Nano-Engineering of Graphene and Related Materials

1. ntroduction

Graphene is the ultimately monolayer material with single-atom thickness.
It possesses many Iascinating properties including massless Dirac electronic
structure, anomalous quantum Hall eIIects, high mobility, extraordinary high
thermal conductivity, stiIIness and strength (see other chapters in this book).
Impressively, these properties have remarkable dependence on its
morphology and atomic structure, e.g. its size and shape (Fig. 1, Xu &
Buehler, 2010a). Moreover, interior and exterior doping eIIects Irom deIects,
molecular adsorptions or electromagnetic Iields are also signiIicant. For
example, hydrogenation,
oxidation and electrical Iield signiIicantly tune its structural, mechanical,
thermal, electronic and optical structures, which is controllable and even
reversible. These sensitive responses oI a graphene sheet to structural and
environmental cues enable us opportunities to engineer its physical and
chemical properties at nanoscale


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Nano-engineering by tailoring nanostructures






Back to year 2004, the Iirst experimental establishment oI
producing graphene sheets is achieved by Andre Geim and Konstantin
Novoselov oI the University oI Manchester, through a so-called 'scotch-
tape technique (Novoselov et al., 2004). In this approach, single- or
Iew-layered graphene sheets can be obtained by repeatedly peeling
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highly oriented pyrolytic graphite (HO!G) using scotch tapes. Although
the graphene sheets thus produced are poor in the production yield and
controllability on the geometry, this mechanical exIoliation technique
Ieatures high reliability and oIIers graphene sheets oI very high quality.
Even at present, the simple but eIIicient 'scotch-tape technique is still a
common one to Iabricate high-quality samples. This seminal work is our
Iirst time to Iabricate and observe two-dimensional crystalline materials.
Geim and Novoselov are thus awarded the 2010 Nobel !rize in physics.
In prior to their work, physicists believed that two-dimensional crystals
couldn`t sustain stabilities in ambient environment at Iinite temperature.
Early work based on elasticity theory shows that the out-oI-plane
displacement Iield diverges Ior inIinite large two-dimensional crystals
(Mermin & Wagner,
1966

The bulk graphene sheet is a semi-metal with a linear dispersion
around the Dirac point. Hoiver when one oI the in-plane dimensions
reduces below 20 nm while maintaining the other dimension, the
graphene ribbon (Fig. 1(c)) will Ieature an edge dependent electronic
structure due to the quantum conIinement and lattice symmetry (Son,
Cohen & Louie, 2006a and 2006b). Armchair-edged graphene
nanoribbons (AGNR) have width dependent energy gaps, while a
zigzag-edged nanoribbons (ZGNR) is always metallic with a localized
state at the edge when the spin is unpolarized.

This unique structure-property relationship suggests
that simple geometrical tailoring could realize eIIective modiIication on
the properties oI graphene.







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Graphene nanostructures as building blocks for
nanoelectronics







As illustrated in Fig. 3, the width oI AGNR structure can be
denoted by the number Na. Tight-binding analysis shows that (Ezawa,
2006; Son, Cohen & Louie, 2006a and 2006b) when Na is 3p2 (where
p is a positive integer), the AGNR is metallic. While when Na is 3p or
3p1, the bandgap oI AGNR is inversely proportional to its width
(Eg(3p) _Eg(3p1)). These results are consistent with density
Iunctional theory (DFT) calculations based on local density
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approximation (LDA). The only diIIerence is that in the DFT simulation,
the reconstruction oI structure and electron density at ribbon edge opens
small gap Ior Na 3p2, and decreases (increases) the gaps oI 3p
(3p1) AGNRs. The structure oI ZGNR is shown in Fig. 3(b). Simple
analysis Irom the tight-binding picture predicts that the spin-unpolarized
eigenstates oI ZGNRs near EF have a peculiar edge-state.

The width-dependence energy gaps in AGNR are soon veriIied by
experiments (Chen et al., 2007; Han et al., 2007). Interestingly, Hanet al.
also Iind that the bandgap Eg shows no direct dependence on the
crystallographic direction (Han et al., 2007). Actually during the
Iabrication processes or during the selI-passivating process aIter the
structure is Iormed, the edge shape (armchair or zigzag) can reconstruct
(Jia et al., 2009; Girit et al., 2009) and this may cause the bandgap to
appear Ior graphene nanoribbons with any crystalline orientation. As
mentioned above, graphene nanoribbons Ieature remarkable size- and
edge-dependent electronic properties.

