nouvelle approche pour la simulation de la croissance monte ......sio2, hig-k (hfo2, zro2) si...

Nouvelle approche pour la simulation de la croissan ce de couches de matériaux réactifs : Monte Carlo cinétique à trajectoires d’atomes hyperthermiques

Anne HémeryckAlain Estève, Mehdi Djafari Rouhani,

Marie Brut, Georges LandaCloé Lanthony, Darius Djafari Rouhani

Collaboration expérimentale : Carole RossiCollaboration : Nicolas Richard

LAAS-CNRS

Feb. 2013 :624 persons work in LAASResearchers and Faculty Members: 501

91 CNRS researchers128 Faculty researchers 9 Associated Researchers30 Post-doc – 243 PhD Students

Engineers, Technicians, Admin Clerks (ITA): 123

LAAS is a CNRS unit located in Toulouse (France) associated withUniversité Paul Sabatier (UPS), Institut National des Sciences Appliquées de Toulouse (INSA),Institut National Polytechnique de Toulouse (INP),Institut Supérieur de l’Aéronautique et de l’Espace (ISAE)Université du Mirail (UTM) and Université Toulouse 1 Capitole (UT1)

various application domains such as aeronautics and space, telecommunications, transports, production, services, security and defense, energy management, healthcare, cyber security, environment and sustainable development.

Scientific Research in 8 main research areas 2 Transversal axes

ADREAM

ALIVE

Critical Infomation ProcessingNetworks and CommunicationsRoboticsDecision and OptimizationMicroNanosystems RF and OpticalNano-Engineering and IntegrationEnergy ManagementMicroNanoBio Technologies

Atomic Scale Modeling and Simulation for Micro, Nano and BioNano Technologies

Members: -2CR, 1MdC, 1DR, 1 Prof-1 doc, 1 PostDoc

� To develop models to address

• Nano Engineering for Biology, Health and Human Agin g

• Nano Engineering for Advanced Microsystems



Oxides (materials) encounteredin Microelectronics

SiO2, Hig-k (HfO2, ZrO2)

Si nanodotsGe condensation

SiGe, SiC oxidationsAl oxidation

Reactive materials(Al/CuO, AlNi, … SiO2)

BioTechnologies

SAMsvdW interactions

DNA Technologies(DNA assembled

Nanoparticles, Aptamers)

Biology, Health

β Amyloid DHFR

HIV-1 proteaseStructural Oncology

(Ras protein)







Characterizing biomolecular flexibility, docking (Collab. Stanford Univ., M. Levitt; INRIA, N. Redon)

�Development of original modeling approach - Static M odes Eur. Phys. J. E 28, 17 (2009)

�Structural oncology modelling and simulation platfo rm(SAMO RITC Project: RAS oncoprotein - Collab. Claudius Regaud Institute, G. Favre)

Providing a new expertise and modelling facilities to achieve physico-chemical characterization of oncomolecules

Objective• restoring Ras switching mechanism (GTP hydrolysis / GAP interaction)• preventing Ras from binding its effectors

Using Static Modes as a “probe” to:• Exploring Ras biomechanical properties• Screening of mutation impact• Proposing custom design modifications • Building a Static Mode databank • Authorizing end users to custom in silico experiments• Guide mutation experiments

Contact : [email protected]






BioTechnologies









Biology, Health

β Amyloid DHFR


(Ras protein)

DNA Nanotechnologies (bio/non bio interactions)

�Self-assembly and chemistry of DNA/surface andnanoparticles interactions

• Thiol or COOH DNA terminations on Au, Al, Cu surfaces and their oxides• Intrinsic DNA interactions on Au, Al, Cu surfaces and their oxides• Role of London interactions on DNA/Surface interactions

�Aptamer sensors (ANR VIBBnano)

• Impact of aptamer spacer termination on aptamer stability• Design of aptamer tweezers

APL 100, 163702 (2012)

AFM 22, 323 (2012)







BioTechnologies









Biology, Health

β Amyloid DHFR


(Ras protein)

Growth of reactive materialsKinetic Monte Carlo with Hot Atoms Trajectories

Context

�NanoEnergetic Materials


nEMHeat

Gas / PressureStimulus

Chemical species

2 Al + 3 CuO � Al2O3 + 3 Cu + ΔHWith ΔH = 21 kJ/cm3

Bimetallics: Al/NiThermites: Al / CuO

Compatible with technologies Integration towards “on a chip” nanoenergetics)

