Introduc)on

to sp2 carbon
nanostructures

(Graphene, Nanotubes and
fullerenes)

Carbon Atomic Orbitals

Carbon is the 12th most abundant element.
Average atomic weight 12.011 amu.
Electronic congura)on: 1s22s22p2

S. Thompson and J. Staley. Orbitals and Molecular Representation, Orbitals.pdf.

Carbon: Hybridized Orbitals

There are four valence electrons.
The 2s and 2p can form hybridized orbitals.

S. Thompson and J. Staley. Orbitals and Molecular Representation, Orbitals.pdf.

Carbon: Hybridized Orbitals 2

Organic Chemistry: and bonds

Two side-to-side 2pz orbitals form a bond.
Two co-axial 2p or sp orbitals form the bond.

McMurray and Fay. Chemistry 4th ed., Prentice-Hall, 2004.

Benzene: the delocalized bond

In a molecule the bond electrons are shared.
These delocalized electrons are the carriers

McMurray and Fay. Chemistry 4th ed., Prentice-Hall, 2004.

Andre K. Geim and K.S. Novoselov, The rise of graphene. cond-mat/0702595

Graphi)c Forms:

Graphene: A Honeycomb LaPce

Modied from: hRp://www.ewels.info/img/science/graphite Dr. Chris Ewels, Inst. of Materials

Graphene: A Honeycomb LaPce

- A atom
- B atom

Graphene has two atoms

per unit cell.

These two atoms for two
interlocking triangular
sub-laPces.

Modied from: hRp://www.ewels.info/img/science/graphite Dr. Chris Ewels, Inst. of Materials

Graphene: A Honeycomb LaPce

- A atom
- B atom

Graphene has two simple

edge geome)es.

The zigzag termina)on
involves only one sub-
laPce site.

The armchair termina)on
involves both sub-laPce
sites.

Modied from: hRp://www.ewels.info/img/science/graphite Dr. Chris Ewels, Inst. of Materials

Types of Graphene:
Theore)cal graphene (1947 -present)
Mechanically exfoliated/cleaved graphene
(1997-2004)
Epitaxially grown graphene (1986-2004)
Chemically exfoliated and intercalated
graphene (c.1980-2004)
Chemical decomposi)on graphene (1997-s)ll
under development)

Graphene: Unit cells

 Graphene: ab ini)o band structure

At low energies there are
only two bands the
bands that arise from the
weak bonding between
the 2pz orbitals.

The Simple Two Band Model (STB)

Bloch wavefunc)ons in the simple two band model

2pz orbitals

The Hamiltonian matrix is generally dened as

and here this becomes for the Bloch eigenfunc)ons:

The overlap matrix: The secular equa)on:

A/B pseudospin label.

NN TBM
Explicitly from the matrix elements to lowest order:

where the transfer integral is

So going out to only nearest-neighbor contribu)ons give the matrices:

Solving the secular equa)on gives:

Second quan)zed form of the Hamiltonian out to nearest neighbors (NN):

NNs have opposite pseudospin

NN TBM t to low energy

FiPng the parameters to the low energy spectrum:

Dispersion:

Ideal Graphene Dispersion

Low energy is like a
massless 2D Dirac
model

There are only two

inequivalent points at
the vertex of the FBZ:
the K and K points.

Called valleys.

The low energy bulk
bands are near these
points.

Dispersion: http://www.ece.mcgill.ca/~ts7kop/images/graphene_lcao.jpg Dr. Thomas Szkopek, McGill University

NN TBM near K points

Expanding the momentum about the K points:
allows us to rewrite:
and approxima)ng
which yeilds:

So the low energy eec)ve Hamiltonian is a massless 2D Dirac equa)on:

chiral eigenstates

, ,

Proper)es of a Dirac spectrum

The number density is given by

The Fermi wavelength and free-electron radius

The density of states:

Graphene Ribbons

zigzag edge

armchair edge

Epoxy
glue

Epoxy
glue

Graphene synthesis

Freshsly cleaved
Bulk HOPG

Oxidized Silicon chip

Mechanical exfolia)on of bulk Graphite / HOPG

(1) Bulk HOPG
(upside G
down)
( scotch tape technique
) B(onding
Novoselov,
eim 2005)

Epoxy
glue
Ishigami et al. Nanolett. 2007

OPG
Graphene
on anything
(4) H
adhesive exfoliation
(3)
Bulk HOPG Scalpel Cleaving

(2) Epoxy glue curing u

Epoxy
glue

Epoxy
glue

Graphene synthesis

Freshsly cleaved
Bulk HOPG

Oxidized Silicon chip

Mechanical exfolia)on of bulk Graphite / HOPG

(1) Bulk HOPG
(upside G
down)
( scotch tape technique
) B(onding
Novoselov,
eim 2005)

