Investigation of the early stages of growth of nanostructured zirconia

produced by Supersonic Cluster Beam Deposition:

from sub-monolayer to thin film regime

Francesca Borghi

LGM laboratory - CIMaINa

Introduction Strategy & Methods Results and Discussion Conclusions

THIN FILMS

Introduction Strategy & Methods Results and Discussion Conclusions

THIN FILMS

Semiconductor technology

Introduction Strategy & Methods Results and Discussion Conclusions

THIN FILMS

Plasmonic nanostructures

Semiconductor technology

Introduction Strategy & Methods Results and Discussion Conclusions

THIN FILMS

Plasmonic nanostructures MC3T3-E1 cells cultured on

(A) as-machined and (B) Ti-coated PEEK

Semiconductor technology

Biomedicine

THIN FILMS DEPOSITION TECHNIQUES

Introduction Strategy & Methods Results and Discussion Conclusions

TOP-DOWN

THIN FILMS DEPOSITION TECHNIQUES

Introduction Strategy & Methods Results and Discussion Conclusions

TOP-DOWN

BOTTOM-UP

THIN FILMS DEPOSITION TECHNIQUES

Introduction Strategy & Methods Results and Discussion Conclusions

TOP-DOWN

BOTTOM-UP

ASSEMBLING

of PRECURSORS

from GAS PHASE

onto a SUBSTRATE

PHYSICAL VAPOUR DEPOSITION

(PVD)

CHEMICAL VAPOUR DEPOSITION

(CVD)

THIN FILMS DEPOSITION TECHNIQUES

Introduction Strategy & Methods Results and Discussion Conclusions

TOP-DOWN

BOTTOM-UP

ASSEMBLING

of PRECURSORS

from GAS PHASE

onto a SUBSTRATE

PHYSICAL VAPOUR DEPOSITION

(PVD)

CHEMICAL VAPOUR DEPOSITION

(CVD)

THIN FILMS DEPOSITION TECHNIQUES

Introduction Strategy & Methods Results and Discussion Conclusions

TOP-DOWN

BOTTOM-UP

BOTTOM-UP APPROACHES

Introduction Strategy & Methods Results and Discussion Conclusions

Venables, J. A., et al. Rep. Prog. Phys. 47, 399 (1984).

Atomic-Layer-Deposited

thin films

BOTTOM-UP APPROACHES

Introduction Strategy & Methods Results and Discussion Conclusions

Venables, J. A., et al. Rep. Prog. Phys. 47, 399 (1984).

PLEASE, NO DEFECTS!

Atomic-Layer-Deposited

thin films

BOTTOM-UP APPROACHES

Introduction Strategy & Methods Results and Discussion Conclusions

Venables, J. A., et al. Rep. Prog. Phys. 47, 399 (1984).

PLEASE, NO DEFECTS!

Atomic-Layer-Deposited

thin films

Nanostructured

clusters-assembled

thin films

5 mm

BOTTOM-UP APPROACHES

Introduction Strategy & Methods Results and Discussion Conclusions

Venables, J. A., et al. Rep. Prog. Phys. 47, 399 (1984).

PLEASE, NO DEFECTS!

Atomic-Layer-Deposited

thin films

Nanostructured

clusters-assembled

thin films

Controlled properties

by disorder organized

at the nano/meso scale

5 mm

DEPOSITION OF CLUSTERS

Introduction Strategy & Methods Results and Discussion Conclusions

DEPOSITION OF CLUSTERS

Introduction Strategy & Methods Results and Discussion Conclusions

DEPOSITION OF CLUSTERS

Introduction Strategy & Methods Results and Discussion Conclusions

Ekin > 1Fragmentation

ε

Ekin > 1Fragmentation

ε

Ekin > 1Fragmentation

ε

FUNCTIONAL PROPERTIES

Ekin > 1Fragmentation

ε

Wettability

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

IsoElectric Point

ns-TiOx

Wettability

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

IsoElectric Point

ns-TiOx

Wettability

ns-ZrOx

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

IsoElectric Point

ns-TiOx

Wettability

ns-ZrOx

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

Electrical properties

ns-Au

IsoElectric Point

ns-TiOx

Wettability

ns-ZrOx

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

Electrical properties

ns-Au

Electrochemical properties

ns-C

IsoElectric Point

ns-TiOx

Wettability

ns-ZrOx

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

Electrical properties

ns-Au

Electrochemical properties

ns-C

Biocompatibility

ns-ZrOx

IsoElectric Point

ns-TiOx

Wettability

ns-ZrOx

From STRUCTURAL to FUNCTIONAL properties

Introduction Strategy & Methods Results and Discussion Conclusions

ns-TiOx

Electrical properties

ns-Au

Electrochemical properties

ns-C

Biocompatibility

ns-ZrOx

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

DESCRIBE

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

DESCRIBE

CONTROL

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

DESCRIBE

CONTROL

ENGINEER

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

DESCRIBE

CONTROL

ENGINEER

STRUCTURAL FUNCTIONAL properties

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

DESCRIBE

CONTROL

ENGINEER

From the early stages, few clusters on the surface

STRUCTURAL FUNCTIONAL properties

GROWTH PROCESS

Introduction Strategy & Methods Results and Discussion Conclusions

Barabási, A.-L. &

Stanley, H. E. Fractal

Concepts in Surface

Growth. (Cambridge

University Press, 1995)

Jensen, P. Rev. Mod.

