The many forms of carbon

Carbon is not only the basis of life, it also provides an

enormous variety of structures for nanotechnology.
This versatility is connected to the ability of carbon
to form two stable bonding configurations (sp
2
, sp
3
)
with different bond geometry (planar, tetrahedral).
sp
2
sp
3
+
p
z
t-bonds
o-bonds
o-

and t-

bonds
t-bond:
o-bond:
o

orbital
t-orbital
(bonding)
o* orbital
t*-orbital
(antibonding)
+
-
Fullerene
0D
Graphite, Graphene (= single sheet)
2D
sp
2
Diamond
3D
sp
3
Nanotube
1D
2D: Graphene, a single sheet of graphite
2010 Nobel Prize in Physics
to Geim

and Novoselov
A graphene

sheet can be
obtained simply by multiple
peeling of graphite with
sticky tape. A single sheet
is visible to the naked eye.
Graphene

is very strong,
has high electron mobility,
and provides a transparent
conductor with possible
applications in displays and
solar cells. The E(p) relation
is linear instead of quadratic.
Energy bands of graphite: sp
2

+ p
z
Brillouin
zone
-
I
M
K
E
Fermi
E
k
x,y
t
t*
p
z
sp
2
sp
2
s
p
x,y
Graphite is a semi-metal,
where the density of states
approaches zero at E
Fermi

.
The t-bands touch E
Fermi

only at the corners K of the
Brillouin

zone, while a free-

electron band would form a
Fermi circle.
o*
o
Two-dimensional t-bands of graphene
Occupied
Empty
E
Fermi
E [eV]
K I=0 M K
Empty
Occupied
k
x,y
In two dimensions one has the
quantum numbers E,

k
x,y

.
This plot of the

energy bands
shows E vertically and k
x

, k
y

in the horizontal plane.
Dirac cones

in graphene
A special feature of the
graphene

t-bands is the
linear E(k) relation

near
the six corners (K) of the
Brillouin

zone (instead of
the parabolic relation for
free electrons).
In a three-dimensional
E(k
x

,k
y
) plot one obtains
cone-shaped energy band
dispersions.
Topological Insulators
A spin-polarized version of a Dirac cone

occurs in topological insulators. These
are insulators in the bulk and metals at
the surface, because two surface bands
bridge the bulk band gap. It is impossible
topologically to remove the surface bands
from the gap, because they are tied to the
valence band on one side and to the conduc-

tion

band on the other.
Hasan

and Kane, Rev. Mod. Phys.
The metallic surface state bands
have been measured by angle-

and
spin-resolved photoemission (see
Lecture 19).
1D: Carbon nanotubes
Carbon nanotubes

are grown using catalytic metal clusters (Ni, Co, Fe,).
(Lecture 7, Slide 7)
Indexing of Nanotubes
armchair
n=m
zigzag
m=0
chiral
n=m
Circumference vector c
r

=m a
1

+ n a
2
Unwrap a nanotube

into planar graphene
Energy bands of carbon nanotubes:
Quantization along the circumference
Analogous to Bohrs quantization
condition an integer number of
electron wavelengths needs to fit
around the circumference of the
nanotube. Otherwise the electron
waves would interfere destructively.
This leads to a discrete number of
allowed wavelengths
n
and wave
vectors k
n
=2t/
n
along the circum-
ference.
Along the axis of the nanotube the
electrons cane move freely. One
gets a one-dimensional band for
each quantized state. The kinetic
energy p
2
/2m of the motion along
the tube is added to the quantized
energy level.
Density of states of a single nanotube
Calculated Density of
States D(E)

:
Each peak shows the
one-dimensional 1/\E
singularity at the band
edge (see density of
states in Lecture 13).
Scanning Tunneling
Spectroscopy:
dI/dV
I/V
1 for V 0
when metallic

D(E)
Two-dimensional

spectroscopy:
Measure both photon absorption (x-axis)
and photon emission (y-axis).
Distinguishing nanotubes

with different n and m
C
60
solution
in toluene
Buckminsterfullerene C
60
has the same hexagon +pentagon pattern
as a soccer ball. The pentagons (highlighted) provide the curvature.
0D: Fullerenes
Buckminster Fuller,
father of the geodesic dome
1996 Nobel Prize in Chemistry to Curl, Kroto, Smalley
Fullerenes with increasing size

Fewer pentagons produce less curvature.
Symmetry
Mass spectrum showing the
different fullerenes generated.
Plasma generation of fullerenes in
a Krtschmer-Huffman apparatus.
Production of fullerenes
Molecular orbitals of C
60
The high symmetry of C
60
leads
to highly degenerate levels. i.e.,
many distinct wave functions
have the same energy. Up to 6
electrons can be placed into the
LUMO of a single C
60
, making
it a popular electron acceptor in
organic solar cells.
The LUMO (lowest unoccupied
molecular orbital) is located at the
five-fold rings:
C
60
can be charged with up to 6 electrons
The ability to take up that many electrons makes C
60
a popular electron
acceptor for molecular electronics, for example in organic solar cells.
Empty orbitals of fullerenes from X-ray absorption spectroscopy
LUMO, located at the strained five-fold rings
C1s
core level
photon
t*
o*