Summary of Electron Collision Data of

C-H &C-F Compound Molecules for Plasma

Modeling
Review of Our Research Proposal 　

　　 Hiroshi Tanaka
　　 Department of Physics
　　 Sophia University, Tokyo, JAPAN

　 3 rd Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Prog

ram on” Atomic and Molecular Data for Plasma Modeling”
IAEA, Vienna, Austria 17-19 Nov. 2008
TITLES OF RESEARCH TOPIC
presented under the CRP, 2005-2008

2005-2006
Electron Collision Data of C-H Compound Molecules
for Plasma Modeling

2007
Electron Collision Data of C-H & C-F Compound Molecules
for Plasma Modeling

2008
Summary of Electron Collision Data of
C-H &C-F Compound Molecules for Plasma Modeling
Review of Our Research Proposal
Summary of WORK PLAN
　 proposed during the CRP

Year 1 (2005):
Evaluation and analysis of related data available in literature but scatt
ered in different places all over the world within the framework of IAEA
International Bulletin on Atomic and Molecular Data for Fusion.
Year 2 (2007):
Compilation and addition of new data from our group as well as from
other research groups to the database. In the same process, data fro
m our group will be systematically compiled for the more than 30 mole
cules studied so far for the collision processes: elastic, vibrational and
electronic excitations, and total cross sections.
Year 3 (2008):
Proposal of new directions for producing missing but necessary experi
mental and theoretical data for these processes related to fusion.
Illustration of a variety of applications wherein cross-section
data
involvingGaseous
atomic & molecular
Solar physical processes are important.
Nebulae Corona Cosmic X-ray Sources
Stellar Stellar
Intersteller Atoms. StarsPhotospheres
High Energy Astrophysics
Medium
Gaseous Electronics
Planetary Ionosphere, Exci X-ray
Atmospheres mer Laser Laser
Particle Accelerator Technology
Combus. M
HD Gen. Lamps Reverse Kinematics
Arc Lepton Pairs
Heaters Controlled Fission &
Chemistry Fusion Fragments Electron Capture
Nuclear
Explosions
-3 -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13
log10  Energy (eV .)
ITER (International Thermonuclear Reactor)

Electron Collision Cross Section Data Needs for

Carbon impurities (H/D-C molecules) produced by

physical and chemical sputtering
CH 4, C 2H 2, C 2H 4, C 2H 6, C 3 H 8

Still difficult to measure the cross section of even

C 2, CH, CH 2, CH 3, …….
Vibrationally (Hot) excited Molecules
H 2, D 2
A. Electron Collision Cross Section Database for Polyatomic
Molecules

B. Developing Electron Collision Cross Sections for

Polyatomic-Molecules
B.1 Electron Interactions with Excited Molecules
B.2. Recent Developments in Electron Collision Experiments
A. SUMMARY of ACTIVITIES for DATABASE (2005- 2008)
Data Compilations in Printed Form

1. Elastic Differential Cross Sections for Electron Collisions with

Polyatomic Molecules (NIFS report, 2008)
2. Cross Sections of Electron-induced Resonant Vibrational Excitations in P
olyatomic Molecules (NIFS report, submitted 2008)
3. Electron-impact Excitation Cross Sections of Electronic States in Polyato
mic Molecules (NIFS report, to be submitted, 2009)
Target Molecules:
H-C Molecules produced from the internal wall materials of fusion cham
bers
H-C & C-F Molecules for plasma processing
Our Database compiled is restricted only to our own elastic DCS
 IAEA & NIFS Report (2007)

Elastic Differential Cross Sections for

Electron Collisions with Polyatomic Molecules
M. Hoshino1, H. Kato1, C. Makochekanwa1, 2, S.J. Buckman2, M. J. Brunger3,
H. Cho4, M. Kimura5, D. Kato6, I. Murakami6, T. Kato6, and H. Tanaka1

1
Department of Physics, Sophia University, Tokyo 102-8554, Japan
2
Center for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Australia
3
Center for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia
4
Department of Physics, Chungnam National University, Daejeon 305-764, Korea
5
Graduate School of Sciences, Kyushu University, Fukuoka 812-8581, Japan
6
National Institute of Fusion Science, Toki 509-5292, Japan

1 Introduction
2 Definition of Cross Sections
3 Experimental Techniques for Precision Measurement of Elastic DCS
4 Benchmark Cross Section for Elastic DCS
A. Fusion Plasma-Related Gases
B. Processing Plasma-Related Gases
C. Environmental Issues-Related Gases
5 Concluding Remarks
This work is supported partially by the IAEA, CUP, MEXT, and ARC
List of Molecules tabulated in this report

A. Fusion Plasma-Related Gases

CH 4, C 2H 6, C 3H 8, C 2H 4, C 3H 6, isomers- C 3H 4

B. Processing Plasma-Related Gases

CF 4, C 2F 6, C 3F 8, C 3F 6, cyclo -C 4F 8, C 2F 4, C 6F 6,
CH 3F, CH 2F 2, CHF 3 , CF 3I
NF 3, SF 6
SiH 4, Si 2H 6, GeH 4.

