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Plasma Nanotechnology: from Microelectronics and Discovery of Carbon Nanotubes to Self-Organized Nanodevices and Safe
Plasma Nanotechnology: from Microelectronics and Discovery of Carbon Nanotubes to Self-Organized Nanodevices and Safe
Plasma Nanotechnology: from Microelectronics and
Discovery of Carbon Nanotubes to Self-Organized
Nanodevices and Safe Nanotech of the Future
Kostya (Ken) Ostrikov CEO Science Leader, Director, Plasma Nanoscience Centre Australia (PNCA), CSIRO Materials Science
Kostya (Ken) Ostrikov
CEO Science Leader, Director, Plasma Nanoscience
Centre Australia (PNCA), CSIRO Materials Science and
Engineering, and Honorary Professor, University of
Sydney, AUSTRALIA
Australia (PNCA), CSIRO Materials Science and Engineering, and Honorary Professor, University of Sydney, AUSTRALIA
Australia (PNCA), CSIRO Materials Science and Engineering, and Honorary Professor, University of Sydney, AUSTRALIA

% of Total Papers published

20 Plasma* AND Fusion* Plasma* AND Astro* Plasma* AND Dust* 16 Plasma* AND Nano* Plasma*
20
Plasma* AND Fusion*
Plasma* AND Astro*
Plasma* AND Dust*
16
Plasma* AND Nano*
Plasma* AND Chemistry*
12 8 4 area we work in 0 0 5 10 Year (from 1990)
12
8
4
area we work in
0
0
5
10
Year (from 1990)

5 out 25 top cited in NANO!!!

0 0 5 10 Year (from 1990) 5 out 25 top cited in NANO!!! 15 is
0 0 5 10 Year (from 1990) 5 out 25 top cited in NANO!!! 15 is

15

is a multidisciplinary subfield at the cutting edge of plasma physics, nanoscience, surface science, astrophysics, materials science and engineering, and structural chemistry, which aims

to elucidate specific roles and purposes of the plasma

environment in assembling nano-things in natural, laboratory and technological situations and find ways to bring this plasma-

based assembly to the deterministic level.

laboratory and technological situations and find ways to bring this plasma- based assembly to the deterministic
Some examples of lab-based highly-controlled synthesis of nanoscale objects 35-50 nm
Some examples of lab-based highly-controlled synthesis of nanoscale objects 35-50 nm
Some examples of lab-based highly-controlled synthesis of nanoscale objects 35-50 nm

Some examples of lab-based highly-controlled synthesis of

nanoscale objects
nanoscale objects
35-50 nm
35-50 nm
Some examples of lab-based highly-controlled synthesis of nanoscale objects 35-50 nm
Some examples of lab-based highly-controlled synthesis of nanoscale objects 35-50 nm
Grand challenge
Grand challenge
Architecture and hierarchically arrange complex functional nanoscale objects in “streets”, “suburbs”, and
Architecture and hierarchically arrange complex functional
nanoscale objects in “streets”, “suburbs”, and “cities” and
then reconnect them at the expected density of integration!
“suburbs”, and “cities” and then reconnect them at the expected density of integration! Electronic Photonic Bio-

Electronic

“suburbs”, and “cities” and then reconnect them at the expected density of integration! Electronic Photonic Bio-
“suburbs”, and “cities” and then reconnect them at the expected density of integration! Electronic Photonic Bio-
“suburbs”, and “cities” and then reconnect them at the expected density of integration! Electronic Photonic Bio-
Photonic
Photonic

Bio-

“suburbs”, and “cities” and then reconnect them at the expected density of integration! Electronic Photonic Bio-
Incident light Ag Islands Amorphous material insulator Si
Incident light
Ag Islands
Amorphous
material
insulator
Si

Scientific approach: “Architecture” – Order Make uniform Connect

Scientific approach: “Architecture” – Order – Make uniform – Connect
Scientific approach: “Architecture” – Order – Make uniform – Connect
Scientific approach: “Architecture” – Order – Make uniform – Connect
Scientific approach: “Architecture” – Order – Make uniform – Connect

Extremely difficult to do for very small nanostructures (e.g., QDs)

difficult to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable
Poor ordering …
Poor ordering …

Unpredictable

shapes…

to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable behaviour …
to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable behaviour …

Uncontrollable behaviour …

to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable behaviour …
to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable behaviour …
to do for very small nanostructures (e.g., QDs) Poor ordering … Unpredictable shapes… Uncontrollable behaviour …
REASON:
REASON:
LARGE (>100 nm) NANOPARTICLES ARE TRAPPED IN ANY STATE THEY WERE CREATED
LARGE (>100 nm) NANOPARTICLES ARE
TRAPPED IN ANY STATE THEY WERE CREATED
NANOPARTICLES ARE TRAPPED IN ANY STATE THEY WERE CREATED SMALL (<10 nm) NANOPARTICLES RETURN TO EQUILIBRIUM
NANOPARTICLES ARE TRAPPED IN ANY STATE THEY WERE CREATED SMALL (<10 nm) NANOPARTICLES RETURN TO EQUILIBRIUM
NANOPARTICLES ARE TRAPPED IN ANY STATE THEY WERE CREATED SMALL (<10 nm) NANOPARTICLES RETURN TO EQUILIBRIUM
NANOPARTICLES ARE TRAPPED IN ANY STATE THEY WERE CREATED SMALL (<10 nm) NANOPARTICLES RETURN TO EQUILIBRIUM
SMALL (<10 nm) NANOPARTICLES RETURN TO EQUILIBRIUM SHAPE *
SMALL (<10 nm) NANOPARTICLES
RETURN TO EQUILIBRIUM SHAPE *
* at least to the next available metastable state closer to equilibrium
* at least to the next available metastable state closer to equilibrium
Solution
Solution
Non-equilibrium Nano- architectronics: APPROACH
Non-equilibrium Nano-
architectronics: APPROACH

Operating under far from equilibrium

conditions [using the laws of kinetics]

Reaching the normally „unreachable‟ less stable states [be quick!]