Elementary building blocks Ior nanoelectronics, such as
metal/semiconductor junctions and quantum dots, thus can be
constructed through a combination oI these structural patterns (Xu,
Zheng & Chen, 2007). As shown in Fig. 4(a), a junction combining
metallic and semiconducting GNRs is easy to Iorm.

Actually during the Iabrication processes or during the selI-passivating
process aIter the structure is Iormed, the edge shape (armchair or zigzag)
can reconstruct (Jia et al., 2009; Girit et al., 2009) and this may cause the
bandgap to appear Ior graphene nanoribbons with any crystalline
orientation.
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Fig 3(c) Bandgap oI armchair graphene nanoribbons calculated Irom
density Iunctional theory


As illustrated in Fig. 3, the width oI AGNR structure can be
denoted by the number Na. Tight-binding analysis shows that (Ezawa,
2006; Son, Cohen & Louie, 2006a and 2006b) when Na is 3p2 (where
p is a positive integer), the AGNR is metallic. While when Na is 3p or
3p1, the bandgap oI AGNR is inversely proportional to its width
(Eg(3p) _ Eg(3p1)). These results are consistent with density
Iunctional theory (DFT) calculations based on local density
approximation (LDA). The only diIIerence is that in the DFT simulation,
the reconstruction oI structure and electron density at ribbon edge opens
small gap Ior Na 3p2, and decreases (increases) the gaps oI 3p
(3p1) AGNRs.


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Synthesis and fabrication of graphene
nanostructures

To achieve a rational design oI graphene nanostructures as
suggested in Section 2.1, experimental techniques such as catalytic
hydrogenation based nano-cutting method are proposed to Iabricate
graphene nanostructures with speciIic geometry.

Ci et al. (Ci et al., 2008) report a controlled cutting process Ior
graphene sheets, using nickel nanoparticles as a kniIe that cuts with
nanoscale precision (Fig. 5). The cutting proceeds via catalytic
hydrogenation oI the graphene lattice, where carbon atoms in graphene
react with hydrogen into hydrocarbon and the catalytic nanoparticles
continue to move due to the adhesion Irom remainder carbon atoms in
graphene. This cutting process generates graphene pieces with specifed
zigzag or armchair edges.

The size oI the nanoparticle dictates the width oI etched channel
and edge structure that is produced during the cutting. The cutting
occurs along straight lines and along symmetry lines, deIined by angles
oI 60 or
120, and is defected at Iree edges or deIects, allowing practical control
oI graphene nano-engineering. DFT calculation shows that the reaction
barrier to remove carbon atoms and leave zigzag edges is much higher
than armchair edges. This explains the experimental
observation where zigzag edges are dominant.

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Effects of external fields

It is reported that the bandgap oI bilayer graphene can be tuned by
electric Iield in perpendicular to the basal plane, e.g. through gating.
The symmetry oI sublattice in AB stacking is broken upon electrical
gating. The electrical displacement Iields in diIIerent graphene layers
produce two eIIects including a net carrier doping (shiIting oI the
Fermi energy) and generation oI a non-zero bandgap. The gate-
tunable bandgap can reach 250 meV and has the unusually strong
oscillator strength Ior the bandgap transitions.

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Thus bilayer graphene under electrical Iield tuning can enable
novel nanophotonic devices Ior inIrared light generation,
ampliIication and detection. Using a double-gate conIiguration, an
insulating state with large suppression oI the conductivity in bilayer
graphene can be Iurther achieved (Zhang et al., 2009; Oostinga et al.,
2008). In comparison to exterior dopants and deIects, the advantage
oI this control method is that the control is non-contact and can be
continuous tuned.



STRAN ENGNEERNG


Strain engineering, or more generally tuning material properties by
applying mechanical loads or deIormation, is a powerIul strategy in
improving material perIormance. In silicon-based semiconductor
industry, strained silicon has much higher mobility, and thus much better
chip perIormance and lower energy consumption. When material goes
down to low dimension, the eIIects oI strain become even more
signiIicant as directional load is more Ieasible. Also bending oI two-
dimensional membranes or one-dimensional ribbons can easily be
excited at ambient condition, resulting in a signiIicant local curvature.

