6000112 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 20, NO.

1, JANUARY/FEBRUARY 2014

Graphene Photonics, Plasmonics,

and Optoelectronics
Phaedon Avouris, Senior Member, IEEE, and Marcus Freitag

(Invited Paper)

Abstract—We review the characteristics of the optical excitations

of graphene involving interband, intraband, and collective (plas-
mon) electronic excitations. We then discuss the different mech-
anisms by which photon energy can be converted to an electrical
current in graphene. Finally, we review applications of graphene as
transparent conductive screens, as photodetectors and light mod-
ulators at different wavelength ranges.
Index Terms—Graphene, plasmons, photodetectors.

I. INTRODUCTION
RAPHENE, a single layer of carbon atoms arranged in a
G hexagonal honeycomb lattice, is the building block of the
familiar graphite. Although there are early published reports on
graphene [1], it was not until 2004, when Geim and Novoselov
at the University of Manchester demonstrated an easy method
for isolating graphene [2], that its properties became a subject
of intense study [3]–[9]. Graphene is a covalent, π-electron 2-D
system with exceptional electrical and optical properties. At low
energies, it has a linear dispersion, no bandgap, a high Fermi
velocity (vF ≈ 106 ms−1 ), and exhibits very high carrier mobil-
ities [3]–[9]. Unlike conventional metals, its density-of-states
and Fermi energy can be tuned by electrostatic or chemical Fig. 1. Optical conductivity of graphene. (a) Optical conductivity of graphene
at high photon energies. In the visible range, the optical conductivity is close to
doping. These characteristics have made graphene a prime can- the universal value πe2 /2h. Trigonal warping and many body effects lead to a
didate for applications in nanoelectronics [8], [9]. Graphene strong resonance in the UV at 4.6 eV. (Reproduced from [13].) (b) Extinction
also interacts strongly with light, absorbing radiation over a spectrum of graphene in the IR. (T G + S is the transmission through graphene
and the substrate, T S is the reference substrate transmission.) Due to Pauli
very wide wavelength range extending from the far-infrared blocking, the absorption drops below the universal value for energies below 2|μ|
(IR) to the ultraviolet [10]–[16]. Interband and intraband single (twice the chemical potential). In the terahertz range, the absorption increases
particle excitations, as well as collective plasmon excitations, due to intraband absorption as in metals (Drude peak). However, the Drude
weight can be tuned in graphene by electrostatic doping.
are supported. The unique combination of outstanding transport
properties, wide absorption range, the ability to modulate the
absorption [17]–[19], and the short excited state lifetimes [20] different mechanisms by which light absorption in graphene can
have attracted strong interest in its use in photonics and opto- generate an electrical current. We briefly review some of the uses
electronics [8], [21]–[23]. of graphene as transparent conductive films for display appli-
Here, we discuss the properties of both single particle and cations, and in passive optical components, such as polarizers,
collective excitations of extended graphene and also of con- EM shielding, and saturable absorbers. Then, we discuss appli-
fined graphene structures (quantum wires and dots) and their cations of graphene and graphene micro- and nanostructures in
interaction with external fields and the substrate. We discuss the photodetection and light modulation.

II. OPTICAL PROPERTIES OF GRAPHENE

Manuscript received April 1, 2013; revised May 23, 2013; accepted June 1, A. Single Particle Excitations
2013. Date of publication July 31, 2013; date of current version August 14,
2013. The optical conductivity of graphene at energies where the
The authors are with IBM T. J. Watson Research Center, Yorktown Heights, dispersion is linear, i.e., in the near-IR and visible, has a univer-
NY 10598 USA (e-mail: [email protected]; [email protected]). sal value given by: σuni = πe2 /2h (see Fig. 1) [10]. Therefore,
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org. the absorption of suspended graphene for normally incident
Digital Object Identifier 10.1109/JSTQE.2013.2272315 light in this frequency range (and T = 0) is A = πα ≈ 2.3%,

1077-260X © 2013 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications standards/publications/rights/index.html for more information.
AVOURIS AND FREITAG: GRAPHENE PHOTONICS, PLASMONICS, AND OPTOELECTRONICS 6000112