Tailoring the barriers [keep the structure!]

the normally „unreachable‟ less stable states [be quick!]  Tailoring the barriers [keep the structure!]

Low temperature plasmas: a unique non-equilibrium system

Low temperature plasmas: a unique non-equilibrium system N Electrons Neutral Gas Ions 2 eV Energy, W
N Electrons Neutral Gas Ions 2 eV Energy, W 0 0.025 eV
N
Electrons
Neutral
Gas
Ions
2 eV Energy, W 0
0.025 eV
• Electrons not in thermal equilibrium with the ions or neutrals • High T e
Electrons not in thermal equilibrium with the ions or neutrals
High T e
dissociates gas
Low T G and T + protects substrates
Negative charge on surfaces protects them from high
electron energy
10
MORE UNIQUE FEATURES
MORE UNIQUE FEATURES
T e >> T i > T n
T e >> T i > T n
N n >> N i ~ N e
N n >> N i ~ N e

Higher complexity system good for self-organization (more effective driving forces)

Electric fields Long-range Coulomb interactions Polarization interactions Isotropic vs anisotropic pressure PLASMA –
Electric fields
Long-range Coulomb interactions
Polarization interactions
Isotropic vs anisotropic pressure
PLASMA – COMMON
INDUSTRIAL TOOL
Non-equilibrium cooling/heating )
Surface stresses due to ion bombardment
Charge, termination etc. – control of surface energy

Virtually unlimited choice of BUs and WUs

Unusual chemical reactivity – plasma etching So, what can the plasma do for nanotech?
Unusual chemical reactivity – plasma etching
So, what can the plasma do for nanotech?
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED IN A PLASMA
FOR STARTERS: CNTs DISCOVERED
IN A PLASMA

Unique vertical alignment of CNTs!

Neutral route
Neutral
route
Plasma route
Plasma
route

http://www.nano-lab.com/nanotube-image.html

Plasma route http://www.nano-lab.com/nanotube-image.html Z. Ren et al Science 1998: vol. 282. no. 5391, pp. 1105 -

Z. Ren et al Science 1998: vol. 282. no. 5391, pp. 1105 - 1107 .

Plasma (nano)etching – common industrial process! PPAP 4 , 612 (2007)

Plasma (nano)etching common industrial process!

PPAP 4, 612 (2007)

Plasma (nano)etching – common industrial process! PPAP 4 , 612 (2007)
Plasma (nano)etching – common industrial process! PPAP 4 , 612 (2007)

Highly-unusual metastable nanomaterials and nanophases

Highly-unusual metastable nanomaterials and nanophases S. Komatsu, JPD, v. 40, 23 Apr 2007

S. Komatsu, JPD, v. 40, 23 Apr 2007

Controlled delivery and redistribution of building units

 Control of surface energetics, diffusion, desorption, etc. I e +I i I e +I
Control of surface energetics, diffusion, desorption, etc.
I
e +I i
I
e +I i =0
f
float
U
s

NON-Equilibrium heating and stress

NON-Equilibrium heating and stress eU k b 3/4 3/4  T  s   ,
NON-Equilibrium heating and stress eU k b 3/4 3/4  T  s   ,

eU

k

b

3/4

3/4

T

s

 

,

Substrate heating due to ion flux, φ [ML/s]
Substrate heating due
to ion flux, φ [ML/s]
  , Substrate heating due to ion flux, φ [ML/s]  Effective substrate temperature in

Effective substrate temperature in presence of an ion flux: T + δT

ENABLING A DETERMINISTIC APPROACH

ENABLING A DETERMINISTIC APPROACH
ENABLING A DETERMINISTIC APPROACH

I. SHAPING

Non-equilibrium plasma turns things upside down

I. SHAPING Non-equilibrium plasma turns things upside down Single crystal, cubic shape silicon nanocrystals produced in

Single crystal, cubic shape silicon nanocrystals produced in a non-equilibrium plasma [U. Kortshagen et al., JNN 9, 39

(2007)]

plasma [U. Kortshagen et al., JNN 9, 39 (2007)] No plasma (no H-termination) Si cube is
plasma [U. Kortshagen et al., JNN 9, 39 (2007)] No plasma (no H-termination) Si cube is

No plasma (no H-termination)

et al., JNN 9, 39 (2007)] No plasma (no H-termination) Si cube is least stable, “unwanted”

Si cube is least stable, “unwanted”

(no H-termination) Si cube is least stable, “unwanted” Effective H-termination Si cube is most stable, “wanted”

Effective H-termination

cube is least stable, “unwanted” Effective H-termination Si cube is most stable, “wanted” A. Barnard, P.

Si cube is most stable, “wanted”

A. Barnard, P. Zapol, J. Chem.

B. Phys. 121, 4276 (2004)

A. Barnard, P. Zapol, J. Chem. B. Phys. 121, 4276 (2004) T. Hawa, M. R. Zachariah,

T. Hawa, M. R. Zachariah, J. Phys. Chem. C 112, 14796 (2008)

A. Barnard, P. Zapol, J. Chem. B. Phys. 121, 4276 (2004) T. Hawa, M. R. Zachariah,
Tailoring Si nanocones and nano- pyramids in Ar + H 2 plasma (S. Y. Huang,

Tailoring Si nanocones and nano- pyramids in Ar + H 2 plasma (S. Y. Huang, S. Xu, I. Levchenko,

K. Ostrikov, 2009)

Si (100)
Si (100)

Si (111)

and nano- pyramids in Ar + H 2 plasma (S. Y. Huang, S. Xu, I. Levchenko,

PV collaboration with PSAC NIE/NTU [S. Xu et al.]

