility χ(1) can be modulated by applying an photonics inspires the design of new structures tar-
electric field across graphene, thus causing changes in geted to improve the figures of merit in optical mod-
both the real and imaginary refractive indices. The ulation, which include modulation speed and depth
change in the real part of the refractive index concerns (extinction ratio), optical bandwidth, insertion loss,
electro-refraction, whereas the change in the imagin- area efficiency (footprint), and power consumption.
ary part concerns electro-absorption. The primary ef- One demonstration may be a buried-type modulator
fects induced by the electric field include Pockels which consists of dual graphene layers separated by
effect, the Kerr effect, the Franz-Keldysh effect, and thin BN spacers and sandwiched between single-crys-
the quantum-confined Stark effect (QCSE), and de- talline Si (bottom) and polycrystalline silicon (top),24 as
pending on which effect is manifesting, the modula- shown in Figure 5e. Graphene is placed at the center of
tors can be classified as either electro-refractive or the waveguide with maximum light intensity, so as to
electro-absorptive. The unique electronic structure in maximize the modulation depth and lower the power
graphene affords a much stronger electro-absorption consumption. Another example is a structure with
effect, which has not yet been observed in bulk graphene incorporated in the silicon ring resonator

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 REVIEW
Figure 4. (a) Schematic illustration of the metal-clad fiber polarizer. (b) Schematic illustration of the graphene-based broad-band
polarizer. (c) Polar image measured at 980 and 1550 nm. The green line indicates the project of the graphene film in the x
y plane
(a). Panels a and c reprinted with permission from ref 43. Copyright 2011 Nature Publishing Group. (d) Schematic illustration of a
switchable graphene polarizer in which the output polarization state can be controlled by an external electrical field.

for translating phase variations into intensity varia- transport of photocarriers in graphene are fundamen-
tions, as illustrated schematically in Figure 5f. The tally different from that in a semiconductor with a band
transmitted signal from the Si/graphene hybrid gap. The absorption of light generates electron
hole
waveguide can be strongly modulated upon the pairs in graphene, which has a lifetime of picoseconds
modification of the resonant wavelength caused by before recombination.53,60 Under an external field, the
tuning the effective index of the ring waveguide. pairs can be separated and transported to give a
Graphene can also be coated on a GaAs microdisk detectable photocurrent. Both photovoltaic effect
resonator to induce whispering gallery mode and photothermoelectric effect can contribute to gen-
(Figure 5g), which can be a new type of optomecha- eration of photocurrent in graphene.9,99,100 The photo-
nical resonators. Lastly, we propose a hybrid gra- voltaic effect relies on the existence of a built-in electric
phene/BN quantum confined Stark effect modulator, field which helps to accelerate the photogenerated
as shown in Figure 5h. The electrons and holes within charge carriers toward the electrodes. Such a built-in
the graphene/BN multilayer quantum well locate field can exist when the source and drain contacts on
within a discrete set of energy sub-bands. An external graphene are constructed of metal of different work
electric field shifts electron and hole states to oppo- functions.25 The photothermoelectric effect is pro-
site sides of the energy well, decreases the overlap duced by light-induced temperature gradient across
integral, and thus changes the absorption of the an interface between two materials wherein one of the
system. materials has a different Seebeck coefficient.
Broadband Photodetector. The spectral bandwidth and The IBM group pioneered a graphene-based
response time are important figures of merit of a photodetector with an ultra-broadband photore-
photodetector. The spectral bandwidth is determined sponse from 514 to 2400 nm.72,74
77 They suggested
by the band gap of the materials, and the response that the operation wavelength range can be further
time is correlated to the carrier mobility. Traditional expanded from 300 nm to 6 μm, which surpasses
photodetectors based on group IV and III
V semicon- state-of-the-art photodetectors. Mueller et al.75 de-
ductors suffer from limited spectral bandwidth as they monstrated a graphene photodetector for error-free
are “blind” to photons with energy smaller than the high-speed optical communications. In their work,75
band gap.98 Graphene can be potentially applied in interdigitated metal electrodes are deposited on top of
an ultrafast broadband photodetector because of its graphene to enlarge the light detection region and
exceptionally high carrier mobility and ultra-wide- shorten the transport length of carriers, as shown in
band absorption window.74
76 The generation and Figure 6a. The use of asymmetric metal electrodes with