Recently, stretchable and Ilexible electronics have attracted many
interests Irom various disciplines.Thus, a mapping between deIormation
oI graphene and its impacts on the properties becomes extremely
important. As introduced in previous sections, molecular
Iunctionalization on graphene sheet usually induces structural distortion
as it disturbs or breaks the underlying sp2 bonding network and Iorms
sp3 bonds locally. Vice versa, mechanical deIormation, which modiIies
the sp2 bonds, provides another method to tune the graphene properties,
reversibly. This approach,
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in combination with molecular doping, is expected to play a critical role
in nano-engineering oI graphene and related materials.




ERARCCAL STRUCTURES OF
MACROSCOPC GRAPENE MATERALS


Graphene and graphene nanoribbons present intriguing properties and
thus have been suggested Ior a wide range oI applications Irom
nanoelectronics to nanoelectromechanical !hysics and Applications oI
Graphene - Experiments 16 systems. However, as introduced beIore
(Fig. 1), the morphology oI this monolayer material has large derivation
Irom the native two-dimensional sheet at elevated structures, especially
Ior the ribbon with high aspect ratio. Also entanglements and scrolls are
easy to Iorm at marked density, instead oI the patterned or selI-
organized structures as required by industrial applications.

To bridge the scales Irom their nanostructural geometrythe key
Ior their unique propertiesto the critical requirements Ior large-scale
electronics and device applications, there we need a hierarchical
approach to assembly macroscopic material Irom Iunctionalized
graphene sheets or nanoribbons. This approach has to (1) be able to
assemble the nanostructures into macroscopic assemblies, while (2)
preserving their nanostructure-speciIic physical signiIicance and novel
properties at larger scales, such as its size- and shape-dependent
electronic structures.

SSUES TO BE RESOLVED N GRAPENE
NANO ENGNEERNG

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Nevertheless, there are still several key issues expected to be
resolved in the Iuture development on the graphene nano-engineering:
Scalability Most oI the nano-engineering techniques modiIy the
properties oI graphene and related materials at the molecular level.
However towards industrial applications, Ieasible
scaling methods have to be developed, such as patterning and selI-
assembly.

Unlike other selI-assembly system, the scaling here on graphene
sheet must be hierarchical, the layer-by-layer or scrolling organizing
have to be exclude in the assembling process as they introduce interlayer
coupling between graphene sheets. The controllable top-down
lithography and bottom-up assembly directed by hydrogen bonds or
covalent bonds that have orientation-speciIication are very promising in
this direction.

1.Tunability. MultiIunctional materials hold great potentials Ior the next-
generation materials including high-perIormance composites,
nanoelectronics, microIluidics, and other microelectromechanical
systems (MEMS) or nano electromechanical systems(NEMS).The non-
covalent Iunctionalization methods treating gaseous molecules, metal
atoms, or covalent Iunctionalization that can be reversibly applied have
great potentials Ior this issue.

2.Applications The multiIunctionality oI graphene oIIers it numerous
applications. Novel applications in emerging Iields still need
exploration, such as quantum inIormation devices
and sustainable energy applications where nanoscale engineering can
play an important role. Moreover, the graphene Ilake, nanoribbon, sheet
and graphite are representative zero-,
one-, two- and three-dimensional materials. This unique Ieature suggests
to use graphene related materials as platIorms or model materials Ior
basic research. Graphene is also a unique material standing between
inorganic and organics materials. Combining materials engineering with
synthetic biological methods also helps to select, design and produce
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new classes oI materials designed Irom the molecular level upwards.
Finally, we close this chapter by calling upon researchers to pay
attention to Iollowing key
scientiIic problems.

.Intermolecular interactions The basic interactions between
molecular dopants, Iunctional groups, supporting substrates and
graphene are still not clear. The physical and chemical Nano-
Engineering oI Graphene and Related Materials properties oI
interactions such as hydrogen bonds, electrostatic, hydrophobic Iorces,
especially those involved in assembling processes, should be
highlighted.

4.Nanoscale interfaces The interIace between graphene and various
materials including semiconductors, metals and polymers dominates the
perIormance oI nanoelectromechanical devices and nanocomposites.

However, it is not clear that iI conventional interIace theories
still hold at this scale, especially those related to the energy transport
processes across. Multiphysics coupling The research on graphene and
related materials towards industrial
applications are intrinsically multiphysical and multiscale. The interplay
between structural, mechanical, electronic and optical properties, which
shapes the unique Ieatures oI these materials outperIorming
conventional materials, must be understood. Multiphysics and multiscale
computational paradigm and experimental platIorms are urged.