where α is the fine structure constant, e2 /c, and c the speed of creased absorption reaching 40% in a single graphene layer was
light [10]. Using a thickness of 0.334 nm for the graphene layer, achieved in the far-IR [32].
one obtains an absorption coefficient of about 7 × 105 cm−1 , Finally, we note that graphene also exemplifies strong non-
which is about 50 times higher than the absorption of GaAs at linear
 (3)  optical response with an effective nonlinear susceptibility
1.55 μm, thus, demonstrating the strong coupling of light and x  ∼ 10−7 esu, i.e., approximately eight orders of magnitude
graphene. At the same time, the reflectivity of graphene, R, is larger than in bulk dielectrics [33]. Furthermore, this nonlinear-
very low: R = 0.25π 2 α2 (1 − A) = 1.3 × 10−4 . At higher pho- ity is essentially dispersionless in the near-IR and visible and has
ton energies (≥3 eV) the trigonal warping of the bandstructure already been utilized in four-wave mixing applications [34], [35]
leads to deviations from the above universal optical conductiv- and Kerr effects [36].
ity. Many body effects also play an increasingly important role
and result in a strong saddle point excitonic resonance near the
M point of the Brillouin zone at 4.6 eV; see Fig. 1(a) [13]. The B. Collective Excitations—Plasmons
absorption of multilayer graphene is essentially additive, at least The ever-increasing use of photonics in global data commu-
at energies above 0.5 eV [10]. nications and the current interest in on-chip optical communi-
A particularly important property of graphene is that it can cations has led to increased efforts to decrease the physical size
be doped electrostatically by a gate or chemically by adding and power consumption of photonic devices [37]. One approach
dopants. The chemical potential, μ, is determined by the result-
√ involves the use of subdiffraction limit photonic devices based
ing carrier concentration η, μ = EF = πη/. An important on surface plasmons. In metals–dielectric interfaces, the time-
consequence of the Pauli principle and of doping is that in- varying electric field associated with the light exerts a force on
terband transitions are essentially blocked for photon energies the metal electron gas and drives it into a collective oscillation,
ω < 2 |μ| [Pauli blocking, Fig. 1(b)] [11], [12]. This property where the restoring force is provided by the resulting gradient of
provides a way of tuning the absorbance of graphene. the self-consistent electron field. The light is “bound” to the elec-
The excited states of graphene produced by photoexcita- trons, its momentum (wave vector) is increased and its apparent
tion or other means decay very fast by different mechanisms. wavelength is strongly decreased so that the resulting surface
An ultrashort pulse generates electron–hole pairs in a highly wave (surface plasmon polariton, SPP) provides a strong field
nonequilibrium state. Electronic interactions, i.e., Coulombic localization beyond the diffraction limit, λ0 /2. The plasmons can
carrier–carrier interactions such as Auger and impact ioniza- be propagating TM or TE waves or localized plasmons in nano-
tion, which also lead to carrier multiplication, provide the fastest and microparticles [38]. Since at a given frequency ω, the mo-
energy redistribution mechanism [24], [25]. Time-resolved mentum of the plasmon is higher than that of the same frequency
fs-scale measurements show that after about 200–300 fs a light in free space, special techniques, such as prisms or gratings,
Fermi–Dirac distribution is attained with an elevated electronic need to be used to launch the SPP [39]. The field of plasmon-
temperature Te [24], [25]. As expected, the electronic decay rate ics, involving primarily the plasmons of metals (Au, Ag, Cu,
is a function of the electron density (doping). Along with the Al) and certain other materials, is currently a particularly active
energy redistribution processes, energy dissipation takes place field [38], [40]–[42]. The plasmon frequencies of the metals are
via phonon emission. The decay via optical phonons is fast, determined by their electron concentration and the surrounding
taking place on a few picosecond time scale [26]. However, dielectric, and for noble metals lie generally in the visible and
when the excitation energy has fallen below the optical phonon near IR range. Localized plasmon frequencies also depend on
energy (about 200 meV), acoustic phonon emission is slow the shape of the particles. Graphene support plasmons, but in this
(nanoseconds), and this leads to the formation of an energy case, in the near and far-IR and terahertz ranges (0.1–10 THz).
dissipation bottleneck [27]. Due to this uncoupling of lattice Most importantly, graphene offers the unique capability of plas-
and electronic temperatures, the resulting “hot” electrons can mon tunability, since, unlike in metals, its charge density can
persist for nanoseconds. Coupling of the electrons with a polar be tuned either by electrostatic or by chemical doping [22],
substrate’s surface optical phonons may become an important [23], [43]. The plasmon frequency in graphene is given by [43]:
decay path in this case [28]. ωpl (q) = [(8EF σuni kpl )/ε]1/2 , where EF is the Fermi energy,
Optical transitions involving the free electrons of doped σuni is the universal conductivity of graphene, kpl is the plas-
graphene lead to absorption that extends into the far-IR and mon momentum, and ε is the dielectric constant of the substrate.
tetrahertz ranges. The optical conductivity in this range has, as Since in graphene EF ∝ η 1/2 it follows that ωpl ∝ η 1/4 [44],
in conventional metals, the Drude form [29]: we note that the plasmons of the massless Fermions in graphene
iDG r are a quantum effect, as is indicated by the presence of  in
σ(ω) = (1)
π(ω + iΓ) the aforementioned equation. The compression of the surface
plasmon wavelength in graphene λsp relative to the excitation
where the Drude weight, D, for graphene has the form [30]:
wavelength λ0 is strong, and is governed, as is the single particle
DGr = 2EF σuni / and Γ−1 is the damping rate. This free
absorption, by the value of the fine structure constant α [22].
electron absorption can, therefore, be made very high, since
√ Specifically,
σ(ω) ∝ EF ∝ η. Using a gate field, especially using elec-
trolytic gates, carrier densities as high as η ∼ 1014 cm−2 can
be generated [31]. Also, using heavy chemical doping an in- λsp /λ0 ≈ (2αEF /εω) ≈ α ≈ 1/137. (2)
6000112 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 20, NO. 1, JANUARY/FEBRUARY 2014

Fig. 3. Dispersion of graphene plasmons on SiO2 . (a) Plasmon dispersion.

