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covering up to 95% of the surface area can mined from the Hall effect. For Vg < Vg,min,
be obtained.9 To fabricate devices, graphene is p-type (current is carried by
graphene can be transferred by polydi- holes in the valence band), and for Vg >
methylsiloxane stamps or by dissolving Vg,min, graphene is n-type (current is car-
the underlying metallic substrate in a ried by electrons in the conduction band).
metal etchant and “scooping” the single- The conductivity σ(Vg) is nearly electron-
layer graphene up with desired substrates hole symmetric, reflecting the symmetric
(e.g., Si/SiO2). Quantum Hall effect and band structure (see Figure 1). At high car-
low-temperature mobilities up to 3700 rier concentration (i.e., far from Vg,min),
cm2/Vs have been observed in these σ(Vg) is roughly linear, indicating a nearly
metal-grown graphene sheets.8 Although constant mobility, approximately 18,000
Figure 2. Optical image of a large
single-layer graphene sheet (courtesy
still in its infancy, recent progress on epi- cm2/Vs for this sample. The on-state resis-
of W. Bao and C.N. Lau). Left inset: a taxial growth represents an important step tivity is as low as 80 Ohms/square.
hair of ~100 μm width shown on the toward the development of large-scale Figure 3b shows the mobility of a
same scale as the main panel. Right graphene-based electronic devices. graphene FET on SiO2 as a function of tem-
inset: Optical image of a graphene perature for a carrier concentration of 1011
sheet with 1-, 2- and 3-layer-thick Graphene Electronics cm−2.11 The experimentally determined
regions and a thicker (≥ 5 layers) region. Gapless Analog Devices mobility is roughly independent of tem-
Scale bar: 50 μm. The first-observed and still most-exam- perature at low temperature and is limited
ined aspect of graphene is its ambipolar by disorder. The disorder in mechanically
way to identify single- and bi-layer FET behavior, in which a gate electrode exfoliated graphene on SiO2 appears to be
graphene. Novoselov and Geim used a sil- can change both the charge carrier density primarily due to charges trapped at the
icon substrate with a 300-nm-thick layer of and type (n or p). Figure 3a shows the surface of the SiO2 or adsorbed on the
SiO2 for their initial experiments.3 Under conductivity as a function of gate voltage graphene.11,12,40–42 Other possible scattering
typical white light illumination, single- σ(Vg) at a temperature of 2.1 K for an exfo- mechanisms include point defects43–45
layer graphene on such a substrate liated graphene device on a SiO2/Si sub- (though expected to be rare in graphene
appears as very pale purple and almost strate, with the heavily doped Si acting as exfoliated from high-quality graphite crys-
transparent, and bi-layer graphene the gate.39 The conductivity σ(Vg) shows a tals), substrate-induced corrugations12,27,29
appears slightly darker in color (see characteristic “V” shape, with the mini- (which may explain the sublinear σ(Vg)
Figure 2). The thickness-dependent color mum conductivity occurring at a gate behavior observed in many devices),12,41,42
arises from a combination of two factors: voltage Vg,min that corresponds closely to or weak neutral impurities.46 Charged
(1) the thin graphene layer adds to the the point of charge neutrality, as deter- impurity scattering11,40,47–49 gives rise to the
optical path of the reflected light, thus
resulting in interference between the
paths that reflect off graphene and the a b
substrate,34 and (2) each graphene layer
14 106
absorbs about 2.3% of light,35–37 due to the Graphene on SiO2
so-called “universal optical conductivity,” Ref. 10, Sample 1
12 Ref. 10, Sample 2
which is another direct consequence of Suspended Graphene
Suspended graphene
graphene’s electronic structure. 10
Mobility (cm2 / Vs)
Conductivity (mS)
Ref. 12
The ease of graphene production by Phonons:
8 105
mechanical exfoliation has made the field LA phonons
SiO2 phonons
of two-dimensional electron physics 6 Impurities:
accessible to practically any investigator. Ref. 10, Sample 1
However, this technique is tedious and Graphene on SiO2 Ref. 10, Sample 2
4
produces randomly placed graphene Ref. 12
4
2 10 Total implied mobilities:
sheets. Obviously, to realize graphene’s Ref. 10, Sample 1
potential as a post-silicon electronic mate- Ref. 10, Sample 2
0 Ref. 12
rial, techniques for large-area synthesis of –80 –60 –40 –20 0 20 40 60 80 10 100
graphene are needed, prompting a return Gate Voltage (V) Temperature (K)
to the surface science techniques for
growth of graphene on metal and semi- Figure 3. (a) Conductivity as a function of gate voltage for a graphene field-effect
conductor substrates. Epitaxial growth of transistor on SiO2 substrate (data courtesy M.S. Fuhrer39). The upright and inverted
graphene on silicon carbide (SiC) sub- cones represent the valence and conduction band structure, and the shading indicates
strates has emerged as a particularly the filling of electronic states. (b) Mobility as a function of temperature for graphene on
promising technique,7,38 as discussed in SiO2 at a carrier density of 1011 cm−2 (blue-filled triangles and red-filled squares);11
detail by First et al. in this issue. Very suspended graphene at a similar carrier density of 2 × 1011 cm−2 (open purple circles;55
recently, there has also been significant similar values are reported in Reference 56). Blue, red, and purple dashed lines show
progress in growing graphene on large- the contribution from impurities for each sample. The gold dashed line shows the
contribution from the longitudinal acoustic (LA) phonons of graphene. The green
area polycrystalline metallic substrates,
dashed line shows the contribution from remote interfacial phonon scattering due to the
such as Ni8,10 and Cu,9 via chemical vapor polar optical phonons of the SiO2 substrate (not applicable to the suspended sample).