What does this mean for PV solar cells?
What does this mean for PV solar cells?
[S. Xu et al.] What does this mean for PV solar cells? Pseudo Light IV curve
[S. Xu et al.] What does this mean for PV solar cells? Pseudo Light IV curve
Pseudo Light IV curve without the effect of Rs 116 mV V oc = 0.04
Pseudo Light IV curve without the effect of Rs
116 mV
V oc =
0.04
0.009
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0.000
0.00
0.05
0.10
0.15
0.20
0.25
Voltage (V)
Current (A/cm 2 )
Power Density (W/cm2)
Pseudo Light IV curve without the effect of Rs V oc = 347 mV 0.04
Pseudo Light IV curve without the effect of Rs
V oc = 347 mV
0.04
0.019
0.035
0.03
0.025
0.02
0.009
0.015
0.01
0.005
0
0.000
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Voltage (V)
Current (A/cm 2 )
Power Density (W/cm2)
Ar : H 2 = 9 : 1; P in = 2.0 kW; T =
Ar : H 2 = 9 : 1;
P in = 2.0 kW; T = 300K,
t=30 min; V b =0.
Ar : H 2 =1 : 3;
P in =1.5 kW;
T = 300 K; t =30 min;
V b = - 50V
2 =1 : 3; P in =1.5 kW; T = 300 K; t =30 min; V
Pseudo Light IV curve without the effect of Rs V oc = 453 mV 0.04
Pseudo Light IV curve without the effect of Rs
V oc = 453 mV
0.04
0.019
0.035
0.03
0.025
0.02
0.009
0.015
0.01
0.005
0
0.000
0.00
0.10
0.20
0.30
0.40
0.50
Voltage (V)
Current (A/cm 2 )
Power Density (W/cm2)
Ar : H 2 = 1 : 3; P in = 2.0 kW; T =
Ar : H 2 = 1 : 3;
P in = 2.0 kW;
T = 300 K; t=30min;
V b = - 50V
Voltage (V) Current (A/cm 2 ) Power Density (W/cm2) Ar : H 2 = 1 :

Tailoring iron oxide nanowires and nanobelts [U. Cvelbar, K. Ostrikov, Crystal Growth Design 8, 4347 (2008)]

Tailoring iron oxide nanowires and nanobelts [U. Cvelbar, K. Ostrikov, Crystal Growth Design 8 , 4347
Tailoring iron oxide nanowires and nanobelts [U. Cvelbar, K. Ostrikov, Crystal Growth Design 8 , 4347
Challenge: controlling nanostructure shapes Solution: control by electric conditions on the surface [APL 94, 211502
Challenge: controlling nanostructure shapes
Solution: control by electric conditions on the surface
[APL 94, 211502 (2009)]

Tailoring microplasma nanofabrication: from nanostructures to nanoarchitectures [Mariotti & Ostrikov, J. Phys D 42, 092002 (2009)]

nanofabrication: from nanostructures to nanoarchitectures [Mariotti & Ostrikov, J. Phys D 42 , 092002 (2009)]
nanofabrication: from nanostructures to nanoarchitectures [Mariotti & Ostrikov, J. Phys D 42 , 092002 (2009)]
nanofabrication: from nanostructures to nanoarchitectures [Mariotti & Ostrikov, J. Phys D 42 , 092002 (2009)]

II. ARRANGING

Predicting nucleation sites
Predicting nucleation sites

[Levchenko, Cvelbar, Ostrikov (June 2009), submitted to APL]

II. ARRANGING Predicting nucleation sites [Levchenko, Cvelbar, Ostrikov (June 2009), submitted to APL]
II. ARRANGING Predicting nucleation sites [Levchenko, Cvelbar, Ostrikov (June 2009), submitted to APL]
II. ARRANGING Predicting nucleation sites [Levchenko, Cvelbar, Ostrikov (June 2009), submitted to APL]

Self-organization of Ni/Si nanodots under plasma exposure [APL 93, 183102 (2008)]

Self-organization of Ni/Si nanodots under plasma exposure [APL 93, 183102 (2008)]
Self-organization of Ni/Si nanodots under plasma exposure [APL 93, 183102 (2008)]
Simultaneous Ni catalyst saturation [I. Levchenko and K. Ostrikov, Appl. Phys. Lett. 92 (2008)]
Simultaneous Ni catalyst saturation [I. Levchenko and
K. Ostrikov, Appl. Phys. Lett. 92 (2008)]
[I. Levchenko and K. Ostrikov, Appl. Phys. Lett. 92 (2008)] Arrows show larger relative ion flux

Arrows show larger relative ion flux

Levchenko and K. Ostrikov, Appl. Phys. Lett. 92 (2008)] Arrows show larger relative ion flux More
Levchenko and K. Ostrikov, Appl. Phys. Lett. 92 (2008)] Arrows show larger relative ion flux More
More uniform CNT arrays !
More uniform CNT arrays !

3D self-organizationnot the case in neutral gas processes [Carbon 45, 2022 (2007)] !!!