Phys. (1999)

EXPERIMENTS and THEORY

STATE OF ART

Introduction Strategy & Methods Results and Discussion Conclusions

Barabási, A.-L. &

Stanley, H. E. Fractal

Concepts in Surface

Growth. (Cambridge

University Press, 1995)

Jensen, P. Rev. Mod.

Phys. (1999)

EXPERIMENTS and THEORY

Bréchignac, C. et al. Für Phys. At. Mol. Clust. (1997)

Bouwen, W. et al. Thin Solid Films, (1999)

Bardotti, L., et al. Surf. Sci. (2000)

Bardotti, L. et al.. Surf. Sci., (1996)

Vandamme, et al. J. Phys. Condens. Matter, (2003)

Fuchs, G. et al. Für Phys. At. Mol. Clust., (1993)

Yoon, B. et al., Surf. Sci. , (1999)

Bouwen, W. et al., Rev. Sci. Instrum., (2000)

STATE OF ART

Introduction Strategy & Methods Results and Discussion Conclusions

Barabási, A.-L. &

Stanley, H. E. Fractal

Concepts in Surface

Growth. (Cambridge

University Press, 1995)

Jensen, P. Rev. Mod.

Phys. (1999)

EXPERIMENTS and THEORY

Bréchignac, C. et al. Für Phys. At. Mol. Clust. (1997)

Bouwen, W. et al. Thin Solid Films, (1999)

Bardotti, L., et al. Surf. Sci. (2000)

Bardotti, L. et al.. Surf. Sci., (1996)

Vandamme, et al. J. Phys. Condens. Matter, (2003)

Fuchs, G. et al. Für Phys. At. Mol. Clust., (1993)

Yoon, B. et al., Surf. Sci. , (1999)

Bouwen, W. et al., Rev. Sci. Instrum., (2000)

STATE OF ART

Introduction Strategy & Methods Results and Discussion Conclusions

Too complex system for

theoretical framework

Low stability and deposition rate of cluster sources

Barabási, A.-L. &

Stanley, H. E. Fractal

Concepts in Surface

Growth. (Cambridge

University Press, 1995)

Jensen, P. Rev. Mod.

Phys. (1999)

EXPERIMENTS and THEORY

Bréchignac, C. et al. Für Phys. At. Mol. Clust. (1997)

Bouwen, W. et al. Thin Solid Films, (1999)

Bardotti, L., et al. Surf. Sci. (2000)

Bardotti, L. et al.. Surf. Sci., (1996)

Vandamme, et al. J. Phys. Condens. Matter, (2003)

Fuchs, G. et al. Für Phys. At. Mol. Clust., (1993)

Yoon, B. et al., Surf. Sci. , (1999)

Bouwen, W. et al., Rev. Sci. Instrum., (2000)

STATE OF ART

Introduction Strategy & Methods Results and Discussion Conclusions

Do NOT focus on single defect but on the MESO/MACRO effects of disorder

Too complex system for

theoretical framework

Low stability and deposition rate of cluster sources

ns-ZrOx

Supersonic Cluster Beam Deposition of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

K. Wegner, Journal of Phys. D Appl. Phys. (2006)

CLUSTER SOURCE

ns-ZrOx

At room temperature

On fragments of polished Si wafers (~ 1x0,5 cm2)

With Helium or Argon as carrier gas

Supersonic Cluster Beam Deposition of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

K. Wegner, Journal of Phys. D Appl. Phys. (2006)

CLUSTER SOURCE

time

ns-ZrOx

At room temperature

On fragments of polished Si wafers (~ 1x0,5 cm2)

With Helium or Argon as carrier gas

Supersonic Cluster Beam Deposition of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

K. Wegner, Journal of Phys. D Appl. Phys. (2006)

CLUSTER SOURCE

Introduction Strategy & Methods Results and Discussion Conclusions

Atomic Force Microscopy

Characterization of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

Atomic Force Microscopy

Characterization of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

Atomic Force Microscopy

Characterization of NS-ZrOx Thin Film

Introduction Strategy & Methods Results and Discussion Conclusions

Atomic Force Microscopy

Characterization of NS-ZrOx Thin Film

EVALUATION OF THE GEOMETRICAL PROPERTIES

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.005μm

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

EVALUATION OF THE GEOMETRICAL PROPERTIES

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.005μm

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Coverage: ratio between the area occupied by clusters on the surface and the scanned area