Context

�NanoEnergetic Materials


2 Al + 3 CuO � Al2O3 + 3 Cu + ΔHWith ΔH = 21 kJ/cm3nEMHeat

Gas / PressureStimulus

Chemical species

Al/CuO NLs ~ 50-100 nm/layer

Al/CuO NPs Ø ~ 50-120

nmAl/CuO NWs

Bimetallics: Al/NiThermites: Al / CuO

Compatible with technologies Integration towards “on a chip” nanoenergetics)

Technological & scientific Issue: interfacial premixi ng


� Called Barrier layers� Define final properties (stability,

reactivity, sensitivity, released Energy)

� Formation still not controlled during deposition process (and asymmetric)

� Final properties neither not mastered nor guaranteed







� Interfaces mastering = performances mastering







� Interfaces mastering = performances mastering

Process requires MODELING

NanoLayers requires ATOMIC SCALE


Preliminary studies on bimetallics Al/Ni

Composition x 0 1 0.5

0

-0.6

-0.4

-0.2

Em

ix (

eV)

EMix(x)=2.865 x2 − 2.865 x

SNi,i Vi + INi,j

SNi,i+1 + ViSNi,i + Vi+1

SAl,i+1 + Vi SAl,i + Vi+1

INi,i Ini,i+1


� Macroscopic 1D model of atomic mix according to chemical

kinetics

� Environment dependent rate equation formulation

� Mixing releases energy that translate into a temperature

increase

∆T=-∆E-dt × (Prad +Pconv )

3kb × ni

LAl( )+ni

LNi( )+ni

INi( )( )i

∑� Thermal part :Translate energy changesinto temperature changes

� Kinetic part : Time evolution 4 differential equations with RK4-5 scheme and a dynamic time step

k i = kBT

h× exp

−∆E i

kBT

� Energetic part : Link between composition and

energetic parameters (activation energies, rate constants &

released energy using DFT calcul.)

Esystem = E layer∑E layer = L Al( ) × EAl+ L Ni( ) × ENi

+ L Al( ) + L Ni( ) ( ) × EMix x( )+ I Ni( ) × E INi x( )+ V[ ] × EV x( )

Composition x 0 1 0.5

0

-0.6

-0.4

-0.2

Em

ix (

eV)

EMix(x)=2.865 x2 − 2.865 x


SNi,i Vi + INi,j

SNi,i+1 + ViSNi,i + Vi+1

SAl,i+1 + Vi SAl,i + Vi+1

INi,i Ini,i+1


JVST A 28, L15 (2010)JPCS 71, 130 (2010)JPCS 71, 125 (2010)

En review à JAP

0 200 400 600 800 1000

2400

2000

1600

1200

800

400

0

Times (µs)

Tem

pera

ture

incr

ease

(°C

)

� Ignition Temperature


� Layers composition


JVST A 28, L15 (2010)JPCS 71, 130 (2010)JPCS 71, 125 (2010)

En review à JAP

0 200 400 600 800 1000

2400

2000

1600

1200

800

400

0

Times (µs)

Tem

pera

ture

incr

ease

(°C

)

0 200 400 600 800 1000

2400

2000

1600

1200

Times (µs)

Sys

tem

Tem

pera

ture

(°C

)

3200

2800

3600

8000 100 150

2800

2000

1600

1000

Times (µs)

Sys

tem

Tem

pera

ture

(°C

)

3200

3600

2400

1200

50

� Influence [Vacancies] � Premixing layer Influence

T=800°C


� Layers composition� Defects: incoming from

deposition process� Premixing layer

� Impact on final properties�Process Simulation

� Ignition Temperature


� Multiscale Modeling of technological process (oxidation, vapor deposition)

Characterization,Process,

Technology…

DFTDFTUp to 200 atoms, Time scale: picoseconds

Local Mechanisms

KINETIC MONTE CARLOKINETIC MONTE CARLOUp to millions of atoms, Time scale: seconds

Material growth as a functionof temperature and pressure

XPS, AES, TEM, EDX …IR, STM

Structures, E ac

Growth phenomena

EXPERIMENTSEXPERIMENTS

Process Scale

Technology and modeling of reactive composite materi als and systems�Al-CuO nanolaminates: basic mechanisms of CuO/Al PV D growth through first principles calculations (DGA-REI funding)

•Mechanisms and energetics using DFT calculations of: • Al adsorption and penetration path on CuO • Dissociative chemisorption of CuO on Al (+ O, Cu separation)• Cu aggregation and penetration• Al extraction through oxygen exposure � Al oxidation• Partial order and orientation of grown alumina ultrathin layer