3D self-organization – not the case in neutral gas processes [ Carbon 45, 2022 (2007)] !!!
3D self-organization – not the case in neutral gas processes [ Carbon 45, 2022 (2007)] !!!
3D self-organization – not the case in neutral gas processes [ Carbon 45, 2022 (2007)] !!!
3D self-organization – not the case in neutral gas processes [ Carbon 45, 2022 (2007)] !!!
3D self-organization – not the case in neutral gas processes [ Carbon 45, 2022 (2007)] !!!
Self-organization near thermodynamic equilibrium leads to relatively simple geometries whereas self-organization far from

Self-organization near thermodynamic equilibrium leads to relatively simple geometries whereas self-organization far from

equilibrium leads to more complex geometries [Whitesides and

Grzbowski, Science 295, 2418 (2002)]

No plasma
No plasma
With plasma
With plasma

III. CONNECTING

Self-Organized Carbon Connections Between Ag Nanoparticles via Atmospheric Microplasma Synthesis [CARBON (Letters) 47, 344 (2009)]

Carbon Connections Between Ag Nanoparticles via Atmospheric Microplasma Synthesis [CARBON (Letters) 47, 344 (2009)]
Carbon Connections Between Ag Nanoparticles via Atmospheric Microplasma Synthesis [CARBON (Letters) 47, 344 (2009)]
Carbon Connections Between Ag Nanoparticles via Atmospheric Microplasma Synthesis [CARBON (Letters) 47, 344 (2009)]
Carbon Connections Between Ag Nanoparticles via Atmospheric Microplasma Synthesis [CARBON (Letters) 47, 344 (2009)]

Also: Si NPs and realistic surface processes. Carbon, in press (2009) doi:10.1016/j.carbon.2009.04.031

Also: Si NPs and realistic surface processes. Carbon, in press (2009) doi:10.1016/j.carbon.2009.04.031
Also: Si NPs and realistic surface processes. Carbon, in press (2009) doi:10.1016/j.carbon.2009.04.031
Also: Si NPs and realistic surface processes. Carbon, in press (2009) doi:10.1016/j.carbon.2009.04.031
IEEE Trans Plasma Sci. 36 , 866 (2008)
IEEE Trans Plasma Sci. 36 , 866 (2008)

IEEE Trans Plasma Sci. 36, 866 (2008)

IEEE Trans Plasma Sci. 36 , 866 (2008)

This will eventually lead to … nano- architectured self-assembled nanoscale systems

This will eventually lead to … nano - architectured self-assembled nanoscale systems
This will eventually lead to … nano - architectured self-assembled nanoscale systems
applications
applications
applications

Links to other academic and industrial areas

Quantum Surface information science Plasma Nano- physics science
Quantum
Surface
information
science
Plasma
Nano-
physics
science
Materials Re‟new‟wable science energy Photonics Life sciences Nano- Chemistry Astrophysics electronics
Materials
Re‟new‟wable
science
energy
Photonics
Life
sciences
Nano-
Chemistry
Astrophysics
electronics
Opto-
Medicine
electronics
Sensors
Advanced
Integrated
Plasma
materials
medicine
Bio-implants Nano- devices circuitry Nanotools Lasers Coatings Plasmonic structures Solar cells Drug/gene
Bio-implants
Nano-
devices
circuitry
Nanotools
Lasers
Coatings
Plasmonic
structures
Solar cells
Drug/gene

delivery Biomarkers

Solar cells Drug/gene d e l i v e r y Biomarkers Electrochem. Environmental batteries remediation
Electrochem. Environmental batteries remediation Chemical LEDs Catalysis synthesis
Electrochem.
Environmental
batteries
remediation
Chemical
LEDs
Catalysis synthesis
Applications: some examples
Applications: some examples
“Self-organised” Nanoelectronics Multipurpose CNTs GAS SENSORS
“Self-organised”
Nanoelectronics
Multipurpose CNTs
GAS SENSORS

E-mail: Kostya.Ostrikov@csiro.au

Ultra-nanoporous materials
Ultra-nanoporous materials
BIOIMPLANTS
BIOIMPLANTS

Optoelectronics/Photonics

PV – collaboration with PSAC NIE/NTU [S. Xu et al.] Plasmonic arrays TCO µc-Si µc-Si

PV collaboration with PSAC NIE/NTU [S. Xu et al.]

Plasmonic arrays

with PSAC NIE/NTU [S. Xu et al.] Plasmonic arrays TCO µc-Si µc-Si Si thin film solar
TCO µc-Si µc-Si Si thin film solar cell Si thin film solar cell
TCO
µc-Si
µc-Si
Si thin film solar cell
Si thin film solar cell
Plasmonic arrays TCO µc-Si µc-Si Si thin film solar cell Si thin film solar cell PV
Plasmonic arrays TCO µc-Si µc-Si Si thin film solar cell Si thin film solar cell PV

PV SOLAR CELLS

Photo-active layers

Plasmonic arrays TCO µc-Si µc-Si Si thin film solar cell Si thin film solar cell PV

Plasma control of nanostructured phases in nc-Si for PV solar cells

control of nanostructured phases in nc-Si for PV solar cells [Cryst Growth Design 9, 2863 (2009);

[Cryst Growth Design 9, 2863 (2009); Nanotechnology 20,

215606 (2009); J. Mater. Chem. (2009) DOI: 10.1039/b904227j]

[Cryst Growth Design 9, 2863 (2009); Nanotechnology 20 , 215606 (2009); J. Mater. Chem. (2009) DOI:

nc-Si : control of nanocrystalline phases, growth rates, and optical bandgap [Cryst Growth Design 9, 2863 (2009); Nanotechnology 20,

215606 (2009); J. Mater. Chem. (2009) DOI: 10.1039/b904227j]

215606 (2009); J. Mater. Chem. (2009) DOI: 10.1039/b904227j] 100 o C Very high growth rates 0
100 o C Very high growth rates 0 – 86% cryst phase + bandgap control
100 o
C
Very high growth rates
0 – 86% cryst phase
+ bandgap control
200 o C
Cryst phase
Amorph phase
300
o C
Also: 1) no hydrogen dilution possible! 2) excellent
transmittance in optical range
Onset of nanocrystallinity + nanophase control
Challenges,
Challenges,

grand or small,

all lead to
all lead to

breakthrough

Challenges, grand or small, all lead to breakthrough

Transforming matter by controlled surface hydrogenation (“what amazing things can the plasma do!”)