Three hybrid plasmon–phonon modes are resolved that arise from the interaction
of the intrinsic graphene plasmon (dashed curve) with two surface polar phonons
of the SiO2 substrate (sp1 and sp2). Data points are experimental peak positions
of plasmons in graphene nanoribbon arrays with different nanoribbon width.
The color plot is calculated. (b) Dependence of the third plasmon–phonon
peak on chemical doping. The broadening at high doping is due to opening
Fig. 2. Standing plasmons in graphene. (a) Image of a graphene microdot of an additional plasmon decay channel via optical phonons, once the energy
array. (b) Extinction spectra of graphene microdot arrays with 1, 2, and 5 exceeds the energy of the graphene optical phonon at 1600 cm−1 . (Reproduced
graphene layers, separated by polymer buffer layers. The disk diameter was from [58].)
d = 4.4 μm, and the triangular lattice constant was a = 9 μm. (c) SEM image
of a graphene nanoribbon array with 100-nm nanoribbon width. (d) Extinction
spectrum of a stacked microribbon array with five graphene layers at 0◦ and
90◦ polarization. The ribbon width was 2 μm and the spacing 500 nm. INSET:
Polarization dependence of the extinction at 1.2 THz. (Reproduced from [50].)
larly polarized to the ribbon
√ axis. The plasmon frequency is
now proportional to 1/ W [50]. The wavelength compression
that takes place upon plasmon excitation in graphene nanorib-
For example, for 10 μm incident light, EF = 0.15 eV and a bons can also be utilized to make very short terahertz antennas
relaxation time of 10−13 s, the plasmon wavelength of graphene that would allow for local communications between microstruc-
on SiO2 will be 155 nm: i.e., a confinement factor λ0 /λsp of tures [51], [52]. The plasmons of more complex graphene struc-
64. Experimentally, confinement factors of 40–60 have been tures can be described in terms of hybridization of the plasmons
reported [45], [46]. The confinement normal to the graphene of different elementary structures, (disks, rings, etc.), as in the
surface is also tight, of the order of λsp /2π. As a result, field case of metal plasmons [53], [54]. The aforementioned con-
concentrations of the order of 106 could develop that can en- siderations involve structures that are sufficiently separated so
hance many linear and nonlinear optical phenomena. Another as not to interact significantly. Interactions lead to shifts and
important metric is propagation length (1/e decay of ampli- broadening of the plasmon resonances [50], [55].
tude) δsp of the surface plasmon determined by the losses in The graphene plasmons can interact rather strongly with the
graphene. In perfect graphene samples and energies below the substrate. Specifically, polar insulator substrates, such as the
onset of interband transitions and the optical frequency, it could commonly used SiO2 , have surface phonons that generate fluc-
in principle reach δsp ∼ 100λsp [23]. However, with currently tuating electric fields that extend above the substrate surface, and
available synthetic graphene samples it will likely be about 3–5 thus, can couple with the plasmons of the supported graphene.
λsp [47]. As a result, hybrid modes involving collective electronic (plas-
Localized plasmons can be excited when the dimension of mon) and ionic lattice (phonon) excitations are generated. The
a micro- or nanostructure is smaller than that of the plasmon, hybrid mode’s energy and plasmon content depends on the rela-
λlp , which is also a function of the shape of the structure. For tive energies and the coupling strengths of the “naked” plasmon
example, for a circular disk structure (see Fig. 2) the localized and the surface phonons [56], [57]. The hybrid modes have life-
plasmon frequency is given by (3), where d is the disk diam- times that are longer than those of pure plasmons because of the
eter, and an array of noninteracting circular dots will have an much longer phonon lifetime, which is typically in the picosec-
absorption given by (4), where f is the fraction of the graphene ond range. Fig. 3 shows the dispersion of graphene plasmon
surface occupied by the dots [48], [49]. interacting with two surface phonons of SiO2 [58]. Along with
 the anticrossing resulting from the interaction of the plasmon
3D with the substrate surface phonon, the effect of coupling with the
ωlp = (3)
8εm εd intrinsic optical phonon of graphene near 200 meV are clearly
fD ω seen. This coupling with the optical phonon allows the plas-
σ(ω) = i . (4) mon to decay to electron–hole pairs drastically increasing the
π (ω − ωp2 ) + iΓω
2
damping of the plasmon [58], [59]. The drastic increase in the
Similarly, localized plasmons with k = π/W can be excited width of the plasmon as its frequency is increased by chemical
in graphene nanoribbons of width W with light perpendicu- doping above the phonon frequency is shown in Fig. 3(b) [58].
AVOURIS AND FREITAG: GRAPHENE PHOTONICS, PLASMONICS, AND OPTOELECTRONICS 6000112

The same behavior is observed at natural inhomogeneities (e.g.,

step and wrinkles) on graphene surfaces that cause carrier con-
finement. Futhermore, Faraday rotation spectra show that each
peak is excited by a different circular polarization [63]. Most
interestingly, the lower energy component becomes narrower,
while the higher becomes broader with increasing field. This
behavior is related to the quantum Hall effect, but can be quali-
tatively understood by considering that the plasmon is acted on
by the centrifugal forces induced by the magnetic field, which
have opposite radial directions for right and left circulating cur-
Fig. 4. Magneto-plasmons in graphene. (a) Extinction spectrum of standing
graphene plasmons in microdisk arrays of 3 μm diameter for different magnetic rents in the microdisk, and also by the disk confinement field.
field strengths as indicated. The single plasmon peak splits in to two peaks, Thus, the two interactions can add or subtract from each other.
associated with edge and bulk plasmons. (b) Width of the two magneto-plasmon As a result, the zero field plasmon splits into a “bulk” and an
peaks as a function of magnetic field. The edge-plasmon width is reduced at
high magnetic field, indicating a longer life time. (Reproduced from [62].). “edge” mode in the magnetic field. As the field is increased,
the edge plasmon is confined more and more toward the edges
of the disks and in effect the 2-D initial plasmon is effectively
Given the interest in the use of patterned graphene in metama- transformed into a 1-D plasmon, which reduces backscattering,
terial structures [60], it is important to consider the losses, i.e., and therefore, also the edge plasmon linewidth [62]. Fig. 4(b)
the damping rates, expected in such graphene structures. Tak- illustrates the changes in the plasmon mode widths as a function
ing as an example the graphene nanoribbon (GNR) arrays, we of the field strength. More recently, the edge plasmon dynamics
can express the scattering lifetime below the onset of interband in graphene disks were also measured using real time tech-
transitions (Landau damping) as niques [64]. The dramatic reduction in backscattering in the
τ (q, ω) ≈ [τ0−1 + τedge (q)−1 + τe−ph
−1
(ω)−1 ]−1 (5) edge plasmon mode was verified and lifetimes as long as 50 ps
(attenuation length δ = 70 ± 30 mm), i.e., about three orders of
where τ0 is lifetime for extended graphene due to scattering by magnitude longer than the Drude relaxation time of the sample
defects. This is approximately the same lifetime as that extracted (0.05 ps for a sample mobility of 5,000 cm2 /Vs), were obtained
from the Drude response. For typical synthetic graphene, τ0 is for the v = 2 Landau level. The aforementioned results indicate
of the order of 50–100 fs. The edges of graphene introduce addi- that magnetic fields provide a powerful way of tuning not only
tional scattering and τedge (q) has the form τedge (q) = 2vF /We , the energy, but also the lifetime of plasmons in graphene.
where We is the electronic ribbon width and vF the Fermi ve-
locity [58]. Finally, as we have shown previously, the electron– III. PHOTOCURRENT GENERATION MECHANISMS IN GRAPHENE
phonon interaction provides an additional inelastic scatter-
The key process that enables most optoelectronic applica-
ing mechanism, effectively defining the usefulness range of
tions is the conversion of photons into an electrical signal. There
graphene plasmonics to wavelengths below about 6.5 μm (about
are several different mechanisms by which this can be accom-
50 THz) [58].
plished in graphene. These involve the photovoltaic effect, the
photothermoelectric effect, the bolometric effect, and the photon
C. Magnetoplasmons drag effect. In the following, we describe briefly these mecha-
At high magnetic field Landau levels are generated in nisms, the situation in which each of them dominates, and their
graphene with energies given by [61]: implementation in graphene photodetectors.