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 REVIEW
Figure 5. Graphene-based optical modulator. (a) Graphene-based electro-optical modulator. A monolayer graphene is on top
of a silicon bus waveguide, which is separated by a thin Al2O3 layer. The silicon waveguide is doped and connected to the right
Au electrode by a thin layer of silicon. Graphene film is connected to the left Au electrode by a thin layer of Pt. (b) Static electro-
optical response of the modulator at different drive voltages. Panels a and b reprinted with permission from ref 43. Copyright
2011 Nature Publishing Group. (c) Schematic structure of graphene plasmon modulator. (d) Propagation of λ0 = 10 μm plasmons
by RPA approach with different carrier density. Top: Low-loss state with high carrier density. Bottom: High-loss state with low
carrier density. Reproduced from ref 97. Copyright 2010 The Optical Society of America. (e) Schematic of a buried-type
modulator which consists of dual graphene layers separated by thin BN spacers. (f) Proposed model of graphene-based ring
resonator. (g) Graphene-based microdisk resonator. (h) Model of a graphene/boron nitride-based QCSE modulator.

different doping effects leads to the built-in potential operate at speeds over 500 GHz, which is not restricted
drop within the graphene channel, allowing maximum by the carrier transit time but the RC time constant
photocurrent to be detected. The 3 dB frequency of the device. From the high photoresponsivity of
bandwidth of 16 GHz was determined from a modu- 6.1 mA W
1 and high bandwidth of the photoresponse
lated optical signal at a wavelength of 1550 nm.75 In at tens of gigahertz, it was suggested that photovoltaic
principle, a graphene photodetector can potentially effect rather than thermoelectric effect is the dominant

