CONTINUITY IN PLASMA PROCESSING:

YESTERDAYS ACCOMPLISHMENTS, TODAYS

INNOVATIONS, TOMORROWS CHALLENGES*
Mark J. Kushner
University of Illinois
Dept. of Electrical and Computer Engineering
Urbana, IL 61801
mjk@uiuc.edu http://uigelz.ece.uiuc.edu
November 2003

* Work supported by SRC, NSF, Sematech, GE and EPRI

AVS03_01

ACKNOWLEDGEMENTS

Andre Anders
Eray Aydil
Kurt Becker
Ned Birdsall
Matt Blain
Nick Braithwaitte
Jane Chang
Frank Chen
Joel Cook
J. Gary Eden
Brett Cruden
Ashok Das
Rajesh Dorai

AVS03_02

Pietro Favia
Bish Ganguly
Valery Godyak
Matt Goeckner
Martin Gundersen
Bill Holber
Alan Howling
Fred Huang
Ulrich Kogelschatz
Uwe Kortshagen
Toshiaki Makabe
Joelle Margot
Dennis Manos

Tom Mantei
Jim Olthoff
Larry Overzet
Ajit Pranjpe
Zoran Petrovic
Louis Rosocha
Karen Seward
Phillipe Schoeborn
Tim Sommerer
L. Tsendin
Peter Ventzek
David Wharmby
Gerald Yin

University of Illinois
Optical and Discharge Physics

AGENDA
What is our legacy in plasma processing?
How have we leveraged that legacy to innovate plasma based
technology?
What challenges and opportunities lie ahead for plasma
technologies? (50th Anniversary PSTD Talks)
Materials Processing and Sources (R. Gottscho, F. Chen, T.
Dalton, J. Schmitt, H. Sawin)
Diagnostics (V. Donnelly)

Lighting
Nanoscience
Bioscience

Concluding remarks

AVS03_03

University of Illinois
Optical and Discharge Physics

WORKING DEFINITION OF PLASMA PROCESSING

Technological plasmas are a power transfer media.
Electrons transfer power from the "wall plug" to internal modes of
atoms / molecules to make benign species into reactive species.
WALL
PLUG
ENERGETIC
ELECTRONS
POWER
CONDITIONING

E
ELECTRIC
FIELDS

COLLISIONS WITH
ATOMS/MOLECULES
A
EXCITATION,
IONIZATION,
DISSOCIAITON
(CHEMISTRY)

PHOTONS
RADICALS
IONS

LAMPS
LASERS
ETCHING
DEPOSITION

Once activated, their physical or chemical potential may be used to

make products (add or remove materials, photons)
Plasma processing is the use of partially ionized gases in
technology to create "products."
AVS03_
AVS03_04

University of Illinois
Optical and Discharge Physics

COLLISIONAL LOW
TEMPERATURE PLASMAS

Thrusters

Lighting

Spray Coatings

Materials
Processing
UTA_1102_05

Displays

CONTINUITY IN PLASMA TECHNOLOGY

Our striking record of innovation in developing plasma based

technologies has relied on leveraging a continuity of progress
through generations of these technologies.

AVS03_05

University of Illinois
Optical and Discharge Physics

(a very incomplete) TIME LINE:

OUR ROOTS IN SCIENCE

1790' s
1830' s
1850' s
1850' s
1880' s
F. Hawsbee

M. Faraday
W. R. Grove W. Siemens W. Crooke
First Glow Discharges Glow Discharges
Sputtering
DBDs
Breakdown
1880' s
1890' s
1900' s
1920' s
1920' s
W. Hittroff
N. Tesla
J. S. Townsend L. Tonks, I. Langmuir P. Debye
ICPs
RF Discharges
Transport
Sheaths, Plasma
Shielding
1920' s
1930' s
1940' s
J. J. Thomson, G. I. Babat
W. Allis

S. C. Brown

ICPs
Distribution Functions Microwave Plasmas
1950' s
1950' s
1960' s
Lax, Allis, Brown Bernstein & Holstein
A. Phelps
ECR
Modern Transport
Modern Gaseous Electronics

R. Powell, S. Rossnagel, PVD for Microelectronics

J. Hopwood and T. Mantei, JVSTA, 2003
Y. P. Raiser, Gas Discharge Physics
J. R. Roth, Industrial Plasmas Part I
Joel Cook, private communication.