En = ±nvF 2 |eBn| (6) A. Photovoltaic Effect
where n is the Landau level index, B the magnetic field strength, In the photovoltaic effect, the built-in electric fields that are
and vF the Fermi velocity. The cyclotron frequency is given by generated at junctions between p- and n-type graphene or be-
ωc = eB/mc , where mc is the cyclotron mass, which, unlike tween differently doped graphene in general, are employed to
the rest mass of graphene, has a finite value dependent on the separate photogenerated electrons and holes to produce a pho-
carrier density. In the cyclotron spectrum, the graphene flake tocurrent [65]–[67]. A similar result can be achieved through
plasmon on a noninteracting substrate, such as a diamond-like an electric field generated by applying an external bias [68]. If
carbon film, appears as a single peak whose frequency increases the photogenerated electrons and holes are separated before re-
linearly with B. In a graphene microstructure, however, the combining, they contribute to a photocurrent. Graphene devices
behavior is more complex. As Fig. 4 shows, with increasing fabricated on SiO2 have been shown to function primarily in the
magnetic field strength, the localized plasmon peak in an array photovoltaic regime [65]–[68]. Opposite doping of two adjacent
of graphene microdisks splits into two peaks which move in regions can be achieved with selective chemical doping [69],
opposite directions with increasing field [62]. Their energies two (split) gates [65], or by taking advantage of the workfunc-
are given by tion difference between graphene and a contacting metal [67].
 The split gate and contact geometries are shown in Fig. 5. In
ω ± = ω02 + ωc2 /4 ± ωc /2. (7) the former case, the doping in both regions can be p- or n-type
6000112 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 20, NO. 1, JANUARY/FEBRUARY 2014

Fig. 5. Photovoltaic effect in graphene. Schematic of the band bending in

(a) double-gated graphene p-n junctions, and (b) contacted graphene. (c) Scan- Fig. 6. Thermoelectric current in a suspended graphene p-n junction. (a) Sign
ning photocurrent images of a graphene field-effect transistor (shown in the of the thermoelectric photocurrent (color coded) as a function of charge density
gray-scale SEM image) for different backgate voltages as indicated. For nega- in two adjacent graphene regions. (b) Sign of the photovoltaic photocurrent for
tive gate voltages, a pp+ junction exist right at the contact. At a gate voltage of comparison. (c) Experimental setup: The supported graphene is doped p-type by
30 V, the flat-band voltage is reached and the photocurrent image is dominated the substrate, while the suspended part is close to intrinsic and can be gated n-
by trapped charges in the oxide. For gate voltages in excess of 50 V, p-n junc- type by a positive back-gate voltage. (d) Schematic of the band-bending for V G
tions are formed about 200 nm away from the contacts. Scale bars on bottom = –10 V, 0 V, and 10 V (top to bottom). (e) Photocurrent as a function of position
right are both 1 μm. Fig. 5 (c) is reproduced from [67]. along the graphene for different gate voltages as indicated. The photocurrent at
the left p-n junction (position −1 μm) switches sign as indicated by the green
line in (a). Fig. 6(c) and (e) are reproduced from [76].
depending on the applied gate voltages, while in the latter case,
the doping in the contacted area is fixed, typically p-type for
ficient such as in p-n junctions, may produce a photocurrent
high workfunction metals, while the graphene channel can be
due to the thermoelectric effect (see Fig. 6). This effect has
p- or n-type. The photocurrent direction depends only on the
been shown to dominate in graphene p-n junctions with atom-
direction of the electric field, not on the overall doping level.
ically flat boron-nitride dielectrics [73]–[75] or in suspended
Thus, it switches sign, when going from pn to np, or from pp+
graphene [76]. Because hot electrons rather than lattice heat-
to p+ p. In terms of responsivity of these junction devices, the
ing generate the electronic response in these references, pho-
photocurrent usually peaks around 10−2 or 10−3 A/W.
tothermoelectric graphene detectors could show similarly high
The speed with which these photovoltaic photodetectors can
bandwidth as in the photovoltaic case. The thermoelectric cur-
be operated has been measured by several groups [70]–[72].
rent is proportional to (S2 − S1 ) dTe /dx, where S1 and S2 are
Bandwidth values up to 500 GHz have been reported in these
the Seebeck coefficients of the p- and n-type regions. The See-
references. Note that energy loss through electron–electron scat-
beck coefficients are related to the electrical conductivity σ
tering is beneficial in terms of efficiency, since it effectively 2 2

