Ab- initio calculation

A.Mauri, N.Castellani* , D.Erbetta

* Mi- Bicocca Student

Introduction
Ab initio calculations can be used to:
Determine material structural properties
Study defects in material
Study molecular dynamics in general (reactions, stoichiometry
etc)
Ab- initio can be applied to:
Crystalline material
Amorphous material
Ab- initio is a general identification for methods of a multi- body
Schrdinger equation solution:
Hatree- Fock
Density functional Theory (LDA, CGA, hybrid method)
Copyright 2008 Numonyx B.V.

Ab- initio calculations

A new time scale ..for electronics industries
Standard approach

KMC approach

Courtesy of: B.Civalleri

Copyright 2008 Numonyx B.V.

Used software
Most of the software for DFT are university- type (some of
them are not free of charge)
Most common software:
Quantum espresso (Theoretical school of Trieste SISSA)
CPMD, CP2K (ETH Zurigh_ _ > Parriniello)
VASP (univeristy of Vienna)
Ab- init (Catholique Un. of Belgium)
Gaussian (commercial tools)
.

Copyright 2008 Numonyx B.V.

Software and super- computing

All the previous sws require high parallization

super- computing resources
Our choice for super- computing is the ENEA
cresco platform: Numonyx- farm is not suitable
The CPMD software has been used as currently
simulator

Copyright 2008 Numonyx B.V.

Physical problem
The first applications is the study of Silicon nitride
amorphous used for charge trapping devices

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Pseudo- potential choice based on dimer

Dimers Si- Si, N- N- SiN has been study in a
isolated system
The dimer total energy
has been calculated to
test wave function cutoff
Functional chosen:
Functional tested:

Wave function optimization

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Geometrical optimization

Dimer energy v.s. distance

Minimum of vibration energies have

been calculated for the different dymer:
Si- Si: 2.359 A
N- N: 1.105 A
Si- N: 1.645 A

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Silicon nitride crystalline phase

Hexagonal Beta phase

Hexagonal Alpha phase

Crystal point group: c1

Crystal point group: c6h

Lattice par.: a= 7.753 , c= 5.618

Lattice par.: a= 7.606 , c= 2.909

Unit cell: 28 atoms

Unit cell: 14 atoms

N.Ruddlesen Acta Crystal. (1958) 11,465

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Silicon nitride super- cell

Hexagonal Alpha phase

Hexagonal Beta phase

Number of unit cells: 8

Number of unit cells: 16

Total atoms: 224 atoms

Total atoms: 224 atoms

Copyright 2008 Numonyx B.V.

G(r): beta phase

Implemented sw to calculate Pair

correlation function (i.e g(r)) from
CPMD output data
G(r) has been evaluated for beta
phase for different temperature
below the melting point

Copyright 2008 Numonyx B.V.

G(r): beta phase pbc

p.b.c off

p.b.c on

To test g(r) we increased the considered cell volume: at long distance

g(r) goes to 1 as expected
G(r) has been evaluated with and without periodic boundary conditions

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G(r): beta phase

F.Alvaretz,.. Solid state com.(2003) 127,483

The calculated distances between the first and the second neighbours are
in agreement with published data

Copyright 2008 Numonyx B.V.

RDF for beta phase

Implemented sw to calculate Radial

distribution function (i.e RDF) from
CPMD output data
RDF has been evaluated for beta
phase for different temperature
below the melting point (comparison
with literature data not meaningful)
T.Fukunaga,.. J.non.cystalline solid.(1987) 1119
Copyright 2008 Numonyx B.V.

Coordination number for beta phase

Implemented sw to calculate
coordination number (i.e CN) from
CPMD output data
CN has been evaluated for beta
phase for different temperature
below the melting point
The number of first neighbour is in
agreement with experimental data
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Crystal vibrations

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Angular distribution: beta phase

Implemented sw to calculate angular

distribution (i.e AD) from CPMD output
data
Comparison with experimental data is
available only for the amorphous phase

P.Kroll,.. J.non.cystalline solid.(2001) 238

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Bands: beta phase

R.Wang,.. Chin.Phys.Letters.(1993) 741

Implemented sw to calculate solid bands from CPMD output data

Comparison with experimental data are in good agreement

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Bands: alpha phase

R.Shaposhnikov,. , Phys.of the Solid states

(2007) 1628

Good agreement found also for the alpha phase

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DOS: beta phase

K.Tastumi,.. PRB (2002) 165210

R.Wang,.. Chin.Phys.Letters.(1993) 741

Implemented sw to calculate DOS (density of states) from CPMD output

data
Comparison with published data are in good agreement
Calculated band- gap: 4.33 eV
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DOS: beta phase

optimized

non- optimized

DOS as band structure depends of the optimized structure

We have performed the test on beta phase structure
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DOS: alpha phase

Calculated band- gap: 4.9eV

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Simulation of defects: Si vacancy

Calculation of the defects formation energy

We have estimated a
formation energy in a perfect
crystal for a silicon vacancy
of:

Ef

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= 3.1 eV

Crystal simulations
We have planned the following simulations for beta phase
MD at 900C and 1500C (..g(r), angular distribution)
MD of the liquid phase T> 1900C (..g(r), angular distribution)
Defects study in a perfect crystal (geometry optimization, energy formation
calculation):
Si vacancy
N vacancy
Si interstitial
N interstitial
Calculation of the structural factor?

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Amorphous simulations
We have planned the following simulations for amorphous phase
MD of the liquid phase T> 1900C (..g(r), angular distribution)
Study of Si and N diffusion in a liquid (sw for diffusion coefficient
calculations is already developed)
Quenched of the amorphous phase to generate defects

Copyright 2008 Numonyx B.V.