Epoxy
glue
Ishigami et al. Nanolett. 2007

OPG
Graphene
on anything
(4) H
adhesive exfoliation
(3)
Bulk HOPG Scalpel Cleaving

(2) Epoxy glue curing u

Graphene synthesis
Mechanical exfolia)on of bulk Graphite / HOPG
( scotch tape technique )

Graphi)za)on of Silicon Carbide surface
by thermal annealing in UHV ( epi-graphene )

Only multilayers, No backgating

De Heer, C. Berger Georgia Tech

SiC is expensive and not at at all

1m

Multi-layers only

Graphene synthesis
Mechanical exfolia)on of bulk Graphite / HOPG
( scotch tape technique )

Graphi)za)on of Silicon Carbide surface
by thermal annealing in UHV ( epi-graphene )

Chemical synthesis (reduc)on of graphite oxide, full
synthesis, etc)







Graphene
liquid crystals, etc

J.Wu et al., Chemical reviews, 2007

Graphene synthesis
Mechanical exfolia)on of bulk Graphite / HOPG
( scotch tape technique )

Graphi)za)on of Silicon Carbide surface
by thermal annealing in UHV ( epi-graphene )

Chemical synthesis (reduc)on of graphite oxide, full
synthesis, etc)

Cataly)c Chemical Vapour Deposi)on

Principle of CVD Growth of NTs

Zhang et al., Appl. Phys. A 74, 325328 (2002) /

Principle of CVD Growth of NTs

PRL 95, 096103 (2005)

Cataly)c CVD

Cataly)c nanopar)cules -> Nanotube

Make Catalyst Flat and Clean -> Graphene ?

Seminal papers 1/2

In the early 90s it was found that graphi)za)on on surface was a by-
product during CVD growth of Diamond lms

Graphite is normally found on any surface (ceramic, Glass) at 2770K , The
eect of the catalyst (Ni, Fe, Pt etc) is to lower the temperature of
Growth and to allow beRer control of the kine)cs / self limi)ng the
reac)on

TEM investigation of CVD graphite on nickel

Ann-Sofie Johansson , et al Thin Solid Films, 252
(1994) p19-25

Seminal papers 2/2

Ethylene on Pt at 1100K

Land T A, et al. Surface Science 264 pp.261-70 (1992).

STM inves)ga)on of single layer graphite

structures produced on Pt(111) by
hydrocarbon decomposi)on

Moir eect

Land T A, et al. Surface Science 264 pp.

261-70 (1992).

STM studies of CVD Graphene

 250 nm wide STM image

Carpet on stair

graphene monolayers grown by low-pressure CVD of

ethylene on hot Ir(111) are fully coherent over step
edges on scales larger than micrometers.

Large Area, Few-Layer Graphene Films on

Arbitrary Substrates by Chemical Vapor Deposi@on
Alfonso Reina, Xiao)ng Jia, John Ho, Daniel Nezich, Hyungbin
Son, Vladimir Bulovic, Mildred S. Dresselhaus, and Jing Kong
Nano Le8., 2009, 9 (1), 30-35 MIT (Boston)

Continuous film, 1-12 graphene layers , up to 20m lateral size

TEM study

Mobility 100-2000 cm /V.s

Let s go Fishing ?

PMMA Transfert on any substrate

Summer 2009 Graphene on Copper

CVD growth on Copper

 Copper Madness

Analy)c Solu)ons for Graphene Ribbons

Analy)cs must apply the appropriate boundary condi)ons to the physically
signicant wavefunc)on along the edge. So the structure at the edge is
important here.

The eigenvectors sa)sfy the eigenvalue equa)on:

Can treat the problem on a semi-innite sheet or as a nite sized

nanoribbon.

Armchair Graphene Ribbons

The boundary condi)on becomes:

which mixes the valley components.

The eigenvectors that sa)sfy the BCs are

And the nite width gives the quan)za)on condi)on to be

Armchair Graphene Ribbons 2

Armchair nanoribbons can be metallic or
semiconduc)ng.

