pressure-induced phase transitions in nanomaterials a thermodynamics panorama denis machon
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Pressure-induced phase transitions in nanomaterials
A thermodynamics panorama
Denis Machon
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Combination of Pressure and size: A perfect cocktail
V. Swamy, Phys. Rev. Lett. 96, 135702 (2006)D. Machon et al. J. Phys. Chem C 115, 22286 (2011)
Pressure-size phase diagram: Interface Energy Impact on Phase Transitions
Stabilizing new materials by these combined effects
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Experimental set-up
Idea: At constant force, drastically reduce the surface
Diamond-anvils cell
+ Raman spectroscopy / X-ray diffraction
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Are we sure that the nanoparticles remain nano at high-pressure?
L. Saviot et al. J. Phys. Chem. C 116, 22043 (2012)L. Saviot et al. J. Phys. Chem. C 118, 10495 (2014)ZrO2 – 4 nm
Nanoparticles as an elastic sphere
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G
PPbulk Pnano
lp
hp
lpG ,0
hpG ,0
r
V lplpm 0..3
r
V hphpm 0..3
First size effect in the literature: shift of the transition pressure
First size effect in the literature: shift of the transition pressure
S.H. Tolbert & A.P. Alivisatos, J. Chem. Phys.102, 4542 (1995)S. Li et al., Scripta Materiala 59, 526-529 (2008)
D. Machon & al. Nanoletters 14, 269 (2014) D. Machon & al. PCCP DOI: 10.1039/C4CP04633A
γ0: interfacial energy
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An Alternative description: Landau theory of phase transitionAn Alternative description: Landau theory of phase transition
Shift of the transition line:
the surface energies are considered as secondary order
parameter
D. Machon & al. Nanoletters 14, 269 (2014)
²..² 40
S
VFF lphp
Coupling term
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How is defined the transition pressure?
width of the transition
Shift of the transition? Spreading of the transition?
Only a size-effect? Other factors?
High defect density
W-ZnO
r-ZnO
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Strong dependence on the interface energy (surface state)Strong dependence on the interface energy (surface state)
Example: 7-nm particles of Y2O3
Sample B
Sample A carbonates
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Exposed to airArgon Atmosphere
(Loaded in glove box)
Amorphization Polymorphic transition
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Defects
sizePressure
Pbulk Pnano
Gbulk
Gnano
Gnano+defects
Gibbs energy
Pressure
Cubic
Hexagonal
Energizing processes
defects, interfacial and elastic energies
Multidimensional phase diagrams(surface-related effects)
L.Piot & al. J. Phys. Chem C 117, 11133 (2013)D. Machon & P. Mélinon, PCCP DOI: 10.1039/C4CP04633A
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The case of ZnO nanoparticlesThe case of ZnO nanoparticles
Size control: D ~ 16 - 20 nm (TEM, XRD)
Influence of the surface state
Samples from different synthesis routes
Approach:
PT theory ~ 13 GPa
Analysis of the surface state
(Luminescence, Raman, …)
1) LECBD (Physical method)Defect-free
2) Sol-gel
3) Hydrothermal
4) Polyol
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200 300 400 500 600 700 800
5.1
16.9
12.810.49.5
0.1
3.3
1.9
8.5
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
1.0
P (GPa)
Sample 1
200 300 400 500 600 700 800
5.4
16.5
14.5
12.9
12.0
10.3
3.0
9.5
Inte
ns
ity
(a
rbit
r. u
nit
s)
Raman Shift (cm-1)
0.1 1.0
7.7
P (GPa)
end
start
w
RS
Sample 2
100 200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
16.0
14.6
11.3
10.2
9.2
7.4
5.2
2.9
1.0
0.1
P (GPa)
Sample 3
200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
8.2
0.1
3.1
5.0
11.9
14.5
10.1
16.7
P (GPa)
Sample 4
200 300 400 500 600 700 800
5.1
16.9
12.810.49.5
0.1
3.3
1.9
8.5
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
1.0
P (GPa)
Sample 1
200 300 400 500 600 700 800
5.4
16.5
14.5
12.9
12.0
10.3
3.0
9.5
Inte
ns
ity
(a
rbit
r. u
nit
s)
Raman Shift (cm-1)
0.1 1.0
7.7
P (GPa)
end
start
w
RS
Sample 2
100 200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