deposition. Typically, such synthesis is Solid blue, red, and purple lines show the total contribution from impurities and phonons
performed by placing the metal substrate (graphene LA phonons and SiO2 optical phonons for graphene on SiO2; graphene LA
in a furnace in a methane/hydrogen phonons only for suspended graphene). Note that contributions to mobility are added
mixture at 1000°C. Single-layer graphene inversely.
linear σ(Vg) observed in graphene on SiO2 tron mobility transistors, for which the different approaches have been proposed.
(see Figure 3a) and also explains the mag- highest mobilities achieved in actual Here we focus on three different
nitude of the minimum conductivity: the devices are ~30,000–40,000 cm2/Vs.54 The approaches that have been experimentally
random charged impurity potential cre- on/off resistivity ratio of graphene FETs is realized.
ates puddles of electrons and holes in only ~100:1 in the best devices, but this is Perhaps the most natural approach to
nominally charge-neutral graphene,48 suitable for analog device applications. bandgap creation is through quantum
leading to a finite minimum conductiv- Removing the SiO2 substrate removes confinement of charges in graphene
ity.4,40,50 Increasing the number of charged RIP scattering and also greatly reduces the nanoribbons (GNRs).59 A GNR is expected
impurities decreases the mobility but charged impurity scattering, presumably to have a bandgap Eg that scales inversely
increases the residual carrier density in the by eliminating the influence of trapped with width (i.e., Eg = Δ0/ Na), where Δ0 is
puddles. The result is that the minimum charges in the SiO2. Suspended graphene an “intrinsic” energy gap, and Na is the
conductivity value is only weakly depend- devices, free from the SiO2 substrate, have number of atoms across the GNR width.
ent on disorder and is, on order, a few shown mobilities as high as 250,000 Theoretical calculations60 predict that Δ0
times the quantum of conductance (G0 = cm2/Vs at low temperature13,55,56 and depends on the edge type (armchair ver-
2e2/h = 7.7 × 10−5 S, where e is the elemen- 120,000 cm2/Vs at 240 K.55 sus zigzag, see Figure 4a and 4b), with an
tary charge). Because it is a gapless semiconductor, additional rapid dependence on Na with
Graphene’s mobility begins to show graphene cannot be directly used for digi- period 3 in the case of armchair nanorib-
strong temperature dependence near room tal electronics (see subsection Bandgap bons. Energy gaps of several hundred
temperature (see Figure 3b).11,12 Engineering in Graphene). On the other meV are expected for widths in the few
Surprisingly, this temperature dependence hand, one can take advantage of its nanometer range for ideal armchair
is dominated not by the phonons of ambipolar transport characteristic to make GNRs, whereas zigzag GNRs may exhibit
graphene itself, but instead by remote inter- analog devices such as frequency multipli- ferromagnetic metallic edge states.61
facial phonon (RIP) scattering from the opti- ers, high-frequency mixers, zero-volt detec- GNRs have been fabricated using a
cal phonons of the SiO2 substrate.51,52 RIP tors, and radio receivers.57 IBM researchers variety of methods, including (1) standard
scattering limits the mobility of graphene have recently demonstrated operation of a electron beam lithography and etching;
on SiO2 to ~40,000 cm2/Vs at room temper- high-frequency graphene FET, with a cut- (2) chemical exfoliation of graphite, fol-
ature.11 Graphene’s longitudinal acoustic off frequency as high as 100 GHz.58 lowed by sonication in special surfactants
phonons give a much weaker contribu- and centrifugation to remove thicker lay-
tion,11,53 limiting the mobility to ~200,000 Bandgap Engineering in Graphene ers; and (3) lithographically or chemically
cm2/Vs at room temperature at a carrier Bandgap creation and engineering is unzipping carbon nanotubes.62,63 In trans-
density of 1011 cm−2. The phonon-limited crucial for realization of graphene’s poten- port experiments on lithographically
mobility of graphene on SiO2 compares tial as an electronic material that supple- defined64,65 and chemically derived
favorably to that of InAs and InSb high elec- ments or replaces silicon. A number of GNRs,66 a gap has been reported, and the
a c e
top
a = 2.46A
zigzag ~ d = 3.35A E
B A
~
B A
bottom
armchair
Energy
0 0 Eg 0 Eg 0 0 Eg
–10
K G M
K K K K
Wave Number Wave Number
Figure 4. Strategies for opening a bandgap in graphene. (a) Atomic structure of graphene nanoribbons with zigzag and armchair edges
(courtesy of M. Bockrath). (b) Schematic band structure of zigzag and armchair graphene nanoribbons. The armchair nanoribbon shows an
energy gap that is inversely proportional to width. The zigzag ribbon shows states at zero energy that are localized at the edges of the ribbon.
