Band Structure Calculations Electronic and Optical Properties

Band Structure Calculations;
Electronic and Optical

Properties
Stewart Clark
University of Durham
Outline
• Introduction to band structures

• Calculating band structures using Castep
• Calculating optical properties
• Examples results
• Some applications
Band Structure Stewart Clark - University of 2

Calculations Durham
Band Structures
• Bloch’s theorem introduces a wavevector k.
• It can always be confined to the 1st BZ (any k
outside the 1st BZ can be mapped back into
it).
• The band index appears in Bloch’s theorem
because for each k there are many solutions.
H!n.k = En ,k !n ,k
This leads to a description of the energy levels of electrons
in a periodic potential in terms of a family of continuous
functions En,k.
This is the band structure of the solid.
Calculations Durham
Simple Methods
Free electrons give Using a basic basis set for the
parabolic bands wavefunctions improves
results slightly
In Castep we use an accurate plane wave basis set.

Calculations Durham
Calculating Band Structures
• After calculating the electronic structure of a material
we have the charge density n(r) , the potential V(r)
and hence the complete Hamiltonian:
1
H = " ! 2 + Ve "e [n(r )] + Vi "e [n(r )] + Vxc [n(r )]
2
n(r) ! V(r)

Calculations Durham
Algorithm
• Calculate self-consistent density and potential.
• For a chosen k-point in the band structure calculate it’s
eigenvalues and eigenvectors (wavefunctions) as follows:
• Start from random wavefunction.
• For the first band, calculate the search direction using self-
consistent potential.
• Assuming parabolic energy curve, step wavefunction
coefficients to bottom in given direction.
• Repeat previous two steps (using orthogonal search
direction) until no change occurs.
• For subsequent bands at this k-point, perform similar
process, ensuring the bands remain orthogonal to all
lower bands.
Calculations Durham
Castep Input Files
• Can control k-points used in band
structures by several cell keywords
- bs_kpoints_list
- bs_kpoints_path
- bs_kpoints_mp_grid
• Controlled by param keyword task
- task : BandStructure

Calculations Durham
Example: Silicon
%block lattice_cart task : BandStructure
2.7 2.7 0.0
2.7 0.0 2.7
0.0 2.7 2.7
%endblock lattice_cart
%block positions_frac
Si 0.00 0.00 0.00
Si 0.25 0.25 0.25
%endblock positions_frac
%block bs_kpoints_path
0.0 0.0 0.0
0.5 0.0 0.5
0.5 0.5 0.5
0.0 0.0 0.0
%endblock bs_kpoints_path
Symmetry_generate

Calculations Durham
Silicon Band Structure

Calculations Durham
Conventional Cell?
• Although the full set of levels can be described with
restricted k, it is often useful to allow k to range over
more of k-space.
• The set of wavefunctions and energy levels for 2
values of k differing by a reciprocal lattice vector K
are identical.
!n ,k + K (r ) = !n ,k (r )
En , k + K = En , k
By not using a primitive cell, the band structure contains redundant
information.
For each of the k=k+K we can map them back into the 1st Brillouin zone
of the primitive cell.

Calculations Durham
Non-primitive Cell

Calculations Durham
Density of States
• Many electronic properties depend on the electronic
structure throughout the whole Brillouin zone.
• A band structure usually shows the electronic states
along lines of high symmetry.
• Instead, we need to sample the whole Brillouin zone
in a method similar to the SCF.

Calculations Durham
Castep Input files
For DOS calculations, get regular sampling grid
using:
bs_kpoints_mp_grid : i j k
Plotting a DOS from k-points on high symmetry

lines (from bs_kpoints_path) is not correct

Calculations Durham
Example of DOS Calculation

Calculations Durham
Magnetic Materials
• By default CASTEP calculations are
non-magnetic
• All bands are doubly degenerate
• To release this constraint use either:
- spin_polarised : true
- nspins : 2

Calculations Durham
Magnetic Materials
• Can also set initial magnetic state (param file):
– spin : 3
• Can constrain spin (param file):
– spin_fix : 6
• Can initialise atom spin states (cell file):
%block positions_frac
Fe 0.0 0.0 0.0 MAGMOM= 0.25
Fe 0.5 0.5 0.5 MAGMOM=-0.25
%endblock positions_frac
(NB: MAGMOM to be obsolete in v4.1. Use SPIN
instead)

Calculations Durham
Magnetic Materials

Calculations Durham
Calculating Optical Properties

• task keyword in param file
- task : Optics
• In the cell file use one of
- optics_kpoints_list
- optics_kpoints_path
- optics_kpoints_mp_grid
• Calculation similar to bandstructure,
but optical matrix elements also
calculated
Calculations Durham
Optical Properties
• Properties include
- Reflectivity
- Absorption
- Refractive Index
- Dielectric Function
- Conductivity
• For
- Polarised light
- Unpolarised light
- Polycrystalline materials

Calculations Durham
BS Application – Band Offsets

• Heterojunctions are formed when two different types
of semiconductor are joined together.
• Heterostructures are used extensively in the
electronic (e.g. transistors) and optoelectronic (e.g.
LED’s) industry.

