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 and
Engineering, and Honorary Professor, University of
Sydney, AUSTRALIA
 5 out 25 top cited
in NANO!!!
20

% of Total Papers published

Plasma* AND Fusion*
Plasma* AND Astro*
16 Plasma* AND Dust*
Plasma* AND Nano*
Plasma* AND Chemistry*
12

area we work in 0
0 5 10
Year (from 1990)
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.
 Some examples of lab-based
highly-controlled synthesis of
nanoscale objects

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

Bio-
Incident light

Ag Islands

Amorphous
material

insulator
Si
Scientific approach: “Architecture” – Order –
Make uniform – Connect
 Extremely difficult to do for very small
nanostructures (e.g., QDs)

Poor ordering … Unpredictable

shapes…

Uncontrollable behaviour …
 REASON:

LARGE (>100 nm) NANOPARTICLES ARE

TRAPPED IN ANY STATE THEY WERE CREATED

SMALL (<10 nm) NANOPARTICLES

RETURN TO EQUILIBRIUM SHAPE *

* at least to the next available metastable state closer to equilibrium

 Solution

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!]

 Low temperature plasmas: a unique
non-equilibrium system
N
Electrons
Neutral
Gas
Ions

Energy, W 0
0.025 eV 2 eV
• Electrons not in thermal equilibrium with the ions or neutrals
• High Te dissociates gas
• Low TG and T+ protects substrates
• Negative charge on surfaces protects them from high 10
electron energy
 MORE UNIQUE FEATURES
Te >> Ti > Tn Nn >> Ni ~ Ne
 Higher complexity system – good for self-organization
(more effective driving forces)
 Electric fields
 Long-range Coulomb interactions
 Polarization interactions
 Isotropic vs anisotropic pressure PLASMA – COMMON
 Non-equilibrium cooling/heating ) INDUSTRIAL TOOL
 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?
FOR STARTERS: CNTs DISCOVERED
IN A PLASMA
Unique vertical alignment of CNTs! Plasma
route
Neutral
route

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

Z. Ren et al Science 1998: vol. 282. no. 5391, pp. 1105 - 1107 .
Plasma (nano)etching – common industrial process!

PPAP 4,
612 (2007)
 Highly-unusual metastable nanomaterials and nanophases

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

  Controlled delivery and redistribution of building units
 Control of surface energetics, diffusion, desorption, etc.

Ie+Ii Ie+Ii=0

ffloat
Us
 NON-Equilibrium heating and stress

eU s 3 / 4 3 / 4
T    ,
kb
Substrate heating due
to ion flux, φ [ML/s]

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

ENABLING A DETERMINISTIC APPROACH
 Non-equilibrium plasma turns
I. SHAPING things upside down
No plasma (no H-termination)

Si cube is least stable, “unwanted”

Effective H-termination

Single crystal, cubic shape silicon

nanocrystals produced in a non-equilibrium Si cube is most stable, “wanted”
plasma [U. Kortshagen et al., JNN 9, 39
(2007)] A. Barnard, P. Zapol, J. Chem.
B. Phys. 121, 4276 (2004)

T. Hawa, M. R. Zachariah,
J. Phys. Chem. C 112,
14796 (2008)
 Tailoring Si nanocones and nano-
pyramids in Ar + H2 plasma
(S. Y. Huang, S. Xu, I. Levchenko,
K. Ostrikov, 2009)

Si (100) Si (111)
 PV – collaboration with PSAC NIE/NTU [S. Xu et al.]
What does this mean for PV solar cells?

Pseudo Light IV curve w ithout the effect of Rs Pseudo Light IV curve w ithout the effect of Rs
Pseudo Light IV curve w ithout the effect of Rs

0.04

0.035
Voc= 116 mV 0.009
Voc= 347 mV
0.04

0.035
0.019 Voc= 453 mV
0.04 0.019

0.035
Power Density (W/cm2)

0.03

Power Density (W/cm2)

Power Density (W/cm2)

0.03 0.03
Current (A/cm 2)

Current (A/cm 2)

Current (A/cm 2)
0.025 0.025 0.025

0.02 0.02 0.009 0.02 0.009

0.015 0.015 0.015

0.01 0.01 0.01

0.005 0.005 0.005

0 0.000 0 0.000 0 0.000

0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.00 0.10 0.20 0.30 0.40 0.50
Voltage (V) Voltage (V)
Voltage (V)

Ar : H2=1 : 3; Ar : H2 = 1 : 3;
Ar : H2 = 9 : 1; Pin = 2.0 kW;
Pin =1.5 kW;
Pin= 2.0 kW; T = 300K, T = 300 K; t=30min;
T = 300 K; t =30 min;
t=30 min; Vb=0. Vb= - 50V
Vb= - 50V
Tailoring iron oxide nanowires and nanobelts [U. Cvelbar, K.
Ostrikov, Crystal Growth Design 8, 4347 (2008)]
 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)]
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)]
Simultaneous Ni catalyst saturation [I. Levchenko and
K. Ostrikov, Appl. Phys. Lett. 92 (2008)]

Arrows show larger

relative ion flux

More uniform CNT arrays !

