Santhosh.18cool@gmail.

com submitted on 25-04-2015

Electronic structure of CuMO2

where M=Al, Ga, Y - An Ab Initio study

Indian Institute of Science, Bangalore

MR308 course project

Advisor: Abhishek singh
MRC dept.
Chittipolu Santhosh kumar
M.Tech CeNSE
SR no: 05-16-00-10-51-14-1-11290

[email protected] submitted on 25-04-2015

Abstract: In this study the electronic band structure of CuAlO2 (delafossite structure) using
GGA approximation in quantum espresso (QE) along -X-K--L bands has been calculated.
We also find the lattice constant and bond length between Cu-O and Al-O in angstrom unit.
The Fermi level was found to be 0.11 eV by plotting density of states (DOS) using QE. The
total energy was found to be -83.27560907 Rydberg (Ry) by keeping kinetic energy cut-off at
12 Ry and kgrid at 8x8x8.
Introduction:
Transparent conducting oxides (TCOs) are electrically conductive and optically transparent to
EM waves in the visible spectrum ranging from 380 nm to 750 nm (photon energy of 3.262 eV
to 1.653 eV). So, to be transparent, the bandgap of the material should be greater than the
energy of the incident photon, i.e., greater than 3.262 eV for 100% transparency. To conduct
electricity, electron-hole pairs must be generated and this happens for incident photon energy
greater than the band gap. This means a wavelength less than that of visible radiation, and thus
falls in the UV region of the spectrum, ranging from 100 nm to 400 nm. So, TCOs are now
defined as optically transparent oxides (which transmits visible light) in which electricity is
generated due to the absorption of ultraviolet photons. Layers of these oxides are prepared by
thin film technologies. The first transparent conducting thin films were of cadmium oxide
(CdO), synthesized in 1907 by Badekar. These films are prepared by thermal oxidation of
sputtered films of cadmium. The general form of TCOs is AyBz, where the non-metal part B
consists of oxygen, in combination with different metals or metal-combinations, A. These can
be doped AyBz:D (D = dopant), with metals, metalloids or non-metals. Hence, metals can be
part of the compound itself A, or can be a dopant, D. Hence, there can be two types of TCOs
p-type & n-type. For example, indium tin oxide (ITO) is prepared using a solid solution of
indium(III) oxide - (In2O3) and tin(IV) oxide - (SnO2) with typically 90%wt In2O3, 10%wt
SnO2. It is transparent and colourless as a thin film, and yellowish to grey as bulk material. ptype doping of ZnO is technologically difficult but, for oxides of the delafossite structure, the
opposite is true. P-type TCOs are difficult to prepare because of the electronic structure of
metal oxides. This is because of the strong localization of holes (either by doping or due to
non-stoichiometry within the material) at the oxygen 2p levels or at the upper edge of the
valence band due to the strongly electronegative nature of oxygen, i.e., this localization is due
to the ionicity of metallic oxides. O 2p levels are far lower lying than the valence orbitals of
metallic atoms, leading to the formation of a deep acceptor level by the holes, i.e., the holes
have a high probability of being localized around the oxygen atoms. Hence, these holes require
high enough energy to overcome a large barrier height in order to migrate within the crystal
lattice, resulting in poor conductivity and low hole mobility.
Delafossite structure: The general form of delafossite structure is AMO2 where A= Pt, Pd,
Ag, or Cu and M a trivalent cation= Al, Sc, Cr, Fe, Co, Ga, Rh, In, La, Y, Pr, Nd, Sm, Eu, Tl
can be used as M. for TCO, A should have fully filled d-orbitals, which gives A=Cu.
Delafossite structure Cu atom is linearly coordinated with two oxygen atoms, forming OCu
O dumbbells parallel to the c axis. Oxygen in these OCuO units are also each coordinated to
three MIII atoms, oriented such that MIII- centered octahedra form MIIIO2 layers, which lie
parallel to the ab plane. Two alternative layer stacking are possible, resulting in a hexagonal
(space group P63/mmc) or rhombohedral (space group R3-mh) unit cell. Hexagonal is
considered in this study.