(“what amazing things can the plasma do!”) Levchenko, Ostrikov, Xu, JPhysD 42 , 125207 (2009) D.
(“what amazing things can the plasma do!”) Levchenko, Ostrikov, Xu, JPhysD 42 , 125207 (2009) D.

Levchenko, Ostrikov, Xu, JPhysD 42, 125207 (2009)

D. C. Elias et al., Science 323, 610 (2009)

Hydrogenation of graphene (inert and conducting) in Ar + H 2 DC plasma leads to
Hydrogenation of graphene (inert and
conducting) in Ar + H 2 DC plasma
leads to graphane (dielectric)

Image: A. Savchenko, Science 323, 589 (2009)

Big challenges:
Big challenges:

1) Epitaxial self-assembled graphene 2) Precise control of surface energetics 3) Switch-over between TD and kinetic modes

1) Epitaxial self-assembled graphene 2) Precise control of surface energetics 3) Switch-over between TD and kinetic
A plasma knife can cut the nanotubes to create GNRs
A plasma knife can cut the nanotubes to create GNRs
Ar plasma (~10s)
Ar plasma (~10s)
knife can cut the nanotubes to create GNRs Ar plasma (~10s) Graphene Nanoribbons (GNRs): L. Jiao
knife can cut the nanotubes to create GNRs Ar plasma (~10s) Graphene Nanoribbons (GNRs): L. Jiao

Graphene Nanoribbons (GNRs):

L. Jiao et al. Nature 458, 877 (2009)

Big challenges:
Big challenges:

1) understanding ion-CNT interactions 2) How to make it precise and “gentle”?

458 , 877 (2009) Big challenges: 1) understanding ion-CNT interactions 2) How to make it precise
458 , 877 (2009) Big challenges: 1) understanding ion-CNT interactions 2) How to make it precise
Superhydrophobic a-C/CNT composites via ion bombardment [Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)]
Superhydrophobic a-C/CNT composites via ion bombardment
[Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)]
[Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)] CA ~ 150 – 170 o Energetic (~1
[Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)] CA ~ 150 – 170 o Energetic (~1
[Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)] CA ~ 150 – 170 o Energetic (~1

CA ~ 150 170 o

Ostrikov, APL 94, 223106 (2009)] CA ~ 150 – 170 o Energetic (~1 kV) ions are
Energetic (~1 kV) ions are focused by the CNTs, push the Ni catalyst particle down
Energetic (~1 kV) ions are focused by the CNTs, push the Ni catalyst particle
down the channel and then create a -C “caps”. Water droplets are suspended
and do not fall down the inter-CNT gaps. Array parameters do matter!

Plasma exposure of CNTs can even convert them into diamond caution and understanding needed!

convert them into diamond – caution and understanding needed! E. Aydil et al, Uni Minnesota (Gordon

E. Aydil et al, Uni Minnesota (Gordon Res. Conf. 2008)

Control of SWCNTs
Control of SWCNTs
Control of SWCNTs Remote PECVD, 90% H2 + 10% CH4, 15 mbar, 400-650 o C; 0.5
Remote PECVD, 90% H2 + 10% CH4, 15 mbar, 400-650 o C; 0.5 nm Al
Remote PECVD, 90% H2 + 10% CH4,
15 mbar, 400-650 o C; 0.5 nm Al / 0.5-1
nm Fe / 10 nm Al 70% purity (30% a-C)
Metallic / Semicond = 1:2
/ 10 nm Al 70% purity (30% a-C) Metallic / Semicond = 1:2 J. Robertson et
J. Robertson et al. APL 93, 163911 (2008) Challenges: chirality control; selective elimination of metallic
J. Robertson et al. APL 93, 163911 (2008)
Challenges: chirality control; selective
elimination of metallic or semicond.
tubes
Example of solution: burning metallic SWCNTs
Example of solution: burning metallic SWCNTs
Example of solution: burning metallic SWCNTs M. Keidar et al., Carbon 44, 1022 (2006); K. Ostrikov

M. Keidar et al., Carbon 44, 1022 (2006);

K. Ostrikov and A. B. Murphy,

J. Phys. D 40, 2223 (2007)

44, 1022 (2006); K. Ostrikov and A. B. Murphy, J. Phys. D 40, 2223 (2007) But

But how to

select

any particular chirality?

44, 1022 (2006); K. Ostrikov and A. B. Murphy, J. Phys. D 40, 2223 (2007) But

Solution: grow thinner SWCNTs much faster than others!

Solution: grow thinner SWCNTs much faster than others! E. Tam and K. Ostrikov (June 2009); see

E. Tam and K. Ostrikov (June 2009); see also APL 93, 261504 (2008)

NEUTRAL CVD
NEUTRAL CVD
NEUTRAL CVD PECVD PECVD
NEUTRAL CVD
PECVD
PECVD
PECVD
PECVD
Towards epitaxial graphene
Towards epitaxial graphene
High-pressure Ar atmosphere
High-pressure Ar
atmosphere
Towards epitaxial graphene High-pressure Ar atmosphere Si sublimates leaving exfoliated graphene behind K.V. Emtsev et

Si sublimates leaving exfoliated graphene behind

K.V. Emtsev et al. Nature Mater. 8 (2009) 203.
K.V. Emtsev et al. Nature Mater. 8 (2009) 203.