16.0
14.6
11.3
10.2
9.2
7.4
5.2
2.9
1.0
0.1
P (GPa)
Sample 3
200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
8.2
0.1
3.1
5.0
11.9
14.5
10.1
16.7
P (GPa)
Sample 4
Low Energy Cluster Beam DepositionDefect-free nanoparticles
(checked by luminescence)
Hydrothermal synthesis
Transition to the rocksalt structure Start 8.5 GPaEnd > 10.4 GPa
Transition to a disordered structureStart 9.2 GPaEnd > 11.3 GPa
Bulk: start 8.5 GPa, end < 8.9 GPa (F. Decremps et al. PRB 65, 092101 (2002))
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Summary
4 different samples = 4 different pressure-induced behaviours
Size effect: spreading of the transition
LECBD Sol gel Hydroth. Polyol
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Ginzburg-Landau theory
²..² 40
S
VFF lphp
Thermodynamics
Kinetics
Master equation to describe 1) polymorphic transition2) Amorphization
)²)(( int pressureerfacedipolar KKK
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Spreading of the transition
Ginzburg-Landau: Polymorphic transition
2/1K Width of the transition
D. Machon & al. Nanoletters 14, 269 (2014)
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Ginzburg-Landau: Amorphization
0
2/1
0
2/1
0
)( rr
CCK
r NN
Radius of the amorphous region
CN : defect concentration at which the amorphous embryo nucleates
rCCc
0 critical concentration for merging of amorphous embryos
2/1KrN
P. Tolédano & al. J.Phys.: Condens. Matter 17, 6627 (2005).D. Machon & P. Mélinon, PCCP DOI: 10.1039/C4CP04633A
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Polymorphism: 2/1K
2/1KrN Amorphization
Slowing down
Favorable
pressureerfacedipolar KKKK int
Dipolar interaction (ZnO is non-centrosym.)
Surface state (defects, capping, etc)
Hydrostaticity
Sample Experiment
Amorphous state is kinetically favoured state
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Conclusions
Interface energy impact on the phase transitionsInterface energy impact on the phase transitions
Behavior at high pressure: a quality control test for the nanoparticles
Point defects, capping moleculesPoint defects, capping molecules
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Acknowledgments
Sylvie Le Floch, Patrice Mélinon, Dimitri Hapiuk
Lucien Saviot, Frédéric Demoisson, Romain Piolet, Moustapha Ariane
Samir Farhat
Stéphane Daniele
Bruno Masenelli
Nanotek organizers
Thank you for your attention
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Nanoparticles LECBDFree-defect (out of equilibrium)
Annealing400K
Defect density(equilibrium)
200 300 400 500 600 700 800
5.1
16.9
12.810.49.5
0.1
3.3
1.9
8.5
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
1.0
P (GPa)
Sample 1
200 300 400 500 600 700 800
5.4
16.5
14.5
12.9
12.0
10.3
3.0
9.5
Inte
ns
ity
(a
rbit
r. u
nit
s)
Raman Shift (cm-1)
0.1 1.0
7.7
P (GPa)
end
start
w
RS
Sample 2
100 200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
16.0
14.6
11.3
10.2
9.2
7.4
5.2
2.9
1.0
0.1
P (GPa)
Sample 3
200 300 400 500 600 700 800
Inte
ns
ity
(a
rb.
un
its
)
Raman Shift (cm-1)
8.2
0.1
3.1
5.0
11.9
14.5
10.1
16.7
P (GPa)
Sample 4
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Conclusions
Different approaches,
Similar results
Interfacial energy impact on the phase transitionsInterfacial energy impact on the phase transitions
Describe the spreading of the transition
ThermodynamicsThermodynamics
Kinetics: Ginzburg-Landau theoryKinetics: Ginzburg-Landau theory
Competition between polymorphic transition and Amorphization
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No PTM PTM: Methanol/Ethanol
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23
Laser YAG pulsé
He + O2
cible
buseDétente supersonique
Évaporation
de matrice
XPS-AES
Cathodo -luminesce
nce
UHV
Synthèse LECBDSynthèse LECBD
23
LECBD (Low Energy Cluster Beam Deposition), D ~ 16 nm (DRX, MET), stœchiométrie contrôlée
Principales caractéristiques:
Ablation laser
Vitesse de trempe (gaz porteur et détente adiabatique) → synthèse hors équilibre thermodynamique
Surpression en O2 pré-déposition
Voies de synthèses (physique)Voies de synthèses (physique)
Plateforme Plateforme
PLYRAPLYRA