increases the number of carriers with excess energy that have through the Mott formula S = − π k 3eb T e σ1 dσdε , and thus, they
a chance of contributing to a photocurrent. Electron–phonon can be calculated from the I −VG characteristic. In contrast to
scattering, on the other hand, transfers energy from the electron the photovoltaic current discussed previously, the thermoelec-
system to the phonon system, which may produce bolometric tric current shows sign reversal in bipolar p-n junctions on the
effects such as will be discussed in Section III-C, but does not one hand, and unipolar p+ p or nn− junctions on the other. This
lead to carrier multiplication. In graphene, the Dirac electron is due to the sign change of the transconductance dσ/dε when
structure and efficient electron–electron scattering means that going from p-type transport to n-type transport. Together with
photogenerated carriers will multiply rapidly and share their the sign reversal when switching the electric field direction, this
excess energy with the electron bath, while electron–acoustic leads to a six-fold sign change in the photocurrent as a function
phonon scattering is weak, so further thermalization is limited. of the doping in the two regions [see Fig. 6(a) and (b)]. This
This effectively produces an elevated electron temperature Te behavior can be used to differentiate between photovoltaic and
above the lattice temperature increase Tph . In traditional opti- photothermoelectric effects [74].
cally active materials, hot electron operation requires very low Typical responsivities on the order of 10−3 A/W have been
temperatures, which reduces electron–phonon coupling. reported for the photothermoelectric effect in graphene simi-
lar to the ones observed in photovoltaic graphene photodetec-
tors. However, particularly high responsivities on the order of
B. Photothermoelectric Effect
10−2 A/W have been measured in suspended graphene p-n junc-
An optically generated gradient dTe /dx in the electron tem- tions [see Fig. 6(e)] [76]. In these, the interaction of substrate
perature Te , together with a spatially varying Seebeck coef- phonons with graphene electrons is prohibited in the suspended
AVOURIS AND FREITAG: GRAPHENE PHOTONICS, PLASMONICS, AND OPTOELECTRONICS 6000112

the carrier density is lowest, the effect of the additional pho-

tocarriers is greatest, while far away from the Dirac point the
mobility reduction dominates.
As a function of both drain and gate bias, a six-fold sign
change is observed [Fig. 7(e)] reminiscent of the six-fold sign
change observed for the thermoelectric effect in double-gated
graphene p-n junctions [Fig. 6(a)]. Here, however, the thermo-
electric effect is weak due to the homogeneity of graphene in the
channel. The six-fold sign change instead is brought about by
the interplay of photovoltaic and bolometric effects with oppo-
site sign. Of course, there could also be a thermoelectric effect
present, since the Seebeck coefficient changes due to a slight
doping gradient induced by the bias. However, this effect should
be strongest near the Dirac point and have a negative sign there,
which is opposite of what was observed in Fig. 7. In [68], the ele-
vated electron and lattice temperatures were calculated from the
photovoltaic and bolometric components of the photocurrent.
It was found that the electron temperature is indeed increased
compared to the lattice temperature by an order of magnitude,
and that the differences are highest near the Dirac point.
Fig. 7. Bolometric (BOL) and Photovoltaic (PV) components of the photocur-
rent in biased graphene transistors. (a) Reflected light image of the device. (b)
Photocurrent amplitude and (c) phase as a function of position in a biased de-
vice. (λ = 690 nm laser wavelength, P = 220 μW laser power, gate voltage
D. Phonon Drag Effect
V G = 5 V.) (d) Transport current and photocurrent as a function of gate voltage. Yet another way to induce a photocurrent in graphene with-
(Drain voltage V D = −1 V; laser power P = 370 μW.) The photocurrent is
positive near the Dirac point due to the PV effect and negative elsewhere due out applying a bias is provided by the photon drag effect. This
to the BOL effect. (e) Photocurrent sign as a function of drain and gate voltage. is a second-order effect that utilizes the transfer of momentum
Schematic of the band bending in the doped (f, green) and intrinsic (g, orange) by incident photons to impart momentum to free carriers via
cases. PC (EXP): experimental photocurrent; TE: thermoelectric photocurrent.
Reproduced from [68]. electron–phonon coupling. The effect depends on the polariza-
tion and incidence angle of the photons and it has been first
demonstrated in nanographite [77]. By this mechanism ultrafast
part, removing a potential electron–phonon decay channel. This currents can be launched in graphene.
shows that electron/substrate polar phonon scattering can be
the dominating electron–phonon decay channel, especially at
room temperature, and removing it by suspending, therefore, IV. DEVICE IMPLEMENTATIONS
increases the hot electron temperature and photocurrent. A. Transparent Conductive Films and Passive
Photonic Devices
C. Bolometric Effect The high conductivity, mechanical flexibility, and optical
The bolometric effect is defined as a change in transport cur- transparency of graphene are widely expected to find a range
rent due to the heating associated with the incident photons. of applications, including LEDs and OLEDs, solar cells, touch-
It thus requires an externally applied bias, and homogeneous screens, smart windows, and LCD films [78]–[84]. Currently,
graphene is used instead of p-n junctions. The transport current the material used in most of these applications is ITO which
is altered by incident light in two main ways: the current can has a transmittance of ∼90% and a sheet resistance between
change due to changes in carrier mobility with temperature, or 10–50 Ωsq−1 . ITO, however, is both expensive and brittle and
the current can change due to the presence of additional pho- graphene is considered as a possible alternative. Different ap-
tocarriers. The latter is simply the photovoltaic effect, with the plications require different properties from the graphene films.
electric field generated by the external bias. If electrons and A typical undoped graphene layer has a sheet conductivity of
lattice are equilibrated after photoexcitation, these effects can about 500 Ωsq−1 . Most applications, on the other hand, require
be lumped together by considering simply the temperature de- much higher conductivities. For example, solar cells and OLED
pendence of the resistivity R(T ). In the case of graphene, since displays require resistances less than ∼50 Ωsq−1 , while touch
Te > Tph , the two mechanisms have to be treated separately, screens are more forgiving [79]. The conductance of graphene
and in [68], it was shown that the two mechanisms have op- can be increased by external doping with agents such as HNO3
posite photocurrent sign in graphene (see Fig. 7). The excess and AuCl3 , although the long-term stability of this type of dop-
carriers lead to a current in the direction of the transport current, ing is currently a problem. The large area graphene needed
while the temperature dependence of the mobility leads to a for these window/display types of applications must come from
negative photocurrent. It is important to note that by changing CVD, since graphene from SiC is limited by the size of available
the Fermi level in graphene, one can choose which mechanism SiC wafers and is prohibitively expensive. The large area CVD
dominates [see Fig. 7(d) and (g)]. Near the Dirac point, where graphene has to be transferred from the metal catalyst (usually
6000112 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 20, NO. 1, JANUARY/FEBRUARY 2014