Images: P. Sutter Nature Mater. 8 (2009) 171.

exfoliated graphene behind K.V. Emtsev et al. Nature Mater. 8 (2009) 203. Images: P. Sutter Nature
Control of Si sublimation through polarization effects: the ionization theory approach [Phys Lett A 373,
Control of Si sublimation through polarization effects:
the ionization theory approach [Phys Lett A 373, 2267 (2009)]
ionization theory approach [Phys Lett A 373, 2267 (2009)] Si atoms tend to diffuse and evaporate
ionization theory approach [Phys Lett A 373, 2267 (2009)] Si atoms tend to diffuse and evaporate

Si atoms tend to diffuse and evaporate faster than C. Electric field/Polarizability additional way to control!

Si atoms tend to diffuse and evaporate faster than C. Electric field/Polarizability – additional way to
Si atoms tend to diffuse and evaporate faster than C. Electric field/Polarizability – additional way to
Si atoms tend to diffuse and evaporate faster than C. Electric field/Polarizability – additional way to
GRAND CHALLENGES
GRAND CHALLENGES
GRAND CHALLENGES 1) 2) 3) 4) 5)
1)
1)
2)
2)
3)
3)
4)
4)
5)
5)
GRAND CHALLENGES 1) 2) 3) 4) 5)

JSAP/NEDO Roadmap:Plasma Process Technology

2010 2020 2030 2040 Device dimension 35nm 25nm 10nm 5nm 2.5nm 1nm Compound Semiconductor Nano-scale
2010
2020
2030
2040
Device dimension
35nm
25nm
10nm
5nm
2.5nm
1nm
Compound Semiconductor
Nano-scale Logic Device
Molecular Device
Atomic Device
High Definition Flexible Display
3-Dimension Display
Ubiquitous Display
Projection in Brain
Health Care Chip Drug-Delivery system Bio-Mechanics-fusion Bio-Self-assembly Self-repairing Genome Device
Ultra Efficient Solar Cell
Super Efficient Photoelectric/Thermoelectric conversion
New Energy Source
Environmental Detox
Hi-Efficient Agricultural/Marine production
Nano Detox
Global Restoration
Hi-Efficient Manufac. Tool
1 Atom-Accurate Manufac. Tool
Self
Assemble Manufac. Tool
Engineering makes Seeds(Principle) to Production Technology
Hi Precision / Hi Productivity / Large Area / Stable Production Technology
Development for Feedback Control Technology using Monitor and Simulation
Navigation Assist Process Tuning  Pin-Point Control  Pin-Point Design
Monitor- ,Simulator - Friendly Reactor Design
Top-down Process
Principle of Species Generation Control Nano, μ - m scale,
Lo - Hi Pressure, Gas/Liquid/Solid(Surface), Phase mix
Principle of Surface Reaction
Monochroic Flux
1 Atom/Molecule Control
Control of Functional Unit Organic/Bio Material
Vertical/Lateral Atomically-controlled Depo/Etch
Bio Molecular Manipulation
Bottom-Up Process
Principle of Selective Reaction/Self-Assemble
Clarify & Realize of No-defect / Ultra Hi-Speed reaction
Ultimate Controlled Beam
Process for
Defect Self-healing
Synergic Reaction in Large area
Common Basic Technology
Perfect No-Defect Hi-Speed Self-
Assembled films / Materials
Diagnostics Ultimate precise No Disturb. 3D Flash Diag.
Nano struct./Elec.Charact. Diag. Prognostic Diag.
Simulation
Ultimate correct
Multi Scaled Time/Space Flash (intuitive) Algorithm
DATABASE : Atom, Molecule Reaction / Surface Reaction / Mechanism
Plasma Electronics Division, JSAP
Research
Development
Output
Manufacturing
Seeds
technology
Products, Application

Process Simulation

Sub map for Plasma Process Technology

Application

Output

Products,

Development

Manufacturing

technology

Seeds

Research

Fundamentals

2010

2020

2030

2040

Learning・Adaptive control software
Learning・Adaptive
control software
Interactive type software Z
Interactive type software
Diagnostics ・ Visualization support tool
Diagnostics ・ Visualization support tool
Linkage with experiments, experiment control (Validation of simulation)
Linkage
with experiments, experiment control (Validation of simulation)
Molecule scale(Molecular dynamics) Mesoscopic scale (Fluid・ Stochastic method) Micro scale (Continuous
Molecule scale(Molecular dynamics)
Mesoscopic scale (Fluid・ Stochastic method)
Micro scale (Continuous model)
Rule mining (Estimation for law of physics & chemistry via simulation)
Rule mining (Estimation for law of physics & chemistry via simulation)
Multi scale (Space, Time) Simulation
Multi scale (Space, Time)
Simulation
Rule mining (Estimation for law of physics & chemistry via simulation) Multi scale (Space, Time) Simulation
Rule mining (Estimation for law of physics & chemistry via simulation) Multi scale (Space, Time) Simulation
Rule mining (Estimation for law of physics & chemistry via simulation) Multi scale (Space, Time) Simulation
Approximation・Modeling Technique including first-principle simulation High speed algorithm Collection & compile of
Approximation・Modeling Technique including first-principle simulation
High speed algorithm
Collection & compile of Fundamental data(Cross-section, Potential, transport co. ,…)
Micro fabrication

Micro fabrication

Micro fabrication Plasma for Nano process
Micro fabrication Plasma for Nano process
Micro fabrication Plasma for Nano process

Plasma for Nano process

Micro fabrication Plasma for Nano process
Micro fabrication Plasma for Nano process
Micro fabrication Plasma for Nano process

2010

25nm

18

fabrication Plasma for Nano process 2010 2 5 n m 1 8 Sub map for Plasma

Sub map for Plasma Process Technology

AtomMolec. Process

Self-assembled Reaction

2.9

2.1

1.4

Miniaturization

Model for process control

2040

1.0

Low damage

Tool monitoring

Atom, molecule process control

Low damage Tool monitoring Atom, molecule process control 9 6 2030 4.2 2020 13 Tr.Gate siza
Low damage Tool monitoring Atom, molecule process control 9 6 2030 4.2 2020 13 Tr.Gate siza
Low damage Tool monitoring Atom, molecule process control 9 6 2030 4.2 2020 13 Tr.Gate siza