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mechanism in their devices because the latter effect is devices with a dual-gate homojunction100,111 or
usually limited by the much slower electron cooling a graphene single-bilayer interface junction112 where
process.25 there is a difference in thermoelectric power (Seebeck
The dark current is relatively high in the graphene- coefficient). For example, in the case of single-bilayer
only system when it is photoexcited at an external bias, junction, the Dirac point of a single layer is expected to
which leads to small photoelectric gain, especially for be lower than the bilayer, and the built-in potential
infrared and terahertz detection under low photon difference causes photoexcited electrons to flow from
incident energy. In these cases, the presence of a small the bilayer to the single layer. However, as the bilayer
energy gap can help to suppress the dark current, has larger thermoelectric power originating from its
similar to the case of quantum-well infrared photo- larger density of states, the hot carriers tend to diffuse
detectors. Ryzhii et al.101 proposed a few prototypes from single layer to bilayer to maximize the entropy,
based on bilayer graphene in which energy gap can be which leads to current flow of the opposite sign. As a
varied by the transverse electric field (Figure 6b) or result, the change in sign of the current as a function
graphene nanoribbons in which the energy gap can be of gate voltage provides a fingerprint of hot-carrier-
tailored by controlling the width of nanoribbons dominated transport and carrier multiplication.109,110
(Figure 6c).102 One strategy to enhance the responsiv- Photoexcitation by ultrafast pulsed laser can identify
ity and detectivity is to apply split gates to form the the contribution of photothermoelectric effect from
electrically induced p- and n-doped sections within that of a conventional photovoltaic mechanism.100
the graphene channel, which operates like the p-i-n The efficient design of a device which takes advant-
junctions in semiconductor photodiodes, as shown in age of the difference in Seebeck coefficients of
Figure 6d.103 Another way to suppress the dark current materials may lead to enhanced performance in these
is the incorporation of dielectric materials (such as TiO2104 devices.
and ZnO105) on graphene to form a hybrid interface; this Broadband Saturable Absorber. The optical loss suffered
can greatly improve the gain due to effective charge by a beam of light passing through graphene can be
injection and separation at the interface. reduced at high optical intensities. This is the property
Another effective approach is to introduce gold
of saturable absorption, which can be used for the
titanium plasmonic nanostructures next to the elec- generation of short pulses using passive mode locking
trical contacts of a graphene photodetector, as shown or Q switching techniques. Even though most semi-
in Figure 6e.78 Due to the built-in potential resulting conductor (i.e., GaAs) or organic materials (i.e., dyes)
from different work function of contact metals, the show saturable absorption, only those which have
detector is analogous to the traditional p
n junction saturation intensity much lower than the optical da-
photodiode. The plasmonic nanostructures are able to mage threshold can be used practically for photonic
convert incident light into plasmonic oscillations and applications.113 Semiconductor saturable absorber
guide electromagnetic energy to the detector. As a mirrors (SESAMs) which operate in the reflection mode
result, the efficiency of graphene-based photodetec- are widely used as mode lockers. SESAMs are fabri-
tors can be increased by up to 20 times because of cated by integrating the semiconductor coatings into a
efficient field concentration in the junction area. In mirror structure.114 The main drawbacks of SESAMs are
another example, Furchi et al.77 recently demonstrated low damage threshold, narrow working wavelength
that the responsivity of a graphene photodetector can range, and high cost.
be increased to a record value of 21 mA/W by mono- Graphene is emerging as a new type of saturable
lithically integrating the graphene sheet in a high- absorber with potential for wide-band operation.80,81
finesse Fabry-Pérot microcavity (shown in Figure 6f), Interband optical excitation produces a non-equilibri-
in which the optical absorption of graphene is 26-fold um carrier population in the valence and conduction
enhanced (>60%) due to the resonant interference. bands of graphene. When a steady state is reached
Similar concept of using the microcavity to enhance between population of excited electrons and the
light detection in the graphene transistor has also been electrons relaxing through electron
hole recombina-
proposed by another group.106 Peres et al. have dis- tion, the absorption will be saturated, as shown in
cussed the physics in this field excellently.107 Figure 1g.115,116 The nonlinear response under inter-
It is worth noting that when hot carriers are gener- band excitation is affected by several physical pro-
ated in abundance, the photothermoelectric effect can cesses (shown in Figure 7a9,117), which are dependent
contribute to the enhancement of the photoresponse. on the pumping conditions. Under conditions of strong
Due to the relatively slow acoustic phonon scattering pumping by ultrafast optical pulses, multiple quantum
rate (∼10 ns), both theory108,109 and experiments100,110 transitions take place and lead to nonlinear regime of
indicate that thermoelectric currents arising from en- energy relaxation and recombination.56 The direct con-
ergy transport of hot carriers have a larger contribution sequence is a saturation of the transient absorption; that
than the photovoltaic effect. The photothermoelectric is, the absorption decreases to a steady level with the
effect can be observed in graphene optoelectronic increase of pumping power. The maximum optical loss is

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Figure 6. (a) Schematic illustration of graphene-based photodetector with asymmetric metal contacts. The inset shows the
REVIEW
scanning electron microscope image of the photodetector. Reprinted with permission from ref 75. Copyright 2010 Nature
Publishing Group. (b) Schematic illustration of graphene bilayer field-effect phototransistor for terahertz and infrared
detection. (c) Schematic model of graphene nanoribbon photodetector. (d) Schematic model of photodetector consisting of
p-i-n graphene junctions. The p- or n-type doping can be obtained by applying opposite bias at two top gates. (e) Au
plasmonic array fabricated on graphene for plasmon resonance enhanced multicolor photodetection. (f) Schematic drawing
of graphene microcavity photodetector. Distributed Bragg mirrors are fabricated to form a high-finesse optical cavity which
can trap light and enable multiple times passing through the graphene. Adapted from ref 77.