Zigzag Graphene Ribbons

A laPce approach is beRer for zigzag ribbons using the discrete coordinates J =1...N
labeling the zigzag chains instead of the y of a con)nuum model. The boundary
condi)ons for a ZGNR with A sites at the J=1 edge are applied on non-physical site
rows:

Then by aRaching amplitudes to the A sites on a semi-innite laPce, we nd

that for the = 0 states:

Zigzag Graphene Ribbons 2

So the semi-innite eigenvector for J>0 is

These states are the at-band edge states found in zigzag ribbons:

N = 76

Ground State of zigzag edge states

There is s)ll an open ques)on about the ground state
of the zigzag edge states when including interac)ons.
The consensus is that it will be magne)c and
probably in a an)ferromagne)c congura)on with
opposite spins along each edge.
We are studying the interac)on Hamiltonian
on the laPce:

where for the operators we use the FT of the at-band states:

Normaliza)on factor

Ground State of zigzag edge states 2

The FT of a at-band solu)on. The asympto)c fall-os have a power-law
decay

If we take

The TBM gives for the E=0 states:

Ground State of zigzag edge states 3

The Hubbard U term can be rewriRen as

which can be evaluated exactly when using the at-band wavefunc)ons:

We are endeavoring to also solve the Coulomb term in a

similar way. If this could be done, then we would be able to
project the interac)on term on the subspace of zero energy
states and diagonalize exactly. In so doing we could solve the
ground state of the edge states bands for semi-innite zigzag
ribbons.

Magne)c elds in graphene ribbons

An external magne)c eld can be added via the Peierls subs)tu)on

For a perpendicular magne)c eld the Hamiltonian becomes

The eigenvectors for this Hamiltonian are

Shon and Ando, JPJS (1998) ; Zheng and Ando, PRB (2002)

Magne)c elds in graphene ribbons

where
cyclotron mass

where
Also, we observe that the h-1 term in the LLL is non-vanishing and somewhat
like an exponen)al. We propose the solu)on

Magne)c elds in the TBM of ribbons

The Peierls subs)tu)on transforms plane-wave wavefunc)ons like
and the ux quantum is

The TBM, generally speaking, deals with electrons hopping

from site i to site j. Let us say that the position of site i is Ri,
that of site j is Rj and thus the hopping vector is R = Rj Ri. So
to add a magnetic field to a nanoribbon calculation requires for
each TBM hopping term the additional phase factor:

For an armchair nanoribbon:

Saito, et. al. Physical Properties of Carbon Nanotubes (1998).

Magne)c elds in the TBM of ribbons

the h-1 term

The LLL (n = 0) wavefunc)on amplitude in an armchair ribbon near

the K point with B = 100 T.
For an zigzag nanoribbon:

Magne)c elds in zigzag ribbons

The LLL (n = 0) dispersion and wavefunc)on amplitude in

an N = 76 zigzag ribbon with B = 0 T.

Magne)c elds in zigzag ribbons

The LLL (n = 0) dispersion and wavefunc)on amplitude in

an N = 76 zigzag ribbon with B = 50 T.

Magne)c elds in zigzag ribbons

The LLL (n = 0) dispersion and wavefunc)on amplitude in

an N = 76 zigzag ribbon with B = 100 T.

Magne)c elds in zigzag ribbons

The LLL (n = 0) dispersion and wavefunc)on amplitude in

an N = 76 zigzag ribbon with B = 150 T.

Magne)c elds in zigzag ribbons

The LLL (n = 0) dispersion and wavefunc)on amplitude in

an N = 76 zigzag ribbon with B = 200 T.
Note: the bulk and edge solu)ons seem to coexist in the LLL of zigzag ribbons.

Gap causing terms

A/B sublaPce asymmetry
This eec)vely adds a mass to the Dirac equa)on, so that
we have that

K to K scaRering
Quantum connement
Spin-orbit coupling

Intrinsic Spin-Orbit Coupling

In general spin-orbit coupling is dened as:
Intrinsic spin-orbit (ISO) coupling is between the electrons and the atomic nuclei on
the laPce sites, so the above becomes:

In the simple two band model, intrinsic SO is an eec)ve NNN term:

spin Pauli matrix

where ij = +1/-1 for le{(right)-hand

turns along the laPce. Near the K points
this reduces to the gap causing term:

Rashba Spin-Orbit Coupling

In general spin-orbit coupling is dened as:
In a purely two-dimensional form, this can be rewriRen in as the Rashba spin-orbit
(RSO) interac)on:

And usually one has that

In the simple two band model, Rashba SO is an eec)ve NN term:

which near the K points the lowest order contribu)on is:

The analy)c solu)on of edge states in graphene

with spin-orbit coupling
We nd analy)c solu)ons for zigzag edge states from
the )ght binding model with intrinsic spin-orbit
coupling.
Using an analy)c con)nuum theory (a Dirac-like
model) we nd solu)ons for armchair edge states
with both intrinsic and Rashba spin-orbit couplings.
We will briey discuss the rela)onship between the
existence of edge states and the topological numbers
of the bulk bands.