AVS03_06

D. Manos, D. Flamm, Plasma Etching: An Introduction

J. Waymouth Electric Discharge Lamps
J. Hecht, Laser Pioneer Interviews
J. Schmitt, AVS 50th Symposium
www.siemens.com

PLASMA MATERIALS PROCESSING:

WHAT DO WE DO WELL?
The fabrication of conventional microelectronics has met and
bested extreme challenges as the nm scale is approached and
exceeded.
Plasma science has played a critical role in virtually all aspects
of meeting these challenges

AVS03_07

Physical Vapor Deposition

Plasma Enhanced Chemical Vapor Deposition
Etching
Cleaning
Passivation
Plasma sources of UV radiation for lithography (Hg lamps
to EUV)
University of Illinois
Optical and Discharge Physics

(very incomplete) TIME LINE:

1960' s
Sterling & Swann

MATERIAL PROCESSING

1970' s
1970' s
1970' s
S. Irving A. R. Reinberg R. A. Heinecke
Photoresist
Selectivity
PECVD
Diode Etcher
Stripping
1950' s
Lax, Allis, Brown - ECR

1970' s
1970' s
1980' s
1990' s
1990' s
Coburn & Winters Batch Processing Single Wafer
Ogle, Keller
ECR
Ion Activation
Bell Labs
Tegal
Planar ICP

1880' s - Hittrof - ICPs

1990' s
1990' s
1990' s

S. Rossnagel
Helicon/PMT Multifrequency RIE
Ionized Metal PVD

Chen, Boswell Helicon

1850' s Grove Sputtering
AVS03_08

Ref: J. P. Chang

Ref: J. P. Chang

ADVANCES IN EQUIPMENT DESIGN ENABLES

ADVANCED DEVICE FABRICATION
Perhaps our most challenging accomplishments have been the
design of reliable plasma sources for these processes.
The continuity of progress through generations of advances in
plasma fundamentals, diagnostics, modeling and empiricism
have been leveraged to produce reliable manufacturing tools.

AVS03_09

University of Illinois
Optical and Discharge Physics

SOPHISTICATED PLASMA TOOLS

AMAT-Komatsu PECVD
AMAT Ionized Metal PVD
Ref: Ashok Das
AVS03_10

University of Illinois
Optical and Discharge Physics

Ref: W. Holber

Ref: R. Dorai

PLASMA DIAGNOSTICS HAVE PLAYED A CRITICAL

ROLE AND ARE MOVING CLOSER TO THE PRODUCT
Plasma process and equipment design have and will continue to
critically rely on advanced plasma diagnostics.
Real time control strategies, a requirement for sub-100 nm
processing, will also rely on robust, cost-effective diagnostics.
The most mature plasma diagnostics are typically too far
removed from critical measurements of activation of surface
processes.
Non-intrusive diagnostics which provide the state of activating
species impinging on surfaces are required for a complete
picture.

AVS03_11

University of Illinois
Optical and Discharge Physics

LANGMUIR PROBES IN HARSH ENVIRONMENTS

Development of basic diagnostics,
such as Langmuir probes, for use in
harsh rf environments improved our
knowledgebase and provided
stringent test of models.

RF CCP in Argon
Ref: V. Godyak
AVS03_12

University of Illinois
Optical and Discharge Physics

80 mTorr SF6, 200 W

Ref: E. Aydil

MATERIALS PROCESSING: CHALLENGES

New materials (metal gates, low-k dielectrics, high-k dielectrics,
SiGe/SOI substrates, porous materials).
Increasing demands on etch selectivity.
Shorter development cycle.
Lower thermal budgets.
More controllable knobs.
Use of plasmas as processing tools (e.g., self assembly) as
opposed to pattern replication.
Reduced cost of ownership through plasma tools which are
used for multiple processes.
Improved and more relevant contributions from modeling.
Ref: J. Cook, T. Mantei, P. Schenborn, P. Ventzek,
D. Manos
AVS03_13

University of Illinois
Optical and Discharge Physics

CHALLENGES IN TAILORING PLASMAS FOR

SELECTIVE ACTIVATION
As in most relationships, its all about control.
Advanced applications will depend on selectively promoting desired
plasma chemical reactions and preventing undesirable reactions.
The ability to tailor the energy distributions of plasma particles is
key to this selectivity.
Tailored electron energy distributions: Control formation of
radicals and ions; best if also spatially segregated.
Tailored Ion energy distributions: Determine activation of
surface processes; must be narrow to differentiate thresholds.
Tailored synergy between ions and neutrals: Necessary for
monolayer control of selectivity, deposition, end-point.