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GRAPENE TRANSSTORS


NTRODUCTON

The recent discovery oI graphene (Novoselov et al., 2004), a single
atomic sheet oI graphite, has ignited intense research activities to
explore the electronic properties oI this novel two-dimensional (2D)
electronic system. Charge transport in grapheme diIIers Irom that in
conventional 2D electronic systems as a consequence oI the conical
energy dispersion relation near the charge neutrality (Dirac) point in the
electronic band structure (Zhang et al., 2005). Field-eIIect mobility as
high as 15 000 cm2/V.s and a Fermi velocity oI ~108 cm/s have been
demonstrated at room temperature (Geim & Novoselov 2007).

These properties make graphene a possible candidate Ior electronic
devices in the Iuture. The major beneIit oI graphene Irequently quoted
is superior electron/hole mobility compared to other semiconductors, but
as Fig. 1 shows, this is not experimentally the case yet when compared
to narrow bandgap III-V semiconductors Ior comparable carrier
densities. In addition, the lack oI a band gap limits the usage oI two
dimensional graphene Ior digital switching, where high on/oII ratios are
necessary. However, several potential advantages may be listed: the
perIect 2D conIinement oI carriers, electron/hole symmetry originating
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Irom a conical bandstructure, and the possibility oI opening bandgaps
lithographically by Iabricating graphene nanoribbons (GNRs).

In Section 2, high Iield characteristics oI 2D exIoliated graphene
are reported on both short-channel and long-channel back gated Iield
eIIect transistors (FETs). We will elaborate on the problem oI metal
contact Iormation and high Iield transport oI 2D graphene. The
comparison oI Iabricated devices based on exIoliated, epitaxial and
chemical vapour deposited (CVD) graphene will Iollow. The large area
graphene opens the possibility to make 2D graphene devices Ior
RF/analog ampliIication (Lin et al., 2010). Superior Irequency
perIormance oI such devices makes it a promising application oI 2D
graphene FETs. The real advantage oI graphene, however, can be
highlighted Irom a novel proposed device architecture that is yet to be
demonstrated (Zhang et al., 2008). II GNRs are made by lithographic
patterning, and are either chemically or electrostatically doped into GNR
p-n junctions, then the planar Iorm yields to a tunnelling Iield-eIIect
transistor (TFET).

Towards the realization oI the GNR TFET we designed a single
but tuneable junction structure to demonstrate the operational principle.
We discuss these GNR p-n junction transistors in Section 3 along with
the developed analytical and device models used to explain the
measured transistor characteristics.


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D GRAPENE TRANSSTORS


DEVCE FABRCATON AND CARACTERSTCS OF D
EXFOLATED GRAPENE TRANSSTORS

Graphene oIIers advantages Ior interconnects due to high current
carrying capacity despite its single layer nature (Murali et al., 2009) but
more oIten graphene is being considered as a possible channel material
Ior transistor technology.

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So Iar, graphene has been studied mostly at low biases, but Ior the
application in practical devices, it is essential to investigate
the high-Iield transport properties. High current drives were measured
by pushing the devices up to breakdown. The saturation current density
Ior many samples has been measured to be in the 1.5 2 A/mm range.
Gate modulation oI the drain current is Iound to depend strongly on the
channel length. For comparable 2D carrier concentrations, saturation
currents in 2D graphene are Iound to be higher than Si MOSFETs and
III-V Nitride HEMTs a Ieature that is attractive Ior various
applications.

We Iirst discuss 2D graphene FETs Iabricated Irom exIoliated
graphene and later we compare the results to graphene devices made oI
catalyzed CVD or epitaxial graphene. ExIoliated graphene Ilakes on
heavily n-type doped silicon waIers with tox 300 nm thick thermal
oxide Irom Graphene Industries (Ior preparation oI samples, see:
Novoselov et al., 2004) were used Ior the experiments. Single layer
graphene Ilakes were identiIied by Raman spectroscopy (inset oI Fig. 2
(a)). The waIers were backside-metalized aIter oxide removal in
HF to Iorm back-gate contacts. E-beam evaporated Cr/Au (2/200nm)
was used to deIine the drain and source contacts, which were patterned
by e-beam lithography. The source-drain separations ranged Irom L
250 nm - 8 m. AIter metal deposition and liIt-oII, the samples were
annealed in Iorming gas at ~650 K Ior ~2 hours to remove the e-beam
resist residue.

