Density Functional Theory;

An Investigation into Effects of a Vacancy

Alayande Oluwaseun, Caroline Dylag, Claudio Lourenco
Communications ManagerUCL Communications and MarketingTel: 020 3108 3854   Ext:
Department of Chemistry - University College London
53854

Introduction
Computational methods are becoming an increasingly popular method to predict bulk and surface properties of
materials. As a result many materials can be theoretically modelled without the consumption of natural resources and
experimental methods. Moreover, variables can be applied to systems and controlled until an ideal material is
achieved. Results from such computer simulations can be verified with actual experimental results.
Computational methods have been applied to model and simulate semi conductive materials. Examples include band gap
determination from the Density of States (DOS) using Density Functional Theory (DFT). From this, the effect of
vacancy defects and doping on systems without extensive experimentation can be established.
In this study, MgO and CaO have been chosen as the selected metal oxides within group 2. The aforementioned
Aims
simulation methods have been performed to determine the band gaps of MgO and CaO. The effect of the vacancy defect
within both metal oxides will be compared. Figure 1 Metal oxide crystal structure

Determine and compare the band gaps of magnesium oxide and calcium oxide.
Determine the effect of including vacancy defects within the systems on the band gaps using DFT.

Methodology

•Periodic DFT calculations

•Prepare VASP input files (INCAR, KPOINTS and POSCAR. Download POTCAR file from the library for GGA calculations with the PBE functional)
•Check for convergence with the number of k points and optimize the geometry using the converged k point mesh.
•To calculate the electronic density of states, the INCAR file is changed to perform a single point calculation. The following lines are added:
#Density of states
LORBIT = 10 # Separate into s, p, d contributions
NEDOS = 1500 # Number of energy points in DOS plot
EMIN = -13 # Minimum energy in DOS plot
EMAX = 17 # Maximum energy in DOS plot
•The values are obtained by inspecting the position of the bands in previous calculations.
•To interpret the electronic structure, plot the DOS against E-Ef. This data can be found in the DOSCAR output files.
•The band gap can be interpreted from the resulting graphs, where the difference between the conduction and valence peaks is the band gap.
•The vacancy defects were added to the created supercells, for each metal oxide (MgO/CaO) simulation, an oxygen vacancy has been added. For
another simulation, a Mg or a Ca vacancy has been added respectively.

Results Discussion
Results for the converging structure at kpoints mesh By introducing a vacancy the total energy of the oxide supercell
5Species
5 5. Supercell Energy (eV) Band Gap (eV) increases meaning that the system becomes more unstable therefore
MgO -382.29 3.82 unlikely to occur naturally.
MgO (Mg vacancy) -372.84 4.16 This trend occurs with both oxygen and metal ion vacancies, with
MgO (O vacancy) -371.04 2.55
the oxygen vacancy showing the a greater increase in energy as
CaO -409.48 3.06 shown in Table 1.
CaO (Ca vacancy) -399.90 3.10
CaO (O vacancy) -398.44 0.74
We observed that the bands gaps obtained with this experiment are
much smaller that the experimentally determinate values. This can
Table 1 – Energies and Band Gap values.
be attributed to two reasons with the first one being the
approximations applied to the exchange correlation functional and
the second to a derivative discontinuity term, arising from the
discontinuity of the density functional with the total number of
electrons in the system. Overall, the band gaps computed using
the calculations within VASP tend to be around 40 – 50% narrower
than experimental values (Jain 2011, Jain et al 2011).

In comparing the band gap, distance between the top of the valence
band and the bottom of the conduction band, you can see that in
the bulk system the MgO band gap is larger than the CaO bulk band
gap. This makes Cao more of a semiconductor, whilst MgO is more
insulating because more energy is required to excite the electrons
Conclusion
into the conduction band.
Figure 2 - Density of states of CaO and MgO bulk supercell.
For both systems, when a defect is introduced into the system,
defect peaks appear in the DOS shown in Figures 2-4. The peaks
The
tendcomputational
to occur in theband gaps
band found
gap for the
because species
of the studiedof
periodicity were
the
3.82eV forzone.
Brillouin MgO and
Due3.06eV fordefect
to these CaO. This value
peaks, is lower
electrons than
can the
travel
experimental
between thesevalue asand
states expected, the experimental
the conductivity value
properties offor
thethe MgO
band gap is
material 7.80eV (Roessler and Walker, 1967) and 7.20eV for CaO
change.
(Jeanloz and Ahrens, 1980). The pattern for the experimental values
and the computational values show that in general, MgO has a larger
band gap. Hence, the values from the computer simulation can be
used as a guideline for experimental trends. The large difference
in the band gaps is due to the way in which VASP uses
approximations and the discontinuity term, explained above.
When a metal vacancy was introduced into the system, the band gap
increased slightly (MgO 3.82eV  4.16eV, CaO 3.06eV  3.10eV).
When an oxygen vacancy was introduced, the band narrowed and in the
Figure 3 - Density of states of MgO bulk supercell and MgO with a Mg and O vacancy respectively. case of CaO virtually disappeared (MgO 3.82eV  2.55eV, CaO 3.06eV
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