AVS03_14

University of Illinois
Optical and Discharge Physics

 f() 5 MHz

TAILORING f() BY FREQUENCY

Plasma tools for multiple processes or
recipes (different chemistries) require
control of electron energy distribution
for optimum generation of precursors.

f() 50 MHz

[e], ICP, 10 mTorr, Ar/Cl2 = 70/30.

AVS03_15

Model results from HPEM

Ref: K. Seaward, S. Samakawa

University of Illinois
Optical and Discharge Physics

TAILORING FLUXES THROUGH PULSING

Processing of thin films depends on the synergy between energetic
ions and radical fluxes. Pulsed plasmas which control these
contributions produce unique films not otherwise attainable.

Deposition of low-k
fluorocarbon film from
perfluoroallyl benzene [L.

Pulsed ICP Ar/C4F8=70/30, 15 mTorr

Han, JVSTB 18, 799 (2000)]

AVS03_16

Model results from GLOBAL_KIN

Ref: K. Seaward

University of Illinois
Optical and Discharge Physics

ROLE OF PLASMA SCIENCE TO MEET CHALLENGES

Multi-process plasma
tools with frequency
and pulse power agility
to selectively activate
species
On wafer and plasma
diagnostics which
enable real-timecontrol to submonolayer accuracy.
Self assembling nanostructures
Non-invasive MEMs based plasma sensors with L < D.

AVS03_17

University of Illinois
Optical and Discharge Physics

PLASMA LIGHTING TECHNOLOGIES

Annual US energy use for lighting is 750 TWH (8.2 quads)
8.3 % of total energy consumption
22% of total electrical energy consumption.
Plasmas are 59% of lighting energy use (13% of total). There
are 2.6 billion plasma lighting sources in the US.
Replacing incandescent lamps with plasma sources will
decrease US electrical energy use 5% [20 nuclear power
plants or 1.2 Million barrels of oil/day (10% of imports)].
Improving efficiencies and utilization of plasma lighting will
enormously impact our economy, environment, foreign
policy.
Ref: U.S. Lighting Market Characterization,
Navigant Consulting, 2002
DOE Annual Energy Outlook 2003
AVS03_18

University of Illinois
Optical and Discharge Physics

(very incomplete) TIME LINE:

1850' s
H. Giessler

Plasma Line radiation

1850' s
W. Siemens

DBDs, Ozonizers

1940' s

1930' s
Fluorescent Lamps

AVS03_19

LIGHTING TECHNOLOGIES

Low Pressure Hg

Excimers

1980' s
Blitzer & Slottow Elliason & Kogelshatz

Radiation Trapping

Commercial PDPs

1910' s
W. Curtis, F. Goldstein

1960' s

T. Holstein

1990' s

1900' s
P.C.Hewitt

Plasma Displays

DBD Excimer Lamps

2000' s
Vollkommer and Hitzschke
Excimer Flat Panel Lighting

LIGHTING: ACCOMPLISHMENTS AND CHALLENGES

Efficient white sources based on Hg plasmas in fluorescent and
arc lamps; and non-white metal vapor lamps. Environmental
impacts are debatable but not ignorable.
Challenges:
Highly efficient non-Hg plasma white-light sources (rare
gases, excimers, metal halides, molecular radiators)
Improving understanding of plasma-surface interactions to
extend lifetimes (cathodes)
Quantum splitting phosphors to improve utilization of UV (2
visible photons from 1 UV reduces US energy use 5-10%).
Leverage advances plasma lighting to other applications
(and vice-versa)
Solid State Lighting? (next talkM.G. Craford, Lumileds
Lighting)
AVS03_20

University of Illinois
Optical and Discharge Physics

ATMOSPHERIC PRESSURE PLASMAS

Atmospheric Pressure Plasmas
(APP) have had tremendous
technological impact
High power lasers (e.g.,
Excimer lasers)
Lighting Sources (e.g., HID
lamps)
Ozone generators
Modification of surfaces
Toxic gas abatement
The potential for APPs to perform
high value manufacturing is
literally untapped.
AVS03_21

Atmospheric pressure DBD

ozone generator
Ref: U. Kogelshatz
University of Illinois
Optical and Discharge Physics

PLASMA SURFACE MODIFICATION OF POLYMERS

Untreated PP

To improve wetting and adhesion of

polymers atmospheric plasmas are
used to generate gas-phase radicals
to functionalize their surfaces.