EVALUATION OF THE GEOMETRICAL PROPERTIES

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.005μm

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Coverage: ratio between the area occupied by clusters on the surface and the scanned area

EVALUATION OF THE GEOMETRICAL PROPERTIES

Objects with dimension in z-direction different from the dimensions of primeval incident cluster

have been called islands

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.005μm

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

SURFACE EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Ns-ZrOx CLUSTER SIZE DISTRIBUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Ns-ZrOx CLUSTER SIZE DISTRIBUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0.5 ± 0.2 nm

Ns-ZrOx CLUSTER SIZE DISTRIBUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

2.5 ± 1 nm 6.3 ± 3.4 nm

0.5 ± 0.2 nm

Ns-ZrOx CLUSTER SIZE DISTRIBUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

2.5 ± 1 nm 6.3 ± 3.4 nm

0.5 ± 0.2 nm

A. Podestà, J. of Appl. Phys., 2015

SURFACE EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

SURFACE EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

Islands

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0 - 10 % : coalescence and fast nucleation

processes

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0 - 10 % : coalescence and fast nucleation

processes

10 - 70 %: (He) x-y juxtaposition and nucleation

of new islands, (Ar) stepwise around

coverage of 50%

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0 - 10 % : coalescence and fast nucleation

processes

10 - 70 %: (He) x-y juxtaposition and nucleation

of new islands, (Ar) stepwise around

coverage of 50%

70 - 100 % : Starting point of ballistic deposition

(without diffusion and coalescence)

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0 - 10 % : coalescence and fast nucleation

processes

10 - 70 %: (He) x-y juxtaposition and nucleation

of new islands, (Ar) stepwise around

coverage of 50%

70 - 100 % : Starting point of ballistic deposition

(without diffusion and coalescence)

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

nearest neighbor B. D.

Sticking probability =1

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

0 - 10 % : coalescence and fast nucleation

processes

10 - 70 %: (He) x-y juxtaposition and nucleation

of new islands, (Ar) stepwise around

coverage of 50%

70 - 100 % : Starting point of ballistic deposition

(without diffusion and coalescence)

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

nearest neighbor B. D.

Sticking probability =1

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Sticking probability ≠1

Robledo, A. et al. Phys. Rev. E 83, 051604 (2011)

0 - 10 % : coalescence and fast nucleation

processes

10 - 70 %: (He) x-y juxtaposition and nucleation

of new islands, (Ar) stepwise around

coverage of 50%

70 - 100 % : Starting point of ballistic deposition

(without diffusion and coalescence)

He Ar

HEIGHT EVOLUTION

Introduction Strategy & Methods Results and Discussion Conclusions

nearest neighbor B. D.

Sticking probability =1

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Sticking probability ≠1

Robledo, A. et al. Phys. Rev. E 83, 051604 (2011)

DENSITY OF CLUSTERS AND ISLANDS

He

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He

Nucleation events

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He

Nucleation events Competition between

nucleation events

and island growth

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He

Nucleation events Competition between

nucleation events

and island growth

Islands coalescence

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He Ar

Nucleation events Competition between

nucleation events

and island growth

Islands coalescence

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He Ar

Nucleation events Competition between

nucleation events

and island growth

Islands coalescence

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

DENSITY OF CLUSTERS AND ISLANDS

He Ar

Nucleation events Competition between

nucleation events

and island growth

Islands coalescence

Nsat ~ 25%Nsat ~ 45%

Introduction Strategy & Methods Results and Discussion Conclusions

F. borghi, et al., Arxiv, submitted to Phys. Rev. B

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

β = 0.24 ± 0.02

β = 0.39 ± 0.02

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

β = 0.24 ± 0.02

β = 0.39 ± 0.02

β = 0.20 ± 0.01

β = 0.39 ± 0.02

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

β = 0.24 ± 0.02

β = 0.39 ± 0.02

β = 0.20 ± 0.01

β = 0.39 ± 0.02

A.G. Konstandopoulos, Powder Technol. 109, 262 (2000)

Sticking probability ≠1

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

β = 0.24 ± 0.02

β = 0.39 ± 0.02

β = 0.20 ± 0.01

β = 0.39 ± 0.02 β = 0.37 ± 0.05

β = 0.32 ± 0.08

A.G. Konstandopoulos, Powder Technol. 109, 262 (2000)

Sticking probability ≠1

Rq ~ hβ

From SUB-MONOLAYER to THIN FILM REGIME

β - growth exponent

Introduction Strategy & Methods Results and Discussion Conclusions

BALLISTIC DEPOSITION

in 2+1 MODEL!