[email protected] submitted on 25-04-2015

Figure 1 Hexagonal Delafossite structure: The green, red, and blue spheres are MIII, O and Cu respectively

Calculations:
1. Bond length: The bonds lengths between atoms is shown below.
a) Cu-O:

Figure 2 Cu-O bond length 1.853

b) Al-O:

Figure 3 Al-O bond length 1.914

[email protected] submitted on 25-04-2015

Figure 4 Al-O bond length 1.914

c) Cu-Cu:

Figure 5 Cu-Cu bond length 5.883

2. Energy band structure calculation:

These calculations are done using QE with input file shown below
Input file CuAlO2.scf.in:
&CONTROL
calculation = "scf",
prefix

= "cualo2",

pseudo_dir = "./",
outdir

= "./",

/
&SYSTEM
ibrav

= 4,

celldm(1) = 5.349815,

[email protected] submitted on 25-04-2015

celldm(3) = 5.7,
nat

= 8,

ntyp

= 3,

ecutwfc

= 12,

/
&ELECTRONS
conv_thr = 1.D-6,
mixing_beta = 0.3D0,
/
ATOMIC_SPECIES
Cu 63.54

Cu.pbe-d-rrkjus.UPF

Al 26.9815385 Al.pbe-rrkj.UPF
O 16.00

O.pbe-rrkjus.UPF

ATOMIC_POSITIONS
Al 2.0000 2.0000 2.0000
Al 2.0000 2.0000 2.5000
Cu 2.3333 2.6667 2.2500
Cu 2.6667 2.3333 2.7500
O 2.3333 2.6667 2.0859
O 2.6667 2.3333 2.5859
O 2.6667 2.3333 2.9141
O 2.3333 2.6667 2.4141
K_POINTS {automatic}
888000

In the above input file PBE pseudopotential files are used which implies generalised gradient
approximation (GGA) has been considered. The atomic positions were obtained from crystal
maker software. The lattice constant = 2.831000384
and = 17.192967 ,
() = 12 . If we give above this value self-consistent will not be
achieved in QE. Kmesh 8x8x8. The energy obtained is -83.27560907 Ry
Unit-cell volume = 755.8259 3
Number of atoms/cell = 8

[email protected] submitted on 25-04-2015

Number of atomic types = 3
Number of electrons = 52.00
Number of Kohn-Sham states = 26
Kinetic-energy cut-off = 12.0000 Ry
Charge density cut-off = 48.0000 Ry
Convergence threshold = 1.0E-06.
Band structure is calculated for 28 bands along -X-K--L bands.

Figure 6 Energy band structure

The band gap was found to be 1.5 eV which is half of the actual bandgap of this material.
Hence this calculation underestimates bandgap.

[email protected] submitted on 25-04-2015

3. Density of states:

Figure 7 density of states (DOS)

The Fermi level obtained was 0.11 eV.

Observations:
parameter
Lattice constant a ()
c()
Direct Bandgap (eV) at
Indirect Bandgap (eV)
Cu-O bond length ()
Al-O bond length ()

obtained
2.831000384
17.192967
1.5
1.853
1.914

Experimental values
2.856
11.340
3.5
1.8
1.909
1.907

Applications: TCOs are being used extensively in the window layers of solar cells, as front
electrodes in flat panel displays (FPD), low-emissivity (low-e) windows, in electromagnetic
shielding of cathode-ray tubes in video display terminals, as electrochromic (EC) materials in
rear-view mirrors of automobiles, in EC-windows for privacy (so-called smart windows),
oven windows, touch-sensitive control panels, defrosting windows in refrigerators and
airplanes, invisible security circuits, gas sensors, biosensors, organic light emitting diodes
(OLED), polymer light emitting diodes (PLED), antistatic coatings, and cold heat mirrors.

[email protected] submitted on 25-04-2015

Conclusion: The delafossite structure is studied and its lattice constant and volume are
obtained. Energy band structure and density of states are calculated.
References:
1. Electronic Structure and Bonding in CuMO2 (M ) Al, Ga, Y) Delafossite-Type
Oxides: AnAb Initio Study by Antonio Buljan, Pere Alemany,* and Eliseo Ruiz
2. Understanding conductivity anomalies in CuI-based delafossite transparent
conducting oxides: Theoretical insights by David O. Scanlon,a Kate G. Godinho,
Benjamin J. Morgan, and Graeme W. Watsonb