The graphene Ilakes were then patterned by O2 plasma reactive
ion etch with !MMA masks to widths ranging Irom W 1 - 10 m. The
SEM image (inset oI Fig. 2 (b)) shows a typical FET. High current
annealing was perIormed to drive oII impurities Ior some FETs to
recover their intrinsic perIormance. The devices were measured using a
semiconductor parameter analyzer in ambient environment and in
vacuum, at room temperature and at 77 K. The drain currents oI the
FETs were Iirst measured at a low bias oI
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VDS 20 mV, while the gate voltage was varied over a wide range.
The gate leakage current was many orders oI magnitude lower than the
drain current.





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Fig. 2 (a) shows the representative transIer characteristics oI a
long- and a short-channel FET. Over the same range oI gate overdrives,
the long channel FET was observed to exhibit higher gate modulation
(~8x) than the short-channel FETs (~2x).The Iield eIIect mobilities were
calculated to be ~2000 4000 cm2/V.s Ior long-channel FET and ~200
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cm2/V.s Ior short-channel FET respectively. These characteristics
remained similar at diIIerent pressures, as well as at lower temperature.

Recently, saturation oI drain current at high source-drain biases has
been reported, and theory oI optical phonon emission limited saturation
current has been proposed (Meric et al., 2008; Luo et al., 2008). In
particular, back- and top-gated 2D graphene FETs showed saturation
current densities in the 0.5 0.7 A/mm range as reported by Meric et al.,
2008. In Fig. 2 (b), the high bias characteristics oI a back-gated FET
(W/L 1.75/4 m) are
Shown

A saturation current oI 1.38 A/mm is measured Ior this device.
Saturation current densities in the 1.5 2.0 A/mm range were measured
on a number oI devices.

In agreement with another earlier report Ior back-gated devices
(Luo et al.,2008). This is ~2x higher than the reported saturation current
densities Ior dual-gate devices, indicating that the top-gate high-k oxide
lowers the current drive through graphene. The eIIective 2D carrier
densities were in the 2 - 4.1012 cm-2 range, as estimated Irom the
eIIective gate voltage. The ~0.5 - 0.7 A/mm saturation current reported
earlier has been attributed to substrate-induced optical phonon
scattering. However the ~2x higher current drives measured here on
SiO2 substrates indicate that the lower current drives are due to the top
gate high-k oxide rather than the SiO2 substrate. This conjecture will be
discussed in detail in the next Section. Such current drives can be
obtained in Si MOSFETs and III-V HEMTs, but only with a) high
2DEG densities (~1013 cm-2), and/or b) very short channel lengths
taking advantage oI ballistic transport. Our measurements show that
graphene FETs are able to achieve these high current densities without
these criteria, implying that even higher current drives are possible when
they are met in the Iuture.

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For a rough comparison, a carbon nanotube with diameter ~2 nm
and a saturation current ~25 A has an eIIective current per the
circumIerential width ~4 A/mm (Chen & Fuhrer, 2005), much higher
than either graphene or other semiconductors. At high drain biases, the
current saturates at more than 1 A/mm,
but with weak gate modulation. Graphene carries over the high current
carrying capacity oI carbon nanotubes, but the absence oI an energy
bandgap hampers the modulation oI this high current density.



























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CONCLUSON

At last it can be conclude that Graphene oers and promises a lot
oI dierent applications, in-cluding conductive ink, terahertz transistors,
ultraIast photodetectors, bendable touch screens, strain tensors and many
other.

The Stone Age, the Bronze Age, the Iron Age ... Every global
epoch in the history oI the mankind is characterized by materials used in
it. In 2004 a new era in the material sci-ence was opened: the era oI
graphene or, more generally, oI two-dimensional materials.

It will not be wrong to conclude thst in short time we will be
having thin Ilexible electronic devices portable and unbreakable all
because oI graphene. Graphene technology is taking over every other
technology in electronic Iield. Other technologies will become obsolete
soon. In near Iuture there will be devices that would use minimal power
and dissipate negligible heat.we would have swimming costumes in
which we could play our i-pods or charge our mobiles.

Textiles could be used Ior making electronic gadgets or we can say
that we would have our clothes made up oI electronic circuits. It is a
picturesque imagination to think that all the integrated circuits will
become too small Ior being spacious.

We could carry anything anywhere with no bulky connections or
heavy circuits oI Iear oI breakage. We would have transparent gadgets
that wont even break on Ialling or bending.Thus we can see our Iuture
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wonder material as graphene which is set to bring revolution in human
liIe.






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