Doping induced effect on optical and band structure properties of
SrLiAl3N4[Eu+2] based Phosphors: DFT approach.
Dr. Sikander Azam
Riphah International University, Islamabad, Pakistan.
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Outline
Motivation
Predictive first principle methods
Results and discussion
• Electronic structure
• Linear Optical Properties
• Thermoelectric properties
Conclusions
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1) As of today, there is no general known method to predict the exact luminescence properties of
phosphors.
2) Therefore, one is inclined to rely on quantum chemical ab-initio calculations, which have shown
a great potential in recent years[2].
[2] Robin Alexander Niklaus, thesis on “Ab-Initio Characterization of Thermal Properties of Phosphor Host Lattices”.
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Motivation
Energy efficiency has become an increasingly important criterion for pervasive
products such as light sources. Replacing energy-wasting traditional light
sources such as incandescent lamps with energy-efficient LED lamps is
considered a major step towards reducing electrical energy consumption
worldwide.
The first studies on Eu2+-doped -M2Si5N8:Eu2+ (M=Ca,Sr,Ba) in 2000[1,2]
Leading to a commercial application in pcLEDs.
Resulting in numerous efforts to develop new high-performance phosphors.
SrLiAl3N4[Eu+2][3]
[1] H. A. Höppe, H. Lutz, P. Morys, W. Schnick, A. Seilmeier, J. Phys. Chem. Solids 2000, 61, 2001–2006.
[2] J. W. H. van Krevel, Dissertation, Eindhoven University of Technology, 2000.
[3] Philipp Pust, VolkerWeiler, Cora Hecht, Andreas Tücks, Angela [Link], Ann-Kathrin Henß, Detlef Wiechert, Christina Scheu, Peter J. Schmidt and
Wolfgang Schnick, Nat. Mater. 2014 (9) 891-6. 4
APW LAPW
DFT
[Link] [Link]
Electronic structure of
solids and surfaces
[Link], [Link], [Link],
hexagonal boron nitride on Rh(111)
Molecular physics, 108, 3147 (2010)
2x2 supercell (1108 atoms per cell)
Wien2k is used worldwide
[Link]. 98, 106802 (2007) by about 8000 groups
A few solid state concepts
Crystal structure
Unit cell (defined by 3 lattice vectors) leading to 7 crystal systems
Bravais lattice (14)
Atomic basis (Wyckoff position)
Symmetries (rotations, inversion, mirror planes, glide plane, screw axis)
Space group (230)
Wigner-Seitz cell
Reciprocal lattice (Brillouin zone)
Electronic structure
Periodic boundary conditions
Bloch theorem (k-vector), Bloch function
Schrödinger equation (HF, DFT)
Unit cell
Assuming an ideal infinite crystal we define a unit cell by
Unit cell: a volume in space that
c
fills space entirely when translated
by all lattice vectors.
The obvious choice:
a parallelepiped defined by a, b, c,
three basis vectors with
the best a, b, c are as orthogonal b
as possible
the cell is as symmetric as possible
(14 types) a
A unit cell containing one lattice point is called primitive cell.
The many-body problem
Task: Solution of Schrödinger equation (ground state)
Hamiltonian
NB:
● Born-Oppenheimer approximation has been used
● Mass of nuclei orders of magnitude larger than mass of electrons
Density Functional Theory
Hohenberg-Kohn theorem: (exact)
The total energy of an interacting inhomogeneous electron gas in the
presence of an external potential Vext(r ) is a functional of the density
E[n( )] Vext n( )dr F [n( )]
But F [n( )]
Kohn-Sham: (still exact!)
1 ( r ) ( r )
E To [ ] Vext ( r )d r dr dr E xc [ ]
2 | r r |
Ekinetic
Ene Ecoulomb Eee Exc exchange-correlation
non interacting
hom .
E LDA
xc (r) [ ( r )] dr LDA treats both, exchange and
xc
GGA correlation effects approximately
E GGA
xc ( r ) F [ ( r ), ( r )] dr
Exchange correlation functional
Standard LDA (GGA) gives good description of most solids
Problems:
Accuracy : functional “adapted” for specific materials or
properties
Solids - molecules; metals - insulators
Geometry - binding energies
“correlated” electrons: 3d transition metal oxides/halides , 4f,5f
e-
Band gaps in semiconductors/insulators
Gap typically underestimated
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Band structure method: APW method
unit cell 1 2 k
2 V ( r )
i i i
k k
Basisset: ul(r,) are the numerical solutions
PW: i ( k K ). r
e of the radial Schrödinger equation
join in a given spherical potential for a
Atomic partial waves particular energy
mu(r, )Ym (rˆ)
A
m
K AlmK coefficients for matching the PW
Crystal Structure
SrLiAl3N4[Eu+2]
Crystal symmetry, Triclinic
Space group (no. 2)
Lattice parameters (Å, °)
a = 5.86631(12), b = 7.51099(15), c = 9.96545(17),
α = 83.6028(12), β = 76.7720(13) and γ = 79.5650(14)
Exp., this material is synthesized by the group of W. Schnick[3].
Make the Super cell
Doped Eu, replaced Sr by Eu atom (25%)
[3] Philipp Pust, VolkerWeiler, Cora Hecht, Andreas Tücks, Angela
[Link], Ann-Kathrin Henß, Detlef Wiechert, Christina Scheu, Peter J.
Schmidt and Wolfgang Schnick, Nat. Mater. 2014 (9) 891-6.