defined as modulation depth and is associated with third- SESAMs,114 which require either chirality (diameter) con-
order optical nonlinearities. The third-order susceptibility trol or band gap engineering, are more difficult to
|χ3| of graphene is measured to be ∼10
7 esu, which is 1 fabricate compared to graphene.
order of magnitude larger than that reported so far for The fundamental principle for pulse shaping by gra-
single-walled carbon nanotubes (SWNTs).15 In principle, phene is similar to that in semiconductors, as shown
monolayer graphene affords the highest saturable ab- schematically in Figure 7b. The broadband nature of
sorption for a given amount of material because of the graphene in the linear optical regime is also valid at the
large capacity of Dirac cone to conserve the electrons and nonlinear regime. However, unlike the constant linear
holes.55 Saturable absorbers made of SWNTs118 or absorption over a wide spectral range, the saturable

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 REVIEW
Figure 7. (a) Schematic illustration of photoexcited electron kinetics in graphene. Reprinted with permission from ref 117.
Copyright 2011 American Institute of Physics. (b) Schematic illustration of pulse shaping by graphene saturable absorber. (c)
Wide-band-tunable Q-switched laser setup using graphene/PVA composite as saturable absorber. Laser diode (LD),
wavelength division multiplexer (WDM), erbium-doped fiber (EDF), isolator (ISO), graphene-based saturable absorber
(GSA), and polarization controller (PC). (d) Output spectra at 14 tuning wavelengths from graphene Q-switched fiber laser.
Panels c and d reprinted with permission from ref 84. Copyright 2011 American Institute of Physics.

absorption is wavelength-dependent. A higher pumping (polyvinyl alcohol) composite as a saturable absorber

power is required to saturate the absorption at higher for mode-locked laser and achieved 34 nm tunability
photon energy (shorter wavelength).56 This poses consid- between 1525 and 1559 nm with the help of a tunable
erable challenges for the pulse shaping in the visible range band-pass filter. However, the saturation-induced ab-
because the saturation intensity is approaching its optical sorption decrease is very limited (∼4.5%), suggesting a
damage threshold. To date, many groups have demon- small modulation depth. Bao et al.80 fabricated a
strated the use of graphene-based saturable absorber in transparent graphene
organic hybrid membrane that
ultrafast pulsed lasers54,55,85,86,119,120 operating in the tele- can be handled with a tweezer and fixed on top of an
communication bands. This is a fast growing area, and the optical fiber. The functionalization of graphene with
figures of merit for laser performance are continuously absorption-enhancing dye molecules maximizes the
being improved. For example, the operation wavelength ratio of saturable-to-nonsaturable absorption, which
range has been extended from ∼1 μm,82 1.03 μm,117 1.25 leads to a large modulation depth of 29%. This mod-
μm,121 C band (∼1530
1565 nm)80,81,122 to 2 μm.83 Sub- ulation depth is close to the saturable absorber made
200 fs pulse generation111,112 and high peak power (up to of graphite nanoparticles.122 The larger modulation
13.8 kW117) laser emission have also been achieved. depth affords the ease of self-starting the mode-lock-
Both CVD graphene as well as solution-processed ing above the pump threshold. Therefore, broadband
graphene have been used as mode lockers. For the operation with tunable working wavelengths between
ease of handling a graphene sheet, solution-processed 1570 and 1600 nm was achieved without using any
graphene can be combined with polymers to form tunable filter. Mode-locking performance by graphene
a physically robust, transparent membrane. This at ∼1 μm in the fiber laser82 as well as the solid-state
combines the mechanical strength of the polymer- laser123 further confirmed the broadband nature of
reinforced composite with the optical absorption graphene-based saturable absorbers. In principle, by
of organic dyes. Sun et al.81 used a graphene
PVA saturating the conduction band electrically (i.e.,