Detailed calculations show that these states may be spin-polarized.61 (c) Atomic structure of graphane. Grey atoms are carbon, white are
hydrogen. (Reprinted with permission from Reference 79. ©2007, American Physical Society.) (d) Band structure of graphane.79 K, Γ, and M
represent high-symmetry points in the hexagonal Brillouin zone (courtesy of J. Sofo). (e) Atomic structure of Bernal-stacked bilayer graphene.
(f) Band structure of Bernal-stacked bilayer graphene without (left) and with (right) perpendicular electric field E.
narrowest GNRs have on/off ratios of bilayer graphene has increasingly shared metallic electronic reservoirs. In the case of
>106 at room temeprature.66,67 There is the spotlight (see Figure 4e). The band graphene, there are at least three distinct
considerable debate over how the structure of bilayer graphene is unusual types of two-layer systems: AB stacked
observed “transport gap” relates to the and distinct from single-layer graphene: bilayers, which are readily obtained by
energy gap (gap in the electronic spec- bilayer graphene has massive (parabolic) mechanical exfoliation of graphite, rotated
trum), given that transport experiments valence and conduction bands but layers, which form in epitaxial graphene
are also influenced by localization effects remains gapless—the conduction and grown on SiC substrates, and two isolated
due to the disordered edges, defects, valence bands touch at the charge neutral- graphene layers, which are separated by a
and/or impurities.68,69 Future experiments ity point82,83 (see Figure 4f [left]). However, dielectric. In all of these cases, an electric
will be necessary to clarify and optimize when an electric field is applied perpendi- potential difference between top and bot-
the nature and magnitude of transport cular to bilayer graphene, a bandgap tom layers acts like an effective magnetic
gaps in GNRs. opens at the charge-neutrality point, and field that favors one pseudospin state over
Ideally, the result of graphene electron- the valence and conduction bands adopt a the other, thus providing a platform for
ics research would be “designer” GNRs “Mexican hat” shape (see Figure 4f single-particle pseudospintronic devices.96
with controlled, crystallographically ori- [right]).84,85 The electric field–induced gap Even more enticing, it now may be possi-
ented edges that enable customization of has recently been measured in photoemis- ble to create two-layer graphene systems
their electronic properties. For instance, a sion86 and optical87,88 experiments to be as that exhibit pseudospin ferromagnetism.
5-nm-wide ribbon may display metallic, large as ~200 mV. Transport measure- Nearly neutral AB bilayers, for example,
semiconducting, or even ferromagnetic ments in gapped bilayer graphene show could be Ising-like pseudospin ferromag-
behavior, depending on its edge orienta- insulating behavior characteristic of disor- nets, in which charge is spontaneously
tion. Recently, it was demonstrated that at dered semiconductors, probably indicat- transferred between layers.97 The electron-
elevated temperatures, Ni or Fe nanopar- ing that the disorder strength is still larger ically isolated bilayer systems could be XY-
ticles etch thin graphite and graphene than the energy gap in current bilayer like pseudospin ferromagnets, in which
sheets,70–72 leaving trenches at abrupt graphene samples.89 phase coherence is spontaneously estab-
angles, suggesting that they move along lished between separate layers. Both types
specific crystallographic directions. This Beyond CMOS of pseudospin ferromagnetism would98
surprising discovery, combined with A number of research efforts seeking lead to spectacular electrical effects in sep-
efforts to functionalize or passivate the electronic technologies “beyond CMOS” arately contacted bilayers.
edges, might enable ribbons with tailored are focused on the realization of comput- Spontaneous interlayer phase coherence
electronic properties. ing devices based on state variables other is a type of condensed matter order that
Chemical modification of graphene than charge. An example is “spintronics,” has been imagined for many years but
(e.g., by reaction with atomic hydrogen73,74 in which information is stored and manip- realized so far only in semiconductor
or through solution chemistry75,76) also ulated in the electron’s spin.90 Because of bilayers and only at low temperatures
offers a promising route for bandgap engi- the low atomic number of carbon and the and in extremely strong magnetic fields.
