PH601, 23/10/2024
Carbon based nanomaterials
• Graphene (2D material) (2010)
• Carbon nanotubes (1D material) (1990)
• Buckminster fullerenes (0D material) (1970)
(Learning objectives: Structure, property and applications)
Structure of graphene
STM image of graphene
Interlayer separation is 0.34 nm
Crystal structures
A crystal structure consists of identical copies of the same physical unit,
called the basis, located at all the points of a Bravais lattice.
Bravais lattice (bigger hexagon)
{(4x1/4)+1}=2 atoms in primitive unit cell
Two dimensional rhombus
Complex lattice
Graphene lattice
1/3 contribution
3 atoms per unit cell
Graphene has both A-type & B-type atoms,
This illustration shows only one type of atom.
Each A-atom is surrounded by
3 B-atoms and vice-versa
Upper left Bravais lattice (bigger hexagon
with one atom at the center)
right
Upper right
Primitive unit cell :
Two dimensional rhombus
left lower left
Two atoms per unit cell,
one is A and one is B
lower right
Lattice constants, a1, a2,
(nearest neighbour distance
C=C, 0.142 nm)
A atoms & B atoms form sub lattices ; COMPLEX lattice
A-atom finds B-atoms at upper left, lower left, and right positions.
B-atom finds A-atoms at upper right, lower right, and left positions.
Concept of k-space is useful
in understanding the
properties of graphene
K-space looks abstract but mathematically it is much simpler
K-space is also called momentum space.
Note: Electrons are under the influence of periodic potential of the lattice in the
crystal, their momentum is called crystal momentum which is different from the
momentum of free electrons.
How graphene looks like in K-space?
Fourier transform is done to get the reciprocal space.
Again, hexagonal lattice and the primitive unit cell is also a parallelogram.
Achieved simply by rotating the direct lattice by 90 degrees.
But, the unit in the reciprocal lattice is 1/length, and it is a momentum space or state
space.
Dirac points
First Brillouin zone
Second Brillouin zone
The primitive unit cell is outlined by the dashed line. Another way of choosing the primitive
unit cell is the hexagon in the middle (called the first Brillouin zone). Obviously this zone is
more symmetric than the parallelogram, and the reciprocal lattice point is exactly in the center.
This lattice point is often set to be the origin of the coordinate system in the reciprocal lattice.
The area of the first, second Brillouin zones and the parallelogram (primitive unit cell) is the
same.
The six corners of the first Brillouin zone are called the Dirac points.
Dirac points
Six corners of the first Brillouin zone are called the Dirac points.
They are very important in graphene. Remember they are not
the reciprocal lattice points. They are just the corners of the
first Brillouin zone.
For mathematical simplicity, physical quantities are described
in the k space. Since the reciprocal lattice is periodical and all
the unit cells are equivalent, it is enough to study the physical
quantities or phenomena in the first Brillouin zone.
For example, when we calculate the electron energy band we
only need to do it in the first Brillouin zone.
(Quantum mechanics, tight binding approximation)
(from first principles numerical calculations)
To have an intuitive view of this relation, we need to plot it in k-space
The K-points (Dirac points) and band structure
E-k dispersion relation in the first Brillouin zone
The upper part is the conduction band
and the lower part is the valence
band.
these two bands are both for the π
electron of graphene
Out of 4 electrons in the outer
electron shell, 3 of them are sp2
hybridized and form σ bonds with
neighboring atoms. The 4th electron is
the π electron here.
π electron has higher energy and is
quasi free. It is shared among all the
carbon atoms in graphene, and is
responsible for graphene’s electrical
conductivity
The other electrons are not that
active and are more confined to their
own atoms. They do not participate in
conductivity.
E-k dispersion relation in the first Brillouin zone
For intrinsic graphene,
Fermi level is exactly at the place
where the conduction band meets the
valence band. There are in total 6 such
points (Dirac points).
6 Dirac points are evenly distributed in
the same plane, which is the surface
of the Fermi sea.
Graphene can be called semi metal or
semiconductor with zero band gap,
anyway, the band structure decides
that graphene is a conductor, because
if we regard the two bands as a whole,
then it is only half filled.
Dirac cone When the energy is not far away from
the Dirac points (±0.6 eV), this cone is
circular and the E-k dispersion is linear.
It is quite unique. In most materials,
the dispersion is parabolic.
The linear dispersion is very useful for
fundamental sciences and it is
responsible for many of graphene’s
extraordinary properties.
For example, why does graphene has
transparency of 97.7% and it is
universal for a very wide wavelength
range? The fundamental reason
behind this is the linear dispersion.
We know photons have linear dispersion too. Photons are relativity particles and their rest mass
is zero. As they can be described by similar mathematical equations, electrons in graphene
behave similar to photons, but at a much lower speed. That is, unusual properties of quantum
electrodynamics where relativity effects are relevant and can be observed without the need to
accelerate the particles close to the speed of light.
Graphene has a linear energy dispersion relation and this has led to this
formula. (using quantum electrodynamics)
Important: This linear relation is valid as long as the electron energy is not far from the Dirac
point. Therefore, the 97.7% transmittance is independent of the incident wavelength unless
the photon energy is too large so that the electrons that absorb this energy enter the nonlinear
dispersion regime.
Optical properties
Usually, TRANSPARENCY and CONDUCTIVITY are incompatible.
Graphene is one among those few materials that are both transparent
and conducting.
Graphene is transparent to a wide range of electromagnetic radiation
starting from infra red to ultra violet.