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 REVIEW
Figure 8. (a) Schematic illustration of Z-scan measurements. (b) Schematic structure of a functionalized sub-GOx sheet. (c,d)
Plot of output versus input fluence (red square) for 3.5 ns pulses at 1064 and 532 nm wavelengths, respectively. (e) Nonlinear
transmittance characteristics of ultrasonically exfoliated graphene, sub-GOx, and heavily oxidized GOx. Panels b-e reprinted
with permission from ref 87. Copyright 2011 Nature Publishing Group.

shifting the Fermi level), the condition of saturable laser with an even larger tuning wavelength range up
absorption can be turned off. One interesting possibi- to 50.6 nm.127 Notably, the graphene Q-switched laser
lity is the fabrication of an electro-optic modulator to delivers up to ∼86.2 nJ energy at ∼29 kHz repetition
switch the saturable absorption properties on and off rate. The pulse energy is many times larger than
by electrostatic gating; in this case, instabilities in the graphene mode-locked fiber lasers120,128,129 and much
laser cavity can be quenched in a controllable manner. larger than values reported for SWNT Q-switched
Apart from the use of graphene in the mode-locked lasers. Such broadband Q-switched lasers are ideal
laser to generate ultrashort laser pulse (picoseconds to candidates in applications where ultrafast pulses are
femtoseconds), a graphene Q-switched laser is known not necessary, such as material processing, environ-
for generating microsecond to nanosecond pulse with mental sensing, and biomedical diagnostics.
a small width but at high peak power and large pulse Broadband Optical Limiter. Optical limiters are materi-
energy (tens of nanojoules). Graphene saturable ab- als that strongly attenuate intense, potentially danger-
sorber functions as a Q-switcher to modulate the ous optical beams while exhibiting high transmittance
quality factor (Q) of a laser cavity by initiating energy for low-intensity ambient light. Passive optical limiters
storage, allowing feedback and the process of optical rely on an effective nonlinear response to dissipate the
amplification through stimulated emission. Passively incident light as a function of its intensity. A good
Q-switched solid-state lasers with different gain optical limiter should have broadband optical limiting
medium (Nd:YAG,85 Nd:LuVO4,124 and Nd:GdVO486) ability, rapid response, and low optical limiting onset
have been developed to generate large energy pulses threshold. Two main mechanisms are responsible for
at ∼1.06 μm. Figure 7c shows a representative laser the optical limiting effect: nonlinear absorption
setup used for broadband operation of a graphene (multiphoton absorption or reverse saturable absorp-
Q-switched fiber laser.84 Using the graphene
PVA tion) and nonlinear scattering (microbubble or micro-
composite as an effective saturable absorber, Popa plasma-induced scattering according to Mie scattering
et al.84 demonstrated a wide-band-tunable Q-switched theory). Reverse saturable absorption occurs in cases
laser from ∼1522 to 1555 nm (Figure 7d), which is where the excited-stated absorption is stronger than
comparable to the 31 nm range reported for doped ground-state absorption, and this manifests as an
crystal Q-switched tunable lasers125 and much larger increase in the total absorption at high incident in-
than the 5 nm achieved for SWNTs Q-switched tensity. This is in contrast to the saturable absorption
lasers.126 Recently, Cao et al. reported a Q-switch fiber case where the absorption cross section of the ground