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
equilibrium leads to more complex geometries [Whitesides and
Grzbowski, Science 295, 2418 (2002)]

No plasma With plasma

S. Y. Huang, J. D. Long, S. Xu, K. Ostrikov (2008):

self-ordering of SiC nanoislands (electric ordering factors)
 Self-Organized Carbon Connections
Between Ag Nanoparticles via
III. CONNECTING 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
IEEE Trans Plasma Sci. 36, 866 (2008)
 This will eventually lead to … nano-
architectured self-assembled nanoscale
systems
applications
 Links to other academic and industrial areas
Surface Quantum Materials
science information Re‟new‟wable science
Plasma energy Photonics Life
Nano-
physics sciences
science Nano-
Astrophysics electronics Chemistry
Opto-
electronics Medicine

Sensors Bio-implants
Nano-
Advanced Integrated
Plasma devices
materials circuitry Nanotools
medicine
Electrochem. Coatings Lasers
Environmental
batteries Plasmonic
remediation
structures
LEDs Chemical Solar cells Drug/gene
synthesis delivery
Catalysis Biomarkers
 Applications: some examples
“Self-organised”
Nanoelectronics

Multipurpose CNTs Ultra-nanoporous materials

Optoelectronics/Photonics

GAS SENSORS

BIOIMPLANTS

E-mail: Kostya.Ostrikov@csiro.au
PV – collaboration with PSAC NIE/NTU [S. Xu et al.]
Plasmonic arrays

TCO
µc-Si

Si thin film solar cell

PV SOLAR CELLS Photo-active layers

Plasma control of nanostructured phases in nc-Si for PV solar cells
[Cryst Growth Design 9, 2863 (2009); Nanotechnology 20,
215606 (2009); J. Mater. Chem. (2009) DOI: 10.1039/b904227j]
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]
100oC 0 – 86% cryst phase
Very high growth rates
+ bandgap control

200oC
Cryst phase
Amorph phase

300oC

Also: 1) no hydrogen dilution possible! 2) excellent

transmittance in optical range
Onset of nanocrystallinity + nanophase control
 Challenges,
grand or small,
all lead to
breakthrough
 Transforming matter by controlled surface hydrogenation
(“what amazing things can the plasma do!”)

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

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

Big challenges:
Hydrogenation of graphene (inert and 1) Epitaxial self-assembled graphene
conducting) in Ar + H2 DC plasma 2) Precise control of surface
leads to graphane (dielectric) energetics
3) Switch-over between TD and
Image: A. Savchenko, Science 323, 589 (2009) kinetic modes
A plasma knife can cut the nanotubes to create GNRs

Ar plasma (~10s)

Graphene Nanoribbons (GNRs):

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

Big challenges:
1) understanding ion-CNT
interactions
2) How to make it precise and
“gentle”?
 Superhydrophobic a-C/CNT composites via ion bombardment
[Han, Tay, Shakerzadeh, Ostrikov, APL 94, 223106 (2009)]

CA ~
150 – 170o

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!

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

 Control of SWCNTs

Remote PECVD, 90% H2 + 10% CH4,

15 mbar, 400-650oC; 0.5 nm Al / 0.5-1
nm Fe / 10 nm Al 70% purity (30% a-C)
Metallic / Semicond = 1:2
Challenges: chirality control; selective
elimination of metallic or semicond.
J. Robertson et al. APL 93, 163911 (2008) tubes
Example of solution: burning metallic SWCNTs

M. Keidar et al., Carbon

44, 1022 (2006);

K. Ostrikov and A. B. Murphy,

J. Phys. D 40, 2223 (2007)

But how to
select
any particular
chirality?
 Solution: grow thinner SWCNTs much faster than others!

NEUTRAL CVD

PECVD PECVD

E. Tam and K. Ostrikov (June 2009); see

also APL 93, 261504 (2008)

PECVD

NEUTRAL CVD
Towards epitaxial graphene

High-pressure Ar
atmosphere

Si sublimates leaving
exfoliated graphene behind

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

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

 Control of Si sublimation through polarization effects:
the ionization theory approach [Phys Lett A 373, 2267 (2009)]

Si atoms tend to diffuse and evaporate faster than C.

Electric field/Polarizability – additional way to control!
GRAND CHALLENGES
1)

2)

3)

4)

5)
 JSAP/NEDO Roadmap:Plasma Process Technology
2010 2020 2030 2040
Products, Application

Device dimension 35nm 25nm 10nm 5nm 2.5nm 1nm

Output

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
Development

Engineering makes Seeds(Principle) to Production Technology

Manufacturing
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
Research

Principle of Surface Reaction 1 Atom/Molecule Control Control of Functional Unit Organic/Bio Material
Monochroic Flux Vertical/Lateral Atomically-controlled Depo/Etch Bio Molecular Manipulation
Seeds

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
Perfect No-Defect Hi-Speed Self- Synergic Reaction in Large area
Common Basic Technology 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
 Sub map for Plasma Process Technology
Process Simulation
2010 2020 2030 2040
Products, Application
Output