Graphene Edges and Ribbons

Take the ribbon length as
innite. Applying Blochs
theorem gives Bloch plane-
waves in that direc)on.
Using a )ght binding model
numerics of ribbons are
constructed from rectangular
unit cells with four atoms.
Analy)cs must apply the
appropriate boundary
condi)ons to the total
wavefunc)on along the edge.
Can treat the problem on a
semi-innite sheet.

Nearest Neighbor Tight Binding Model (NN

TBM)
spin Pauli matrix

Gap inducing terms

The nearest neighbor hopping: t0 = - 2.7 eV

A/B pseudospin

The intrinsic spin-orbit coupling:

Pauli matrix

An onsite sub-laPce poten)al dierence: m

Neglect conven)onal spin-independent NNN hopping.
Where ij is +1( -1) for carriers that make a LH(RH) turn as j -> i.
Introduced by:
Popularized by:

F.D.M. Haldane, PRL 61, 2015 (1988).

C.L. Kane and E.J. Mele, PRL 95, 226801 (2005)

ZIGZAG: 38 unit cells @ 18 nm

= 0.0 eV

m = 0.5 eV

Zigzag Edge States: m

Dispersionless edge states. Graphene ribbon is semiconductor.

ZIGZAG: 38 unit cells @ 18 nm

= 0.5 eV

m = 0.0 eV

Zigzag Edge States:

Current carrying edge states in the gap. They go far from K points.
QSHE:

C.L. Kane and E.J. Mele, PRL 95, 226801 (2005)

ZIGZAG: 38 unit cells @ 18 nm

= 0.5 eV

m = 0.0 eV

Zigzag Edge States: and m

Discrete y-coordinate

Ansatz:


Use the discrete
Schrdinger eqn. to solve
the semi-innite problem.
Dispersion (, m << t0) for
spin-up right movers:

where pxa is measured from .

= 0.00 eV
= 0.25 eV
= 0.50 eV

ZIGZAG:

From the discrete TBM:

By Cramers rule:

which gives the rela)onship between the energy and the eigenvalues z:

ZIGZAG:

Keeping up to second order in and m, we nd the physical solu)ons localized near

J=0 as

with unnormalized eigenvectors:

General edge state:

The requirement of the BC at J=0
again allows us to use Cramers
rule:
which yields for spin up right movers:

ZIGZAG: 38 unit cells @ 18 nm

= 0.5 eV

Zigzag Edge States: and m

Discrete y-coordinate

Ansatz:


Use the discrete
Schrdinger eqn. to solve
the semi-innite problem.
Dispersion (, m << t0) for
spin-up right movers:
= 0.5 eV
m= 0.5 eV

where pxa is measured from .

2D Dirac Equa)on
At low energy the TBM is eec)vely described by a
massive con)nuum 2D Dirac model:

8-spinor

With the dispersion of the bulk bands:

valley index

Where s =+(-) for spin-up(down) and = +(-) labels the valleys.

The low energy armchair edge state bands are in the valleys.
So they are described well by the con)nuum Dirac model.

ARMCHAIR: semi-innite

Armchair Edge States: Dirac Solu)on

The unnormalized wavefunc)ons:

The contraints for a semi-innite system

Eigenvalue Problem:

8 constraints

Vanishing Amplitude: + 8 constraints

Total real constraints 16 constraints

Gap closes when m ;

the dispersion of edge state bands is

where r =+1(-1) for right (le{) movers;

ARMCHAIR: semi-innite

(m = 0)

Armchair Edge States: Rashba Solu)on

Include Rashba spin-orbit coupling:
The semi-innite dispersion is

The unnormalized wavefunc)ons (m=0):

Find two inverse localiza)on lengths:

25 unit cells
40 unit cells
67 unit cells

ARMCHAIR: nite size

(m = 0)

Armchair Ribbons: Rashba Solu)on

The unnormalized wavefunc)ons (m = 0), where x = 0 is at the center of the ribbon:

Rashba induces a polariza)on near

the ribbon edges that can oppose
the localiza)on at the edge due to
intrinsic SO.

Gap closes and no edge state solu)ons

exist when ;

= 0.2 eV
= 0.1 eV

BULK: innite plane

(m = 0)

Topological numbers

The 2D bulk dispersion:

The Berry Curvature:

There contribu)ons from near other

crystallographic points.
Without Zeeman spliPng, the Z2
topological number is the
characteris)c topological number of
the system with Rashba spin-orbit
coupling.

Conclusion and Outlook

Some progress made in calcula)ng the ground state
of interac)ng zigzag edge states.
We found analy)c solu)ons for zigzag and armchair
edge geometries in the presence of spin-orbit
couplings and checked them with numerics.
When armchair ribbons are topological insulators yet
can be described by an eec)ve low energy theory.
Would be interes)ng to do these calcula)ons in
bilayer graphene.