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 REVIEW
Figure 9. Schematic illustration of integrated graphene
silicon hybrid photonic circuit, which consists of a graphene mode-
locked laser with a ring cavity (left), graphene optical modulator (middle), and microcavity enhanced graphene photo-
detector (right). In the ring laser, minimized optical components will be used to incorporate into the optical chip, which
includes wavelength division multiplexer (WDM), isolator (ISO), single-mode fiber (SMF), erbium-doped fiber (EDF),
polarization controller (PC), and graphene-saturable absorber (G-SA). In the optical modulator, graphene is sandwiched
between two pieces of the Si waveguide to achieve high modulation depth. Each modulator is separately controlled by the
electrical chip so as to encode the optical signals. In the photodetctor, the microcavity with two mirrors is integrated to
enhance the light absorption by graphene and the responsivity of the device. The end of the Si waveguide has a wedge shape
so as to direct light signals into the photodetector with in-plane configuration. The electrical signals from each photodetector
are collected by the electrical chip. The Si waveguide between the modulator and the photodetector can also be prolonged
and adapted with optical fiber for long-distance signal transmitting.

state is stronger compared to the excited state. The excited state. For example, an alkyl-functionalized
lifetimes involved in reverse saturable absorption have substoichiometric graphene oxide was shown to give
to be in the same order as the time between two superior broadband nonlinear optical properties at
consecutive pulses to prevent complete relaxation of fluencies well below the damage threshold.87 Different
the excited state to the ground state. In organic from pure graphene, the existence of the small
molecules, this is aided by slow relaxation and inter- π-conjugated domains surrounded by an insulating
system crossing to the triplet state, such that the next matrix affords the confinement of long-lived electron

pulse of the pulse train can probe a different popula- hole pairs which can interact with surrounding media
tion in the electronic states than the first pulse did.130 (shown in Figure 8b), resulting in excited-state absorp-
Optical limiting properties of graphene are com- tion (reverse saturable absorption) extending over a
monly studied using solution-dispersed graphene wide vis
NIR region. This in turn leads to a new
oxide derivatives,48,131,132 where the limiting effects benchmark for optical energy limiting with onset of
arise from thermally induced nonlinear scattering. 10 mJ cm
2 for a linear transmittance of 70%, demon-
These usually involve the formation of scattering cen- strated in both solvents and polymer composites, as
ters by microplasmas or microbubbles (Figure 8a), illustrated in Figure 8c
e. As claimed by Lim et al.,87
which happen in the nanosecond time scale. There- such sub-stoichiometric graphene oxide (sub-GOx)
fore, such a type of thermally induced scattering is films exhibit performance which exceeds that of other
operational when the pulse laser operates in the carbon nanomaterials by a factor of 5
10 times.
nanosecond time scale. For femtosecond lasers, photo- The synthesis of a graphene
organic hybrid is
induced charge transfer between graphene and a dye motivated by the fact that the formation of new energy
which occurs at the same time scale may contribute to dissipation channels via photoinduced electron trans-
the optical limiting effect. Due to the ultrafast fer will further expand the optical limiting capability of
(femtosecond) relaxation time scale of excited-state graphene. The aromatic structure of graphene pro-
electrons in pure graphene, reversed saturable absorp- vides a platform for functionalization with molecular
tion from pristine graphene has not been reported. If dye with the possibility of forming a charge transfer
the electronic structure of the graphene is modified by complex due to donor
acceptor pair interactions.
chemical functionalization, as in the case of graphene Organic dyes exhibit excellent reverse saturable ab-
oxide, it may be possible to modify the relaxation sorption effects but have relatively low damage thresh-
dynamics and allow further absorption from the old and narrow dynamic range,133 and bonding to

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 REVIEW
graphene improves the damage threshold due to from Wafer-Scale Epitaxial Graphene. Science 2010,
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financial interest. Phys. Rev. B 2001, 64, 035104.
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Q.B. acknowledges financial support from the Lee Kuan Yew
Postdoctoral Fellowship. We thank N. M. R. Peres for helpful 22. Rummeli, M. H.; Bachmatiuk, A.; Scott, A.; Borrnert, F.;
discussion. Warner, J. H.; Hoffman, V.; Lin, J. H.; Cuniberti, G.; Buchner,
B. Direct Low-Temperature Nanographene CVD Synth-
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