Calculations Durham
Calculating Band Offsets
• Knowledge of the band structures of the two
individual materials is not sufficient to
determine the band offset.
• Band energies are determined with respect
to the average potential in the solid.
• It is also necessary to perform a supercell
calculation to determine how the potentials
are lines up with respect to each other.

Calculations Durham
The Average Potential

• The potential can be averaged across the x-y planes
(junction normal to z).
• This is the microscopic average potential.
• The macroscopic average potential is calculated
over the period over the microscopic potential.
• The band structures are measured relative to the
macroscopic average.
z + # / 2 z ' + # '/ 2
1
V tot ( z ) = V tot ( z ' ' )dz ' ' dz '
## ' z "!# / 2 z '"!# '/ 2

Calculations Durham
Band Line-up Using Potential
( ) (
"E v = V totL + E vbmL # V totR + E vbmR )
Calculations Durham
An Example: FeSi2 on Si
Offset is 0.4eV – useful for LED’s and near-IR detectors

Calculations Durham
Applications - Surfaces
• We can also use the supercell method to calculate
the band structures of surfaces.
• The wavefunctions at surfaces decay exponentially
into the vacuum region.

Calculations Durham
Details of GaAs Surface
There is reconstruction of the

surface – this is calculated first.
A band structure of the supercell is
then used for the surface band
structure.
Surface supercell
Calculations Durham
The GaAs Band Structure
• K-points are chosen
using the surface
Brillouin zone.
• Many regions have a
continuous energy
spectrum, while gaps
still exist.
• The details of the
surface band structure
depend on the details
of the surface
reconstruction.

Calculations Durham
Applications - Orbitals
• In addition to the energy eigenvalues for a given
material, a band structure calculation also gives the
eigenvectors (wavefunctions) for any point in the
Brillouin zone.
• It should be noted that no proof exists which
confirms that the DFT single particle wavefunctions
generated here correspond to the many particle
wavefunction.
• However, the orbitals generated can lead to useful
physics and give further insight in the the nature of
the bonding in materials.

Calculations Durham
Example of DFT Orbitals
• Instead of summing up the squares of all the
wavefunctions from each electron, we can look at
each one individually.
• Each one will be the charge density for a Kohn-
Sham orbital.
• This gives a chemistry point of view!
• We can examine the electronic structure electron by
electron.
• Note: Kohn-Sham orbitals/one electron orbitals:
meaning is not necessarily well defined!

Calculations Durham
Example of Orbitals
Example shown is for LaMnO3 – a magnetic material.

Calculations Durham

Band Structure Calculations Electronic and Optical Properties

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Band Structure Calculations;

Electronic and Optical

• Introduction to band structures

Band Structure Stewart Clark - University of 2

In Castep we use an accurate plane wave basis set.

Band Structure Stewart Clark - University of 5

Band Structure Stewart Clark - University of 7

Band Structure Stewart Clark - University of 8

Band Structure Stewart Clark - University of 9

Band Structure Stewart Clark - University of 10

Band Structure Stewart Clark - University of 11

Band Structure Stewart Clark - University of 12

Plotting a DOS from k-points on high symmetry

Band Structure Stewart Clark - University of 13

Example of DOS Calculation

Band Structure Stewart Clark - University of 14

Band Structure Stewart Clark - University of 15

Band Structure Stewart Clark - University of 16

Band Structure Stewart Clark - University of 17

Calculating Optical Properties

Band Structure Stewart Clark - University of 19

BS Application – Band Offsets

Band Structure Stewart Clark - University of 20

Band Structure Stewart Clark - University of 21

The Average Potential

Band Structure Stewart Clark - University of 22

Offset is 0.4eV – useful for LED’s and near-IR detectors

Band Structure Stewart Clark - University of 24

Band Structure Stewart Clark - University of 25

Details of GaAs Surface

There is reconstruction of the

Band Structure Stewart Clark - University of 27

Band Structure Stewart Clark - University of 28

Band Structure Stewart Clark - University of 29

Example shown is for LaMnO3 – a magnetic material.

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