Learning・Adaptive
Ｚ
Interactive type software
control software

Diagnostics ・ Visualization support tool

Development
Manufacturing
technology

Linkage with experiments, experiment control (Validation of simulation)

Rule mining (Estimation for law of physics & chemistry via simulation)

Molecule scale（Molecular dynamics）

Seeds
Research

Multi scale （Space, Time）

Mesoscopic scale （Fluid・ Stochastic method） Simulation
Micro scale （Continuous model）
Fundamentals

Approximation・Modeling Technique including first-principle simulation

High speed algorithm

Collection & compile of Fundamental data（Cross-section, Potential, transport co. ,…）
 Sub map for Plasma Process Technology
Micro fabrication Atom･Molec. Process
Plasma for
Atom, molecule ＋
Nano process process control Self-assembled Reaction
2010 2020 2030 2040
Tr.Gate siza 25nm 18 13 9 6 4.2 2.9 2.1 1.4 1.0

CMOS Miniaturization
Model for process control
Precise <±1.0nm以下 Prediction・simulation
±3.0nm ±2.0nm Low damage
etching （Lower limitation）
Fundamental database Tool monitoring
（Crosssection, Reactivity,…）
Large area 675mmΦ
300mmΦ 450mmΦ Large wafer Very Edge control
Real-time monitoring

Tool control & FDC/EES

Effect for Run-to-Run In-Situ Control Real-time control
Operation technol. Equipment
Availability
Control Virtual Metrology
(Productivity)
Fault Prediction
Culture change
Fault Prediction
Fault Detection
& Classification
EEC Real Time Feed Back
*Equipment
Engineering
Contribution
The Present
Plasma for MEMS fabrication
Wafer Quality
ピ プロセス特性
(Yield)
・Ultra hi density Ne:～1016/cm3
Real time prediction of fluctuation Autonomous ajustment Radical： ～1018/cm3
・Thermal plasma, ATP
Max Aspect ration
MEMS Precise 150 Hi Integrationレシピ 250 Revolutional
プロセス特性 500
50 Fusion w/Semi, Optics Robot, Bio, Ecology
Sensor, Mirror, Switch
Ultra hi-speed, directional etching Si /Quartz: ～300 / ～30 um/min ～500 / ～50 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
 Plasma Nanoarchitectronics – a way towards
SAFE, CLEAN, and ENVIRONMENTALLY
FRIENDLY nanotechnology
 Constantly raising concerns about nano-safety issues
 Plasma nanotech offers safe, clean, and green solutions:

 Vacuum processing – no human exposure

 No chemical vaste (all “burns”)

 Surface supported nanoparticles – nothing to inhale

 Hazards “burn” yet no CO2
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!
More details: Kostya.Ostrikov@csiro.au
Magnetic control factors of self-organization
[Meletis and Jiang, JNN 6, 1-4 (2006)]
nanocolumns

Co NPs

DLC
 Solar cells: low dimensional single junction

Plasma

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

(a) Before (b) Plasma on (c) After

 The maximum open-circuit

voltage Voc is 522 mV, and the
corresponding fill factor is
80.8%.
 Voc strongly depends on the r
the shape of the structure.
 Solar cells: single junction

(a) Voc=116 mV; (b) Voc=287 mV; (c) Voc=347 mV;

FF=39.1% FF=76.7% FF=77.4%

(d) Voc=453 mV; (e) Voc=480 mV; (b) Voc=522 mV;

FF=82.1% FF=79.2% FF=80.8%
 Collaboration with IHPC – plasmonic enhancement

Size, density,
and arrangement
Akimov, Koh, Ostrikov,
of metal NPs are
Optics Express 17,
VERY important!
10195 (2009).
Nuclear fusion device (DPF) for making ZnO nanoparticles
100% made of ions and featuring room-temp PL !!!

[a]

Malhotra, Roy, Srivastava, Kant, Ostrikov [submitted to

J. Phys. D, May 2009]
OUTLINE:

1. PLASMA NANOSCIENCE - AREA WE WORK IN

2. GRAND CHALLENGE FOR NANOSCIENCE: INTRODUCING

NON-EQUILIBRIUM NANOARCHITECTRONICS

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

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?
 Our International Network: > 15 countries
NUS, IHPC, IMRE,
Rochester Uni Zhejiang, China IME (Singapore)
Technol, USA
Chartered NTU, NIE
Semiconductors Singapore Uni Sydney, AUS
MFG

SJTU, China Uni Sydney, AUS Josef Stefan Inst,

Slovenia, EU
PNCA@
LHMTI, Belarus Uni Michigan, Ruhr-Uni,
USA Germany, EU Nagoya Uni, Japan
George Plasma Nanotech
Washington Kharkiv National Uni + Natl CoE
Uni, USA Aerospace Uni, Ukraine

Fudan Uni, China Huazhong Uni, China Uni Delhi, India

 Nanocrystalline Si for PV solar cells applications

28
600
24
500 20

Jsc (mA/cm )
Voc (mV)
400 16

300 12

2
8
200
4
100
0
2007 2008 2009
Year

Cover image: J. Mater Chemistry (June 2009)