copper) surface to the appropriate substrate without tearing or

wrinkling. This offers a big challenge, but significant efforts
are made to achieve roll-to-roll transfer by companies such as
Samsung [78] and Sony [85].
The high absorption of doped graphene in the microwave
and terahertz regions can be used as an effective shield for
EM radiation. Traditionally, materials such as ferrite or metal
nanocomposites are employed for that purpose and millimeter
thicknesses of these materials are needed for effective shielding
[86], [87]. Graphene, on the other hand, is ∼1,000 times thinner,
light, flexible and strong, and only about five layers are needed
to produce a >20 dB shielding efficiency [32].
Two different types of polarizers based on graphene have
been demonstrated. One is an in-line fiber polarizer, which re-
lies on polarization-selective coupling between the evanescent Fig. 8. Optical modulator. (a) Schematic of an optical modulator based on a
field and graphene [88]. The authors demonstrated that the out- silicon waveguide and graphene absorber. The graphene is contacted by the left
Au/Pd electrode, while the silicon waveguide is contacted through a thin layer
coupled light in the telecommunication band shows a strong of silicon by the right electrode. Graphene is separated from the silicon by a
s-polarization effect with an extinction ratio of 27 dB. The thin layer of aluminum-oxide. A bias between graphene and silicon is used to
other is based on graphene nanoribbon arrays, where the light electrostatically dope the graphene. Optical modulation by 0.1 dBμm−1 of the
guided light (1.35 to 1.6 μm) was demonstrated with a swing voltage of a few
can couple to the localized plasmons of the ribbon only when volts. (b) Cross section through the device and mode profile of the single-mode
polarized perpendicular to the ribbon axis [50]. waveguide. The mode was designed to maximize the electric field at the position
Another application of graphene is as a saturable absorber. of the graphene. (Reproduced from [93].)
Saturable absorption describes the condition where the absorp-
tion of light by a material decreases with increasing light in- ticularly in optical communications. More recently, optical in-
tensity. Most materials show saturable absorption, but often terconnects were also investigated as alternatives to electrical
only at very high optical intensities, close to the optical break- wiring in ultrahigh bandwidth intra- and interchip links. In this
down threshold. Saturable absorbers are used in laser cavities respect, it is important to be able to integrate the silicon CMOS
for mode-locking and Q-switching. Graphene with its wide ab- technology and photonic devices on a single chip. Graphene is
sorption range, fast decay and high stability is well suited for compatible with the silicon technology and this, in conjunction
this application in the IR, and indeed has been successfully used with its unique optical and electrical properties, have resulted in
to produce picosecond laser pulses [89]–[92]. an intense effort to utilize graphene for these critical photonic
functions.
B. Optical Modulators The first demonstration of a graphene photodetector was
based on a metal–graphene contact. In that case, a graphene–
The ability to modulate the Fermi level of graphene by a gate
metal junction was irradiated by light in the IR and visible
field naturally leads to its application as a fast electro-absorption
parts of the spectrum [72]. Fig. 9 shows the measured ac
modulator. High speed, small footprint, and high bandwidth
photoresponse of a single metal (Pd)–graphene junction to a
modulators are highly desirable for optical communications.
1.55 μm intensity modulated light beam. A nearly constant
However, although the light–graphene interaction is strong, the
response was observed up to 40 GHz, which was the upper fre-
extent of absorption of a light beam by a single graphene layer
quency limit of the measurement system used. Modeling, how-
is insufficient. For this purpose, the graphene was coupled with
ever, suggested that eventually the detector response of such de-
a silicon waveguide to increase the absorption, and a modula-
vices will be limited by their RC constant to about 0.6 THz [72].
tion by 0.1 dBμm−1 of the guided light (1.35 to 1.6 μm) at
In such a symmetric junction device, simultaneous illumination
frequencies over 1 GHz was demonstrated (see Fig. 8) [93]. An
of both opposite contact regions would produce equal but op-
alternative modulator design involving two layers of graphene,
posite polarity currents, and therefore, no net photocurrent. An
separated by a thin dielectric on top of the silicon waveguide,
improved design shown in Fig. 9(b) provided a significantly
has also been successfully demonstrated [94]. A different ap-
increased photoresponsivity (photocurrent/input optical power)
proach to electro-optic modulation involved the modulation of
and allowed one to utilize the full surface of the device for
a photonic crystal nanocavity by an electrically gated graphene
photodetection [97]. This device utilized interdigitated metal
layer. By tuning the Fermi level of graphene, one can modulate
electrodes made of two different metals, one with a high work
the reflectivity of the cavity at telecom wavelengths by more
function (e.g., Pd) and the other with a low work function (e.g.,
than 10 dB [95]. Graphene-based modulators operating in the
Ti). These two different work functions produced different dop-
terahertz range have also been proposed [96].
ing and band-bending in graphene that allowed photodetection
over the entire area of the device. This device was used to test its
C. Photodetectors
suitability in optical communications. It was shown that it could
Silicon, germanium, or compound semiconductors like reliably detect optical data streams of 1.55 μm light pulses at
InGaAs have traditionally been used for photodetection, par- the highest available rate of 10 GBits/s [97].
AVOURIS AND FREITAG: GRAPHENE PHOTONICS, PLASMONICS, AND OPTOELECTRONICS 6000112

