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!!!
% of Total Papers published

20 16 12 8 4 0

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

area we work in
0 5

10

15

Year (from 1990)

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 plasmabased 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 Nanoarchitectronics: 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

0.025 eV

2 eV

Energy, W 0

• • • •

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 PLASMA – COMMON Isotropic vs anisotropic pressure 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?

FOR STARTERS: CNTs DISCOVERED IN A PLASMA

Unique vertical alignment of CNTs!
Neutral route

Plasma 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

Us

ffloat

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

I. SHAPING

Non-equilibrium plasma turns 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 plasma [U. Kortshagen et al., JNN 9, 39 (2007)]

Si cube is most stable, “wanted”
A. B. Barnard, P. Zapol, J. Chem. Phys. 121, 4276 (2004)

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

Tailoring Si nanocones and nanopyramids 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

0.04 0.035 0.03
Current (A/cm 2)

Voc= 116 mV

0.009

Voc= 347 mV
0.04 0.035 0.03
Current (A/cm 2)

0.019

0.035

Voc= 453 mV
0.04 0.03 0.02 0.01

Pseudo Light IV curve w ithout the effect of Rs

0.019

Power Density (W/cm2)

Power Density (W/cm2)

0.025 0.02 0.015 0.01 0.005 0 0.00

0.025 0.02 0.015 0.01 0.005

0.025

0.009

0.009

0.015

0.005

0.05

0.10

0.15

0.20

0.000 0.25

0 0.00

0.05

0.10

0.15

0.20 Voltage (V)

0.25

0.30

0.35

0.000 0.40

0 0.00

0.10

0.20

0.30

0.40

0.000 0.50

Voltage (V)

Voltage (V)

Ar : H2=1 : 3; Ar : H2 = 9 : 1; Pin =1.5 kW; Pin= 2.0 kW; T = 300K, T = 300 K; t =30 min; t=30 min; Vb=0. Vb= - 50V

Ar : H2 = 1 : 3; Pin = 2.0 kW; T = 300 K; t=30min; Vb= - 50V

Power Density (W/cm2)

Current (A/cm 2)

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)

III. CONNECTING

Self-Organized 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

IEEE Trans Plasma Sci. 36, 866 (2008)

This will eventually lead to … nanoarchitectured self-assembled nanoscale systems

applications

Links to other academic and industrial areas
Materials Surface Quantum science science information Re‟new‟wable energy Photonics Plasma Life Nanophysics sciences science NanoAstrophysics electronics Chemistry OptoMedicine electronics Sensors Advanced Integrated Plasma materials circuitry medicine Nanodevices Bio-implants Nanotools

Electrochem. Coatings Lasers Environmental Plasmonic batteries remediation structures Chemical Solar cells Drug/gene LEDs synthesis delivery Catalysis Biomarkers

Applications: some examples
“Self-organised” Nanoelectronics

Multipurpose CNTs

Optoelectronics/Photonics

Ultra-nanoporous materials

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 Very high growth rates 0 – 86% cryst phase + bandgap control

200oC
Amorph phase

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

Hydrogenation of graphene (inert and conducting) in Ar + H2 DC plasma leads to graphane (dielectric) Image: A. Savchenko, Science 323, 589 (2009)

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
Products, Application
Device dimension 35nm 25nm

2020
10nm

2030
5nm 2.5nm

2040
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

Manufacturing technology

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

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 SelfSynergic 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

Process Simulation
2010
Products, Application

Sub map for Plasma Process Technology

2020

2030

2040

Output

Interactive type software Z

Learning・Adaptive control software

Development

Diagnostics ・ Visualization support tool
Linkage with experiments, experiment control (Validation of simulation) Rule mining (Estimation for law of physics & chemistry via simulation)

Manufacturing technology

Research

Seeds

Molecule scale(Molecular dynamics) Mesoscopic scale (Fluid・ Stochastic method) Multi scale (Space, Time) 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. ,…)

Micro fabrication
Plasma for Nano process
2010
Tr.Gate siza 25nm 18

Sub map for Plasma Process Technology

Atom, molecule process control
2020
13 9 6

Atom・Molec. Process + Self-assembled Reaction
2030
4.2 2.9 2.1 1.4

2040
1.0

CMOS
Precise etching
±3.0nm ±2.0nm

Miniaturization
Model for process control

<±1.0nm以下 Prediction・simulation (Lower limitation) Fundamental database 675mmΦ

Low damage

Tool monitoring (Crosssection, Reactivity,…)

Large area
300mmΦ 450mmΦ

Large wafer

Very Edge control Real-time monitoring FDC/EES Virtual Metrology Fault Prediction Real Time Feed Back

Tool control & Operation technol.

Effect for Equipment Availability (Productivity)

Run-to-Run Control

In-Situ Control

Real-time control

Fault Prediction Culture change Fault Detection & Classification EEC *Equipment
Engineering Contribution

The Present

Plasma for MEMS fabrication
Wafer Quality (Yield)

プロセス特性

Real time prediction of fluctuation

Autonomous ajustment

・Ultra hi density Ne:~1016/cm3 Radical: ~1018/cm3 ・Thermal plasma, ATP

MEMS

Max Aspect ration

50

レシピ プロセス特性 Revolutional Precise 150 Hi Integration 250 500 Fusion w/Semi, Optics Robot, Bio, Ecology Sensor, Mirror, Switch

Ultra hi-speed, directional etching

Si /Quartz: ~300 / ~30 um/min ・Large area,

~500 / ~50 um/min

・Thru via, both sides, 3D

・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

 Plasma – “nano-pioneer” (nano-etching, CNTs)  Self-organized arrays/devices are vitally needed

CONCLUSIONS

 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
p-type substrate Si p-type substrate Si p-type Si substrate

E

(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; FF=39.1%

(b) Voc=287 mV; FF=76.7%

(c) Voc=347 mV; FF=77.4%

(d) Voc=453 mV; FF=82.1%

(e) Voc=480 mV; FF=79.2%

(b) Voc=522 mV; FF=80.8%

Collaboration with IHPC – plasmonic enhancement

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

Size, density, and arrangement of metal NPs are VERY important!

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
Rochester Uni Technol, USA Chartered Semiconductors MFG SJTU, China
LHMTI, Belarus

Zhejiang, China NTU, NIE Singapore Uni Sydney, AUS PNCA@ Ruhr-Uni, Germany, EU

NUS, IHPC, IMRE, IME (Singapore)
Uni Sydney, AUS Josef Stefan Inst, Slovenia, EU Nagoya Uni, Japan Plasma Nanotech CoE Uni Delhi, India

Uni Michigan, USA

George Washington Uni, USA Fudan Uni, China

Kharkiv National Uni + Natl Aerospace Uni, Ukraine Huazhong Uni, China

Nanocrystalline Si for PV solar cells applications
28 600 500
Voc (mV)

24 20 16 12 8 4 0 2007 2008 Year 2009
Jsc (mA/cm )

400 300 200 100

2

Cover image: J. Mater Chemistry (June 2009)

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