neering, with the advantage of being scal- predominance of the spin-zero carbon-12 Spontaneous coherence is associated with
able and inexpensive. Recently, graphene nucleus (making up 99% of naturally exciton condensation and is closely analo-
was found to display semiconducting occurring carbon), carbon atoms have gous to superfluidity due to 3He-3He pair
behavior after exposure to a hydrogen weak spin-orbit and hyperfine couplings, formation in liquid 3He. It has been pre-
plasma (Figure 4d).73,74 During hydrogena- hence a potential for very long spin life- dicted99 that spontaneous phase coher-
tion, each hydrogen atom removes a pi times. When combined with its very large ence might occur in electrically isolated
electron from graphene via a sp2-to-sp3 current-carrying capacity, these attributes graphene bilayers that have high densities
transformation of the carbon atom bond- make graphene an attractive candidate for of electrons and holes in opposite layers and
ing pattern. The fully hydrogenated com- spin-conserving, conducting elements in a layer separation that is comparable to or
pound, graphane, is predicted to be a spintronic circuits. Experimental studies smaller than the distance between carriers
semiconductor with a 3.5 eV energy of spin lifetimes and spin propagation in within a layer. Given the disorder present in
gap.77–79 Graphane is stable at room tem- graphene are promising but are still at an graphene samples on substrates, realization
perature, exhibiting semiconducting trans- early stage91–94 and not yet completely of this exotic state appears to require
port properties. Remarkably, upon understood. In particular, the measured electron and hole densities ~1013 cm−2 and
annealing at 450°C, graphane reverts to the spin lifetime is much shorter than layer separations of not more than a few
gapless graphene state, and metallic con- expected,94 possibly due to disorder or nm. Progress is being made in engineering
duction (including even the quantum Hall edge chemistry. circumstances favorable for this form of
effect) can be recovered.73 Looking further into the future, pseudospin ferromagnetism.100
The discovery of graphane opens up a graphene is also a promising material
new front for chemical bandgap engineer- for pseudospintronics. Pseudospintronics Other Applications of Graphene
ing and synthesis of novel graphene-related refers to the storage and manipulation of In addition to being an excellent con-
materials. In general, one can expect an any two valued quantum degree-of- ductor with fascinating electrical proper-
intricate interplay between electronic struc- freedom other than spin.95,96 Unlike spin- ties, graphene is also nature’s thinnest
ture, hydrogen ordering,80,81 and corruga- tronics, pseudospintronics has so far elastic membrane, opening the door for
tion of the graphene sheet, resulting in remained almost exclusively a theoretical new electromechanical applications.
higher stability of some of the configura- notion. The most attractive degree of free- Graphene can sustain >20% strain without
tions/coverages than others. In fact, we dom for pseudospintronics appears to be breaking,23 and the strain dependence of
expect an entire family of stable macromol- the which-layer degree of freedom of a two- its conductivity can be exploited to enable
ecules bridging graphene and graphane. layer two-dimensional electron system, in piezoelectric materials,8 strain sensors, or
So far most attention has focused on which separate contacts to the individual flexible electronics. Despite being only one
single-layer graphene. Recently, however, layers provide a ready source of half- atomic layer thick, graphene is also an
amazingly strong material, with a Young’s Conclusions 8. K.S. Kim, Y. Zhao, H. Jang, S.Y. Lee, J.M.
modulus of ~1 TPa23,101 and a breaking Graphene is a fundamentally new elec- Kim, J.H. Ahn, P. Kim, J.Y. Choi, B.H. Hong,
strength of ~130 GPa.23 These attributes tronic material, whose electrons are Nature 457, 706 (2009).
make graphene an ideal candidate for 9. X.S. Li, W.W. Cai, J.H. An, S. Kim, J. Nah,
strictly confined to an atomically thin two- D.X. Yang, R. Piner, A. Velamakanni, I. Jung,
nanoelectromechanical applications, such dimensional plane and exhibit properties E. Tutuc, S.K. Banerjee, L. Colombo, R.S. Ruoff,
as mass detection with unparalleled sensi- mimicking those of ultrarelativistic parti- Science 324, 1312 (2009).
tivity. Nanomechanical resonators based cles. In this review, we have attempted to 10. A. Reina, X.T. Jia, J. Ho, D. Nezich, H.B. Son,
on freestanding graphene membranes provide a brief snapshot of this extremely V. Bulovic, M.S. Dresselhaus, J. Kong, Nano Lett.
have been demonstrated102 and may lead rapidly moving field. Graphene is imme- 9, 30 (2009).
to ultrasensitive position, force, and mass diately applicable to high-speed analog 11. J.H. Chen, C. Jang, S.D. Xiao, M. Ishigami,
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