Hydrophobic
Plasma Treated PP

Hydrophilic

Polyethylene, Humid-air
Akishev, Plasmas Polym. 7, 261 (2002).
M. Strobel, 3M
AVS03_22

University of Illinois
Optical and Discharge Physics

POLYMER TREATMENT
PLASMA TOOL
Web based corona plasmas
treated sheet polymers for
improved surface
functionality.

Tantec Inc.
AVS03_23

University of Illinois
Optical and Discharge Physics

FUNCTIONALIZATION OF POLYPROPYLENE
Control of surface energy by plasma treatment results from
functionalization with hydrophilic groups.
Carbonyl (-C=O)
Peroxy (-C-O-O)

Alcohols (C-OH)
Acids ((OH)C=O)

Functionalization depends on process parameters such as

gas mix, energy deposition and relative humidity (RH).

Air, 300 K, 1 atm

AVS03_24

University of Illinois
Optical and Discharge Physics

OPPORTUNITIES: ATMOSPHERIC

PRESSURE PLASMAS
THE CHALLENGE

APPs provide the potential to selectively generate activated

species (radicals, ions and photons) for modification and
cleaning of surfaces.
Most (many) industrial processes performed with liquid solvents
could in principle be performed with APP generated radicals.
The environmental impact of eliminating liquid solvents for
cleaning of parts, removal of paint, functionalizing or sterilizing
surfaces would be immense.
Advanced concepts include improvement of combustion
processes, homeland defense (chemical and biological
remediation), and microplasma devices.

Ref: B. Ganguly
AVS03_25

University of Illinois
Optical and Discharge Physics

Ref: L. Rosocha

Ref: M. Gundersen

University of Illinois
Optical and Discharge Physics

In-situ H2 Generation for Small Scale (i.e. Low Power) Fuel

Cells Using a Microhollow Cathode Discharge
60

Partial Pressure (Torr)

Plasma on

Plasma off

50

NH 3

40

30

H2

20

N2

10

0
0

20

40

60

80

100

120

140

Time (min)

High throughput is facilitated by

microplasma arrays
Ref: Kurt Becker

THE ROLE OF PLASMAS IN BIOSCIENCE

Plasmas, to date, have played
important but limited roles in
bioscience.
Plasma sterilization
Plasma source ion
implantation for hardening
hip and knee replacements.
Modification of surfaces for
biocompatibility (in vitro and
in vivo)
Artificial skin
The potential for commodity use of
plasmas for biocompatibility is
untapped.
AVS03_26

Low pressure rf H2O2 plasma

(www.sterrad.com)
University of Illinois
Optical and Discharge Physics

cell adhesive surfaces

PE-CVD

-COOH functional coatings

PLASMA TREATMENT

N-grafted polymer surfaces

cell growth

covalent binding of molecules

KEY ISSUES
retention of monomer structure
low power, modulated discharges
process control
density of groups

NH3

COOH
CH2=C
H

-COOH

>C=O
-COOH

-OH

-OH
-COOH

>C=O

-COOH

-NH2

-CN

=NH

--OH

--NH2
-CN

>C=O

-CN

-NH2

stability

Ref: P. Favia

ATMOSPHERIC PRESSURE PLASMAS:THE CHALLENGE

Controlling functional groups on polymers through fundamental
understanding of plasma-solid interactions will enable
engineering large area biocompatible surfaces.
10,000 square miles of polymer sheets are treated annually with
atmospheric pressure plasmas to achieve specific functionality.
Cost: < $0.05 /m2
Low pressure plasma processing technologies produce
biocompatible polymers having similar functionalities.
Cost: up to $100s /cm2 ($1000s/cm2 for artificial skin)
Can commodity, atmospheric pressure processing technology
be leveraged to produce high value biocompatible films at low
cost? The impact on health care would be immeasurable.