β = 0.24 ± 0.02

β = 0.39 ± 0.02

β = 0.20 ± 0.01

β = 0.39 ± 0.02 β = 0.37 ± 0.05

β = 0.32 ± 0.08

A.G. Konstandopoulos, Powder Technol. 109, 262 (2000)

Sticking probability ≠1Barabási, A.-L. & Stanley, H. E. Fractal Concepts in

Surface Growth. (Cambridge University Press, 1995)

SURFACE GROWTH ON SPHERICAL GEOMETRY

Introduction Strategy & Methods Results and Discussion Conclusions

SURFACE GROWTH ON SPHERICAL GEOMETRY

Introduction Strategy & Methods Results and Discussion Conclusions

SURFACE GROWTH ON SPHERICAL GEOMETRY

Introduction Strategy & Methods Results and Discussion Conclusions

F. Borghi, M. Chighizola, L. Marfori

SURFACE GROWTH ON SPHERICAL GEOMETRY

Introduction Strategy & Methods Results and Discussion Conclusions

F. Borghi, M. Chighizola, L. Marfori

SURFACE GROWTH ON SPHERICAL GEOMETRY

Introduction Strategy & Methods Results and Discussion Conclusions

July 9-14, 2017 - Boston

SURFACE GROWTH WITH ANNEALING

Introduction Strategy & Methods Results and Discussion Conclusions

Cluster-assembled

Rq =20 nm

Sputtered

Rq=1 nm

Ns-TiOx

SURFACE GROWTH WITH ANNEALING

Introduction Strategy & Methods Results and Discussion Conclusions

Cluster-assembled

Rq =20 nm

Sputtered

Rq=1 nm

Ns-TiOx

Rq =52 nmRq =5 nm

C. Lenardi & A. Podestà

SURFACE GROWTH WITH ANNEALING

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.01μmCluster-assembled

Rq =20 nm

Sputtered

Rq=1 nm

Ns-ZrOxNs-TiOx

Rq =52 nmRq =5 nm

C. Lenardi & A. Podestà

SURFACE GROWTH WITH ANNEALING

Introduction Strategy & Methods Results and Discussion Conclusions

2μm x 1μm x 0.01μm

F. Borghi, et al. Journal of Applied Physics (2016)

Cluster-assembled

Rq =20 nm

Sputtered

Rq=1 nm

Ns-ZrOxNs-TiOx

Rq =52 nmRq =5 nm

C. Lenardi & A. Podestà

Growth dynamics in sub-monolayer regime determines

different morphological properties of the cluster-assembled thin film

Introduction Strategy & Methods Results and Discussion Conclusions

CONCLUSIONS

Growth dynamics in sub-monolayer regime determines

different morphological properties of the cluster-assembled thin film

The morphological properties of cluster-assembled samples

in thin-film regime evolve according to a ballistic deposition model

(2+1), irrespective of the incident cluster dimensions

Introduction Strategy & Methods Results and Discussion Conclusions

CONCLUSIONS

Growth dynamics in sub-monolayer regime determines

different morphological properties of the cluster-assembled thin film

The morphological properties of cluster-assembled samples

in thin-film regime evolve according to a ballistic deposition model

(2+1), irrespective of the incident cluster dimensions

Thin films preserve their morphological properties and their

history even after a quite severe annealing process

Introduction Strategy & Methods Results and Discussion Conclusions

CONCLUSIONS

MAIN RESULT

We can describe and control the growth of

nanostructured thin films in order to tune the functional

properties of the interface by changing its morphology

Growth dynamics in sub-monolayer regime determines

different morphological properties of the cluster-assembled thin film

The morphological properties of cluster-assembled samples

in thin-film regime evolve according to a ballistic deposition model

(2+1), irrespective of the incident cluster dimensions

Thin films preserve their morphological properties and their

history even after a quite severe annealing process

Introduction Strategy & Methods Results and Discussion Conclusions

CONCLUSIONS

PERSPECTIVE

Introduction Strategy & Methods Results and Discussion Conclusions

Novel nanostructured scaffolds to investigate

signalling in reconstructed neuronal networks

PERSPECTIVE

Introduction Strategy & Methods Results and Discussion Conclusions

Novel nanostructured scaffolds to investigate

signalling in reconstructed neuronal networks

100 μm

PERSPECTIVE

Introduction Strategy & Methods Results and Discussion Conclusions

Novel nanostructured scaffolds to investigate

signalling in reconstructed neuronal networks

Control on morphological properties functional ones

100 μm

LGM laboratory - CIMaINa

LGM laboratory - CIMaINa