9

Low damage Tool monitoring Atom, molecule process control 9 6 2030 4.2 2020 13 Tr.Gate siza
Low damage Tool monitoring Atom, molecule process control 9 6 2030 4.2 2020 13 Tr.Gate siza

6

2030

4.2

2020 13
2020
13

Tr.Gate siza

CMOS

Precise

etching

Large area

±3.0nm

±2.0nm

<±1.0nm以下

Predictionsimulation

Lower limitation

Prediction ・ simulation ( Lower limitation ) Fundamental database ( Crosssection, Reactivity,… )
Prediction ・ simulation ( Lower limitation ) Fundamental database ( Crosssection, Reactivity,… )
Prediction ・ simulation ( Lower limitation ) Fundamental database ( Crosssection, Reactivity,… )

Fundamental database Crosssection, Reactivity,…

675mmΦ
675mmΦ

300mmΦ

450mmΦ

Large wafer

Reactivity,… ) 675mmΦ 300mmΦ 450mmΦ Large wafer Effect for Equipment Availability (Productivity)

Effect for

Equipment

Availability

(Productivity)

Run-to-Run In-Situ Control Control Fault Prediction Culture change Fault Detection EEC & Classification
Run-to-Run
In-Situ Control
Control
Fault Prediction
Culture change
Fault Detection
EEC
& Classification
*Equipment
Engineering
Contribution
TheThe PresentPresent

Wafer Quality

(Yield)

Very Edge control

Real-time monitoring

FDC/EES

Virtual Metrology

Fault Prediction

Real Time Feed Back

Virtual Metrology Fault Prediction Real Time Feed Back Tool control & Operation technol. Real-time control

Tool control & Operation technol.

Real-time control

Plasma for MEMS fabrication

Ultra hi density Ne:10 16 /cm 3

Radical: ~10 18 /cm 3

Thermal plasma, ATP

Real time prediction of fluctuation

Autonomous ajustment

Robot, Bio, Ecology
Robot, Bio, Ecology

MEMS

Max Aspect ration Precise 150 Hi Integration 250 Revolutional 500
Max Aspect ration
Precise
150
Hi Integration
250
Revolutional
500

50

Sensor, Mirror, Switch

Fusion w/Semi, Optics

500 / 50 um/min

Ultra hi-speed, directional etching

~ 500 / ~ 50 um/min Ultra hi-speed, directional etching Si /Quartz: ~ 300 / ~

Si /Quartz: 300 / 30 um/min

Thru via, both sides, 3D Large area, Ultra flatness :~1nm

New field

Magetic, Organic, Bio, Ecology

Low density Low temp/energy, Low damage, UV/VUV control

:~ 1nm New field Magetic, Organic, Bio, Ecology ・ Low density ・ Low temp/energy, Low damage,

Plasma Nanoarchitectronics a way towards SAFE, CLEAN, and ENVIRONMENTALLY FRIENDLY nanotechnology

SAFE, CLEAN, and ENVIRONMENTALLY FRIENDLY nanotechnology  Constantly raising concerns about nano-safety issues 

SAFE, CLEAN, and ENVIRONMENTALLY FRIENDLY nanotechnology  Constantly raising concerns about nano-safety issues 

Constantly raising concerns about nano-safety issues

 Plasma nanotech offers safe, clean, and green solutions:
 Plasma nanotech offers safe, clean, and green solutions:

Plasma nanotech offers safe, clean, and green solutions:  Vacuum processing – no human exposure 

Vacuum processing no human exposure

 No chemical vaste (all “burns”)
 No chemical vaste (all “burns”)
no human exposure  No chemical vaste (all “burns”)  Surface supported nanoparticles – nothing to

Surface supported nanoparticles nothing to inhale

“burns”)  Surface supported nanoparticles – nothing to inhale  Hazards “burn” yet no CO 2
 Hazards “burn” yet no CO 2 emission
 Hazards “burn” yet no CO 2
emission

CONCLUSIONS

Plasma – “nano-pioneer” (nano-etching, CNTs)

Self-organized arrays/devices are vitally needed

Deterministic non-equilibrium nanoarchitectronics based on guided self-organization is the way to achieve these goals

Non-equilibrium low-temp plasma environments offer

many exciting possibilities to enable determinism

Platform for future SAFE and GREEN nanotechnologies

A lot of exciting work ahead to solve the Grand

Challenges for the Science and Imagination!

GREEN nanotechnologies  A lot of exciting work ahead to solve the Grand Challenges for the

More details: Kostya.Ostrikov@csiro.au

More details: Kostya.Ostrikov@csiro.au

Magnetic control factors of self-organization [Meletis and Jiang, JNN 6, 1-4 (2006)]

Magnetic control factors of self-organization [Meletis and Jiang, JNN 6, 1-4 (2006)] nanocolumns Co NPs DLC
nanocolumns Co NPs DLC
nanocolumns
Co NPs
DLC
Solar cells: low dimensional single junction
Solar cells: low dimensional single junction

Plasma

Solar cells: low dimensional single junction Plasma p-type substrate Si (b) Plasma on p-type substrate Si

p-type

substrate

Si

(b) Plasma on

p-type

substrate

Si

(a) Before

p - (n)-type Si p-type Si substrate
p - (n)-type Si
p-type Si substrate

(c) After

E

(a) Before p - (n)-type Si p-type Si substrate (c) After E  The maximum open-circuit

The maximum open-circuit voltage V oc is 522 mV, and the corresponding fill factor is

80.8%.

V oc strongly depends on the r the shape of the structure.