Fig. 10. Graphene bolometers. (a) Dual-gated bilayer graphene hot-electron

bolometer. The plot shows the photoresponse as a function of top and bottom
Fig. 9. Graphene photodetectors. (a) High-speed graphene photodetector mea- gate voltages. The device was dc biased at 255 nA and the temperature was
sured up to 40 GHz with no degradation in signal level. The IR light at 1.55μm 6 K. Along the diagonal, the Fermi level is balanced at charge neutrality. In
wavelength was focused onto a graphene–metal contact. (b) Graphene photode- this range, the photoresponse increases strongly for increasing perpendicular
tector design optimized for collection over larger areas by utilizing interdigitated electric field due to opening of a bandgap in bilayer graphene. (b) Bolometer
finger electrodes with different metal composition. (c) Enhanced photoresponse based on tunnel junctions between graphene and superconducting aluminum
due to integration of a graphene photodetector with a silicon waveguide. The with thin TiOx tunneling barrier. The plot shows the dynamic resistance as a
main figure shows the photocurrent versus optical power injected into the wave- function of bias voltage for increasing radio-frequency power. The graphene
guide. Inset: detector layout using one centrally located signal electrode and acts as the absorber, whereas the tunneling junction, cooled below the critical
two grounded electrodes contacting graphene. (d) Remarkable uniformity in temperature of aluminum, acts as the temperature-sensitive element. (c) SEM
photocurrent over different telecommunication bands for the device in (c). (Re- image of a plasmonic photodetector utilizing a graphene nanoribbon array.
produced from [72], [97], and [100].) (d) Normalized conductance change as a function of gate voltage. The 140-nm
GRN array shows a strong plasmonic enhancement for light at 10.6 μm and
polarization perpendicular to the GNRs. The response is gate-voltage tunable.
To further increase the photoresponse, graphene can be in- (Reproduced from [106], [109], and [57].)
corporated inside Fabry–Pérot microcavities. In one case two
semitransparent metallic mirrors were utilized to form the res- resonance of the nanoparticle not graphene. A similar approach
onant cavity and the graphene was placed at the position of involved sandwiching gold nanoantennas (heptamer gold parti-
the maximum field leading to a 20-fold enhancement of the cle arrays) between two layers of graphene. The photocurrent
photocurrent at the resonant wavelength [98]. Another study was enhanced both by the field enhancement and by hot electron
utilized Bragg reflectors and achieved 60% absorption at a reso- injection leading up to a 20% internal quantum efficiency [104].
nance wavelength of 850 nm [99]. The most recent study [100] Semiconductor nanoparticle (PbS) arrays on graphene have also
[see Fig. 9(c) and (d)] combined graphene with a silicon wave- been utilized to enhance photodetection. Photoexcitation of the
guide to both enhance the responsivity of graphene and also to nanoparticle lead to charge transfer to graphene, a large enhance-
demonstrate the ability to integrate with silicon (this approach ment of the device capacitance, and a huge, 108 , gain [105]. The
has also been utilized in the case of light modulators discussed large RC, however, limits the speed of the device and the narrow
previously). In this way, the authors demonstrated photodetec- spectrum of the nanoparticle, the operating wavelength.
tion with a responsivity of 0.03–0.05 AW−1 over all fiber-optic Since electrons in graphene are coupled very weakly to the
communication bands, from O- to U-band, that is beyond the thermal bath, and thermalization within the electron gas is very
1605-nm wavelength range of strained germanium photodetec- fast, the bolometric effect is of particular interest (see Section
tors [101] and with a much smaller footprint than ion-implanted III-C). However, since graphene does not have a bandgap, the
Si detectors [102]. temperature dependence of its resistivity is generally weak. For-
Other approaches to further increase the response of graphene tunately, there are several approaches that could make the basic
photodetectors involved a combination of graphene and other bolometric response much more sensitive. It has, for example,
photoactive materials. Charge transfer between the photoex- been shown that gapped bilayer graphene can have advantages
cited material and graphene leads to residual opposite charges over single-layer graphene [see Fig. 10(a)] [106]. Applying an
on that material and amplification due to the graphene tran- electric field perpendicular to the graphene sheets opened a
sistor action. For example, by decorating graphene with gold bandgap in Bernal-stacked bilayer graphene [107], [108]. The
nanoparticles and exciting in the visible the plasmonic reso- increased resistance and temperature-dependence of resistance
nances of the nanoparticles, a large plasmonic field enhance- lead to higher responsivity and a very low noise equivalent
ment was obtained [103]. This is the same effect that leads to power (33 fW Hz−1 /2 at 5 K) [106]. Another approach of pro-
the giant enhancement of the Raman spectra by such localized viding large temperature dependence and low noise equivalent
plasmon resonances. A disadvantage of this approach is that power is the utilization of superconducting leads in combina-
the excitation/detection wavelength is now determined by the tion with tunnel junctions between graphene and the lead [see
6000112 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 20, NO. 1, JANUARY/FEBRUARY 2014