AVS03_27

University of Illinois
Optical and Discharge Physics

THE ROLE OF PLASMAS IN NANOSCIENCE

Plasma science has been absolutely critical to the development
of conventional microelectronics structures.
What will the role of plasma science be in facilitating these
advances in truly nanoscale science and technology?
Atomic layer processing (etch and deposition)
Plasma aided lithography (trimming)
Selective activation or functionalization of materials on
molecular scales (inanimate and living)
Self- and directed-assembly
Commodity production of nanostructures

AVS03_28

University of Illinois
Optical and Discharge Physics

SELECTIVE, ALIGNED PLASMA

GROWTH OF CARBON NANOTUBES
Aligned CNT growth can be obtained
in a low pressure rf and dc plasmas
using different feedstocks.
Catalyst choice and configuration may
dominate.
RF Plasma (C2H4/NH3)

DC Plasma CVD

Ref: B. Cruden
Cruden et al., J Appl Phys, 12, 363 (2001).

DC Plasma (C2H2/NH3)

PLASMA BASED SELF- AND DIRECTED ASSEMBLY

J. Appenzeller et al, Trans. Nanotech. 1, 184 (2002)

W. Choi, Appl. Phys. Lett. 79, 3697 (2001)
J. Zou et al, Trans. Microw Theory Tech. 51, 1067 (2003)
M. Meyyappan et al, PSST 12, 205 (2003)
AVS03_29

University of Illinois
Optical and Discharge Physics

MODELING IMPROVES FUNDAMENTAL UNDERSTANDING:

ANAMOLOUS SKIN DEPTH EFFECTS IN ICPS

As plasma tools become more sophisticated and
reproducibility more critical, mastery of the fundamentals
becomes essential.

Ref: V. Godyak, Electron

Kinetics of Glow Discharges
AVS03_29

Ar, 10 mTorr, 7 MHz, 100 W

ANIMATION SLIDE

University of Illinois
Optical and Discharge Physics

Ref: V. Kolobov

Ref: F. Huang, P. Ventzek, P. Stout

CHALLENGE FOR MODELING AND SIMULATION

Challenge..Become a tool for design and optimization of
equipment and processes as reliable as Computational Fluid
Dynamics.
Requirements
Knowledge bases (cross sections, sticking coefficients):
The time required to generate knowledge bases for new
materials must be weeks-to-months, not months-to-years.
Manufacturing friendliness:
Autocad Prediction/Recommendation Autocad
Acceptance:
Realistic expectations and critical assessment of ROI (one
scrapped 300 mm wafer funds a modeling activity for a year).

AVS03_30

University of Illinois
Optical and Discharge Physics

THE CONTINUUM OF
PLASMA TECHNOLOGIES
Werner von
Siemens, 1872

Ozone Tube of W. Siemens

Annalen der Physik und Chemie (1857)

Ref: U. Kogelschatz,
www.siemens.com, www.samsung.com
AVS03_31

The road to PDPs began

in a lab in Germany in
1857
University of Illinois
Optical and Discharge Physics

STATUS OF OUR DISCIPLINE

The diversity of technological plasmas is its strength.

Interdisciplinary
Wide range of applications
Entry point from many educational backgrounds
Extraordinary economic and social impact

The weakness of this diversity is there is no recognized

discipline of plasma processing (as for fusion plasmas).
No home in funding agencies
Lack of formal programs in universities resulting in lack
of hiring priorities.
Excessive reliance on supporting disciplines
Often indirect path from academic innovation to
commercialization

AVS03_32

Ref: Frank Chen

University of Illinois
Optical and Discharge Physics

NURTURING OUR DISCIPLINE

Our greatest challenge: Create a self-sustaining, self identified
discipline of plasma processing. The result will
Attract the best-and-the-brightest
Provide educational and professional opportunities for
young scientist and engineers (and replace rapidly
graying university faculty)
Insure critical funding to improve core competencies
and motivate relevant work in supporting sciences
Recognize and advertise social and economic benefits
Provide a lobbying base for proactiveness by academics
and industry
Establish paths for innovation to be commercialized
Create and benefit from unrealized synergies

AVS03_33

University of Illinois
Optical and Discharge Physics

OUR GREATEST CHALLENGE:

NURTURING OUR DISCIPLINE

Recommend Executive Summary from:

"The Impact of Academic Research on Industrial Performance"

(National Academies Press, Washington DC, 2003, www.nap.edu)

AVS03_34

University of Illinois
Optical and Discharge Physics