Solar cells: single junction
Solar cells: single junction
Solar cells: single junction (b) V o c =287 mV; FF=76.7% (e) V o c =480
Solar cells: single junction (b) V o c =287 mV; FF=76.7% (e) V o c =480

(b) V oc =287 mV;

FF=76.7%
FF=76.7%

(e) V oc =480

FF=79.2%

mV;

(a) V oc =116 mV;

FF=39.1%
FF=39.1%

(d) V oc =453 mV;

FF=82.1%

o c =116 mV; FF=39.1% (d) V o c =453 mV; FF=82.1% (c) V o c

(c) V oc =347 mV;

FF=77.4%
FF=77.4%

(b) V oc =522 mV;

FF=80.8%

c =116 mV; FF=39.1% (d) V o c =453 mV; FF=82.1% (c) V o c =347
Collaboration with IHPC – plasmonic enhancement Size, density, and arrangement of metal NPs are VERY

Collaboration with IHPC plasmonic enhancement

Collaboration with IHPC – plasmonic enhancement Size, density, and arrangement of metal NPs are VERY important!

Size, density, and arrangement

of metal NPs are

VERY important!

Size, density, and arrangement of metal NPs are VERY important! Akimov, Koh, Ostrikov, Optics Express 17
Size, density, and arrangement of metal NPs are VERY important! Akimov, Koh, Ostrikov, Optics Express 17

Akimov, Koh, Ostrikov, Optics Express 17, 10195 (2009).

Size, density, and arrangement of metal NPs are VERY important! Akimov, Koh, Ostrikov, Optics Express 17

Nuclear fusion device (DPF) for making ZnO nanoparticles 100% made of ions and featuring room-temp PL !!!

100% made of ions and featuring room-temp PL !!! [a] Malhotra, Roy, Srivastava, Kant, Ostrikov [submitted

[a]

100% made of ions and featuring room-temp PL !!! [a] Malhotra, Roy, Srivastava, Kant, Ostrikov [submitted

Malhotra, Roy, Srivastava, Kant, Ostrikov [submitted to J. Phys. D, May 2009]

of ions and featuring room-temp PL !!! [a] Malhotra, Roy, Srivastava, Kant, Ostrikov [submitted to J.

OUTLINE:

OUTLINE: 1. PLASMA NANOSCIENCE - AREA WE WORK IN 2. GRAND CHALLENGE FOR NANOSCIENCE: INTRODUCING NON-EQUILIBRIUM

1. PLASMA NANOSCIENCE - AREA WE WORK IN

2.

GRAND CHALLENGE FOR NANOSCIENCE: INTRODUCING NON-EQUILIBRIUM NANOARCHITECTRONICS

NANOSCIENCE: INTRODUCING NON-EQUILIBRIUM NANOARCHITECTRONICS 3. WHY PLASMA AND WHAT CAN PLASMA/IONS/E-FIELDS DO? 4.
NANOSCIENCE: INTRODUCING NON-EQUILIBRIUM NANOARCHITECTRONICS 3. WHY PLASMA AND WHAT CAN PLASMA/IONS/E-FIELDS DO? 4.

3. WHY PLASMA AND WHAT CAN PLASMA/IONS/E-FIELDS DO?

3. WHY PLASMA AND WHAT CAN PLASMA/IONS/E-FIELDS DO? 4. IMPLEMENTATION: TAILOR – ARRANGE – CONNECT 5.

4. IMPLEMENTATION: TAILOR ARRANGE CONNECT

5. MORE RESULTS AND EXAMPLES OF APPLICATIONS

6. SO, WHERE IS THE CUTTING EDGE AND WHERE WILL IT

LEAD TO?
LEAD TO?
– CONNECT 5. MORE RESULTS AND EXAMPLES OF APPLICATIONS 6. SO, WHERE IS THE CUTTING EDGE
Our International Network: > 15 countries
Our International Network: > 15 countries

Rochester Uni Technol, USA

Chartered

Semiconductors

MFG

Zhejiang, China

NTU, NIE Singapore
NTU, NIE
Singapore

NUS, IHPC, IMRE,

IME (Singapore)

Uni Sydney, AUS

Singapore NUS, IHPC, IMRE, IME (Singapore) Uni Sydney, AUS SJTU, China Uni Sydney, AUS Josef Stefan
Singapore NUS, IHPC, IMRE, IME (Singapore) Uni Sydney, AUS SJTU, China Uni Sydney, AUS Josef Stefan
SJTU, China Uni Sydney, AUS Josef Stefan Inst, Slovenia, EU PNCA@ Uni Michigan, USA Ruhr-Uni,
SJTU, China
Uni Sydney, AUS
Josef Stefan Inst,
Slovenia, EU
PNCA@
Uni Michigan,
USA
Ruhr-Uni,
Germany, EU
EU PNCA@ Uni Michigan, USA Ruhr-Uni, Germany, EU Kharkiv National Uni + Natl Aerospace Uni, Ukraine

Kharkiv National Uni + Natl Aerospace Uni, Ukraine

Nagoya Uni, Japan Plasma Nanotech CoE

LHMTI, Belarus

George Washington Uni, USA

Fudan Uni, China

Huazhong Uni, China

Uni Delhi, India

Nanocrystalline Si for PV solar cells applications
Nanocrystalline Si for PV solar cells applications

J sc (mA/cm 2 )

Si for PV solar cells applications J sc (mA/cm 2 ) Cover image: J. Mater Chemistry

Cover image: J. Mater Chemistry (June 2009)

600 500 400 300 200 100 2007 2008 2009 V oc (mV)
600
500
400
300
200
100
2007
2008
2009
V oc (mV)

Year

28

24

20

16

12

8

4

0

image: J. Mater Chemistry (June 2009) 600 500 400 300 200 100 2007 2008 2009 V