Fig. 10(b)] [109]. This approach makes use of the supercon- absorption of graphene coupled with its excellent conductiv-
ducting gap of the contacts with high temperature dependence ity, mechanical strength, lightness, flexibility and compatibility
around the critical temperature TC , rather than the temperature with silicon technology make an ideal candidate for photonic
dependence of the graphene itself. In this case, graphene acts and optoelectronic applications. Although the light absorption of
as the absorber and heat conductor, while the superconducting graphene via interband excitations is strong, for a single atomic
tunnel junctions act as the active elements. Finally, Johnson layer, it is not sufficient for most photonic applications. How-
noise thermometry on single-layer graphene contacted by reg- ever, as we have seen, integration with silicon waveguides or in
ular metals, may also be a viable approach for ultrasensitive photonic cavities can significantly enhance the absorption, al-
graphene bolometry [110]. lowing graphene to be utilized in a variety of photonic functions
A photodetection scheme based on plasmonics of graphene, such as light guiding, routing, and light modulation and detec-
patterned into metamaterials structures such as nanoribbons, tion. In the far-IR and tetrahertz frequency ranges, light absorp-
was proposed recently [see Fig. 10(c) and (d)] [57]. As tion in graphene involves intraband transitions whose strength
we discussed in Section II-B, GNRs exhibit well defined, can be large and tunable by electrostatic or tunable doping.
width-dependent plasmonic resonances that can be excited by Just a few layers of graphene provide sufficient absorption. By
s-polarized light. The basis of this approach is to use the exci- coupling to graphene localized plasmons the light–graphene in-
tation of the intrinsic plasmons of the nanoribbons to enhance teraction can be further enhanced and wavelength-selective ab-
the photoresponsitivity of the detector. Moreover, because of the sorption is possible. Graphene plasmonics may enable, besides
dual tunability provided by choosing the width of the nanorib- transparent and conductive screens, detectors and modulators,
bon and the gate dependent tuning of the plasmon resonance, other applications such as terahertz communications, mid- and
the detector can be made frequency selective for frequencies in far-IR imaging and spectroscopy. This is just the beginning of
the IR and terahertz ranges [57]. Due to the interaction of GNR the exploration of graphene in photonics and is to be expected
plasmon with surface phonon polaritons of the SiO2 substrate that many innovations will result from future studies of this
these resonances are hybrids of the two types of excitations. fascinating material.
In the implementation of this approach, arrays of nanoribbon
with widths ranging between 80 and 200 nm were fabricated ACKNOWLEDGMENT
lithographically. Their plasmon resonances were then tuned by
gate modulation of the chemical potential to be brought succes- The authors would like to thank their coworkers H. Yan, F.
sively in coincidence with the frequency of the exciting beam, Xia, T. Low, T. Mueller, W. Zhu, V. Perebeinos, and Z. Li for all
in this case, a CO2 laser beam at 943 cm−1 . The resulting pho- their contributions to the work described here and many valuable
tocurrent was measured with both s- and p-light polarization discussions.
to determine the effect of plasmon versus interband (electron–
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AVOURIS AND FREITAG: GRAPHENE PHOTONICS, PLASMONICS, AND OPTOELECTRONICS 6000112

[109] H. Vora, P. Kumaravadivel, B. Nielsen, and X. Du, “Bolometric response Marcus Freitag received the Diplom degree from
in graphene based superconducting tunnel junctions,” Appl. Phys. Lett., the University of Tuebingen, Tuebingen Germany,
vol. 100, p. 153507, 2012. in 1998, the M.S. degree from the University of
[110] K. C. Fong and K. C. Schwab, “Ultrasensitive and wide-bandwidth ther- Massachusetts Boston, Boston, MA, USA, in 1995,
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p. 031006, 2012. of Pennsylvania, Philadelphia, PA, USA, in 2002.
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W. Knap, M. Polini, V. Pellegrini, and A. Tredicucci, “Graphene field- gies, Inc., he joined the Research Division of IBM
effect transistors as room-temperature terahertz detectors,” Nat. Mater., in 2004. He is currently a Research Staff Member
vol. 11, pp. 865–871, 2012. in the Nanoscience and Nanotechnology group, IBM
[112] F. Rana, “Graphene terahertz plasmon oscillators,” IEEE Trans. Nan- T.J. Watson Research Center, Yorktown Heights, NY,
otechnol., vol. 7, pp. 91–99, 2008. USA. He has previously worked on scanning probe microscopy and electronic
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hertz generation from graphite,” Opt. Exp., vol. 17, pp. 16092–16099, graphene. Dr. Freitag has published more than 50 scientific papers. He has au-
2009. thored and coauthored several book chapters and reviews on carbon nanotube
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A. W. Holleitner, “Time-resolved ultrafast photocurrents and terahertz Physical Society.
generation in freely suspended graphene,” Nat. Commun., vol. 3, p. 646,
2012.

Phaedon Avouris received the B.Sc. degree from

the Aristotle University, Thessaloniki, Greece and
the Ph.D. degree in physical chemistry from Michi-
gan State University in 1974. He did postdoctoral
work at the University of California, Los Angeles,
CA, USA and was a Research Fellow at AT&T Bell
Laboratories before joining the staff of IBM’s Re-
search Division at the Watson Research Center in
1978. He is currently an IBM Fellow and the Man-
ager of Nanoscience and Nanotechnology at the T.
J. Watson Research Center, Yorktown Heights, NY,
USA. Dr. Avouris has published about 500 scientific papers. He has been elected
Fellow of the American Academy of Arts and Sciences, the American Physical
Society, the Institute of Physics of the U.K., the National Academy of Greece,
the IBM Academy of Technology, Materials Research Society, American Asso-
ciation for the Advancement of Science, the New York Academy of Sciences,
and the American Vacuum Society. He has received many awards including the
APS Irving Langmuir Prize for Chemical Physics, the IEEE Nanotechnology
Pioneer Award, the MRS David Turnbull Lectureship, the AVS Medard W.
Welch Award for Surface Science, the Julius Springer Award for Applied
Physics, the Richard E. Smalley Research Award of the Electrochemical So-
ciety, and the Richard Feynman Nanotechnology Prize. He has also received
many IBM Corporate and Outstanding Technical Achievement awards.