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Calculation details
WIEN2k (FP-LAPW)
– relaxed geometry (GGA)
Shows close agreement with experimental value
– even though Eu is included, until now no SOC
– calculations with SOC are in progress
Electronic structure and optical properties calculated within GGA+U
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Program structure of WIEN2k
init_lapw
initialization
symmetry detection (F, I, C-
centering, inversion)
input generation with
recommended defaults
quality (and computing time)
depends on k-mesh and [Link]
(determines #PW)
run_lapw
scf-cycle
optional with SO and/or LDA+U
different convergence criteria
(energy, charge, forces)
save_lapw tic_gga_100k_rk7_vol0
cp [Link] and clmsum files,
mv [Link] file
rm [Link]* files
Flow Chart of WIEN2k (SCF)
Input n-1(r)
lapw0: calculates V(r)
Calculated the valance band
lapw1: sets up H and S and solves
the generalized eigenvalue problem
lapw2: computes the
valence charge density
lcore
mixer
no yes
converged? done!
WIEN2k: P. Blaha, K. Schwarz, G. Madsen, D. Kvasnicka, and J. Luitz
Workflow of a WIEN2k calculation
• individual FORTRAN programs linked by shell-scripts
• the output of one program is input for the next
• lapw1/2 can run in parallel on many processors
SCF cycle LAPW0
LAPW1
Iteration
LAPW0 3 %*
LAPW2
LAPW1 75 %
Iteration
LAPW2 20 %
SUMPARA
LCORE 1%
LCORE
MIXER 1%
MIXER
self
consistent? END self
no yes END consistent?
yes no
single mode parallel mode
k-point parallelization
* fraction of total computation time
w2web GUI (graphical user interface)
Structure generator
spacegroup selection
import cif file
step by step initialization
symmetry detection
automatic input generation
SCF calculations
Magnetism (spin-polarization)
Spin-orbit coupling
Forces (automatic geometry
optimization)
Guided Tasks
Energy band structure
DOS
Electron density
X-ray spectra
Optics
Spacegroup P42/mnm
Structure given by:
spacegroup
lattice parameter
positions of atoms
(basis)
Rutile TiO2:
P42/mnm (136)
a=8.68, c=5.59 bohr
Ti: (0,0,0) 2a
O: (0.304,0.304,0) 4f
Wyckoff position: x, x, 0
O
Ti
Quantum mechanics at work
thanks to Erich Wimmer
SrLiAl3N4---- Using GGA
Results and Discussion
Band gap is 2.94 eV
Indirect band gap----------- VBM occurs in between “R-T” while the CBM at “R”
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Band Structures--- for Eu+2 doped
GGA GGA+U
The band gap for GGA 2.91 eV, While for GGA+U is 2.98 eV
Indirect band gap----------- VBM occurs “T” while the CBM at “R”
This wide band gap material may be suitable in applications for high frequency UV devices.
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Density of states
•Now about some generalized picture of how density of states is quantized in this material.
•TDOS for SrLiAl3N4[Eu+2] Using GGA+U
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PDOS
An understanding of the PDOS is fundamental
because the optical spectra are directly derived from
interband transitions.
Partial density of states is the terms which refers to
number of possible states at certain energies.
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Electronic charge density
Charge density maps serve as a complementary
tool for achieving a proper understanding of the
electronic structure of the system being studied.
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Optical properties
1. Since the investigated compound has a triclinic symmetry so there are many
nonzero components of the dielectric tensor.
2. We will concentrate only on the major components, corresponding to an
electric field perpendicular and parallel to the C-axis.
3. We will use our calculated DOS and BS to identify the transitions which are
responsible for the spectral structures of the optical dielectric function.
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Dielectric functions
Anisotropy in epsilon, Ist peaks due to from VB (Eu-f) to CB (Eu-d or Sr-d)
The spectrum shows the anisotropic behavior between 4.0 to 10.0 eV.
It is significant to recognize that these peaks in
are not due to only transition from single band, but
numerous direct transitions are concerned which might be found in the BS.
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Other related optical properties
Absorption spectra Refractive index spectra
The Photoconductivity and electrical conductivity Crossing zero means the material becomes superluminal for high
increases as a consequence of absorbing photons energy photon
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Energy loss function
a. The electron energy loss spectroscopy is a valuable tool for investigating various aspects of
materials.
b. The energy-loss spectrum is related to the energy loss of a fast Electron traversing in the material
and is large at the plasma energy.
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Conclusion
We reported first principle study of electronic structure and electronic charge density
(within GGA+U).
Our calculated band structure semiconductor nature of the investigated material.
The linear optical properties like, real and imaginary part of dielectric constant,
reflectivity, absorption coefficient and energy loss function were calculated.
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OUTLOOK
– Eu doped system will be calculated by means of other codes
Spin-orbit coupling
Eu dopant is responsible for luminescence in this phosphors
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Collaborators
My guide Prof. Dr. Jan Minar (Germany)
Prof. Dr. Ondrej Sipr (Czech Republic)
Professor Dr. Xavier GONZE (Belgium)
Prof. Dr. Souraya Goumri-Said (Saudi Arabia)
Dr. Shabbir Muhammad (Saudi Arabia)
Prof. Dr. Rabah Khenata (Algeria)
Prof. Dr. Iwan Kityk (Poland)
Dr. Dibya R Prakash (India)
Dr. Wilayat Khan (Pakistan)
Dr. Saleem Ayaz Khan (Czech Republic)
So many other National and international
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