Al oxide after 2 ML of Oxygen atom deposition

J. Chem. Phys. 137, 094707 (2012)

Thin Solid Films 520, 4768 (2012)


Al on CuO

Cu on Al

O on Al

Technology and modeling of reactive composite materi als and systems�Al-CuO nanolaminates: basic mechanisms of CuO/Al PV D growth through first principles calculations (DGA-REI funding)

•Mechanisms and energetics using DFT calculations of: • Al adsorption and penetration path on CuO • Dissociative chemisorption of CuO on Al (+ O, Cu separation)• Cu aggregation and penetration• Al extraction through oxygen exposure � Al oxidation• Partial order and orientation of grown alumina ultrathin layer

Al oxide after 2 ML of Oxygen atom deposition

J. Chem. Phys. 137, 094707 (2012)

Thin Solid Films 520, 4768 (2012)


6.6 eV3.15 + 0.55 eV

5-8 eV

5.1 + 2.3 eV

Al on CuO

Cu on Al

O on Al


λm

= ν.exp −E

m≠

kBT

Arrhenius law derived acceptance

Transition state theoryMinimum energy pathalong a saddle point(transition state) ΔE

Δx

Em

Advance time by( )

mm

Zt

λlog−=

Eventsfiltering

Occurrence timesCalculation,

and Comparison

Pick next event, Atomistic config.

change

Limitation of conventional kMC

�No more valid when ‘reactive’ materials �� why?


λm

= ν.exp −E

m≠

kBT


Transition state theory

ΔE

Δx

Em

Local reactions involving atoms carrying extra energy

Q

Advance time by( )

mm

Zt

λlog−=

Eventsfiltering


and Comparison


change



Minimum energy pathalong a saddle point(transition state)


λm

= ν.exp −E

m≠

kBT


Transition state theory

ΔE

Δx

Em

KMC procedure no more valid when energetic particles are introduced

Energy release can not be neglected

New KMC approachCoupling motion of the energetic atom to the vibrational state of the system

Local reactions involving atoms carrying extra energy

Q

Advance time by( )

mm

Zt

λlog−=

Eventsfiltering


and Comparison


change



Minimum energy pathalong a saddle point(transition state)

0 5 10 15 20 25 30 35-8

-7

-6

-5

-4

-3

-2

-1

0

∆∆ ∆∆E (

eV)

Reaction coordinates

A

B

C

D

E

F

B

E

D

SILANONE

C

0.08 eV

7.29 eV

0.27 eV

2.21 eV

4.14 eV

A

F0.94 eV

[J. Chem. Phys. 126, 114707 (2007)]




�Hyperthermal module for the treatment of atomistic motions and mechanisms related to exothermic reactions


KMC Core

Final Time# max event

Classical Mechanisms List

Em, struct.

� Jump driven by activation barrier



KMC Core

Final Time# max event

Hot AtomClassical

Mechanisms ListEm, struct.

Mechanisms associated with Hot

Atoms, arrivals, energetic particles

Vibrational frequencies

..,)(/).(

,),(

ccpktu eeAtwtuki

pkpk

+= −−∑

τ

Each normal mode is defined by a vibration angular frequency ω and a reduced displacement vector

A pk ),( )(ou )(ov

� Coupling motion of the hyperthermal atom to the vibrational state of the system (phonons)

� trajectories

� Jump driven by activation barrier

=f( ),


• Validation on a 2D scheme coupled with analytical phonon description

Hyperthermal migration

and trapping of anInterstitial atom


KMC includes:

Migrations

Defect generation

One vacancy can be created

Only on the 4 nearest neighbour sites

Conclusions

� New methodology to deal with exothermic reactions i n kMC procedure

� Applications

� Mechanisms occurring in material oxidation (Si, Al)

� Deposition and ignition of nanostructured energetic materials, such as bimetallic (Ni/Al) or metal-oxide (CuO/Al) layers

� Creation of defects under energetic radiations effects (NIEL: Non Ionizing Energy Loss) as in electronic devices in harsh environments, particularly in spatial applications or subject to solar wind.


COCOA KMC

Thank you

Sujet de thèse proposé au LAAS-CNRS

� “ Vers une intégration optimisée des matériaux énergé tiques : Modélisation multi-échelles et multi-physiques de l a croissance de multicouches Al/CuO “

� A diffuser largement … Merci


nouvelle approche pour la simulation de la croissance monte ......sio2, hig-k (hfo2, zro2) si...

Documents