C. Environmental Issues -Related Gases

CF 3Cl, CF 3Br
H 2O, CO 2, N 2O
 IAEA & NIFS Report (2008)

Cross Sections of Electron-induced

Resonant Vibrational Excitations in Polyatomic Molecules
H. Kato1, M. Hoshino1, H. Kawahara1, C. Makochekanwa1,2, S. J.Buckman2,
M.J. Brunger3, H. Cho4, M. Kimura5, D. Kato6, I. Murakami6, T. Kato6 and H. Tanaka1.

1 Department of Physics, Sophia University, Tokyo 102-8554, Japan.

2Centre for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Austral
ia.
3Centre for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia

4Department of Physics, Chungnam National University, Daejeon 305-764, Korea.

5Graduate School of Sciences, Kyushu University, Fukuoka 812-8581, Japan.

6National Institute of Fusion Science, Toki 590-5292, Japan.

1 Introduction
2 Experimental Techniques for Precision Measurement of EELS and Vibrational
Excitation Functions
3 Benchmark Cross Section for Vibrational Excitation
A. Fusion Plasma-Related Gases
B. Processing Plasma-Related Gases
C. Environmental Issues-Related Gases
5 Concluding Remarks
List of Molecules tabulated in this report

A. Fusion Plasma-Related Gases

CH4, C2H6, C3H8, C2H4, C3H6, isomers- C3H4

B. Processing Plasma-Related Gases

CF4, C2F6, C3F8, cyclo -C4F8, C2F4, C6F6, C3F6
CH3F, CH2F2, CHF3 , CF3I
NF3
SiH4, Si2H6, GeH4, SiF4
F2CO

C. Environmental Issues -Related Gases

CF3Cl, CF3Br, CF3I
CO2, N2O, CO, OCS, CS2
(CH3)2O, (CH3)2CO
C6H6, C6H5CH3, C6H5CF3, 1,1-C2H2F2
 IAEA & NIFS Report (2008)

Electron-impact Excitation Cross Sections of

Electronic States in Polyatomic Molecules
-Application Examples of the BEB- scaling model in Optically-allowed Transitions-

H. Kawahara1, H. Kato1,M. Hoshino1, M. C. Garcia1#, S. J. Buckman2, M. J.Brunger3,

H. Cho4, Yong-Ki Kim†, D. Kato5, I. Murakami5, T. Kato5, and H. Tanaka1

Department of Physics, Sophia University, Tokyo 102-8554, Japan

1

Center for Antimatter-Matter Studies, Australian National University,

2

Canberra ACT 0200, Australia

3Center for Antimatter-Matter Studies, Flinders University,

Adelaide SA 5001, Australia

4Department of Physics, Chungnam National University, Daejeon 305-764,, Korea

5National Institute of Fusion Science, Toki 590-5292, Japan

1 Introduction
2 Overviews of the BEf-scaling method theory
3 Experimental Techniques for Precision Measurement of integral cross sections.
4 Benchmark Cross Section and BEf-scaling model for Optically allowed Electronic Excitation
5 Concluding Remarks
6 Acknowledgements
 List of Molecules tabulated in this report

CO 、 H 2 、 CO 2, H 2O, ( N 2, O 2, N 2O, CH 4, C 6H 6 )

Concepts of Yong –ki Kim’s Theory

　 We use the BEf -scaling on  Born

 f accu   T 
σ BEf (T)     σ Born(T)
 f Born   (T  B  E) 

where T = incident energy of the electrons, B = Binding energy, E = Excitation

Energy, f accu = accurate optical oscillator strength (OOS) value, f Born = value of
the optical oscillator strength obtained from the same wavefunctions used to
calculate  Born
　 CO (A 1Π) J. Chem. Phys . 126 (2007) 064307-1-13,
H 2 （ 1Bu and 1Cu ） Phys. Rev. A (2008)
CO (C 1Σ + + c 3Π, E 1Π) Phys. Rev . A 77 (2008) 012713(1)-(7)
CO 2 ( 1Σ+u , 1Πu ) J. Phys. B 41 (2008) 085203(1)-(6)
 B. Developing Electron Collision Cross Sections for
Polyatomic-Molecules
Collision Processes to be investigated
Quantitative Differential Cross Section Measurements
1) Electron Energy-loss Spectroscopy (EELS):
Elastic Scattering DCS
Resonant Phenomena in Vibrational Excitation
Electronic Excitation Process, GOS
2) Quadra- Pole- Mass Spectroscopy (QMSS)
Non-radiative Dissociation Products
(Threshold Ionization Spectroscopy)
Dissociative Attachment Processes
3) Low Energy Electron Diffraction (LEED) (not done since 2007)
Surface and Phase Transition
proposed at 1 st RCP
meeting
 Collision Data for Molecules Electron Impact
investigated at Sophia University

CH 4, C 2H 6, C 3H 8, C 2H 4, C 3H 4, C 3H 6
CF 4, C 2F 6, C 3F 8, C 2F 4, c-C 4F 8, C 6F 6, C 3F 6
CF 3H, CF 2H 2, CFH 3, CH 3I, CH 3Br, CH 3Cl
CF 3Cl, CF 3Br, CF 3I
CF 2Cl 2, CFCl 3, 1,1-C 2F 2H 2
SiH 4, Si 2H 6, SiF 4, GeH 4
NF 3, C 60 , C 6H 6, C 6H 5CH 3, C 6H 5CF 3, (CH 3) 2CO
N 2O, CO 2, COS, H 2O, CS 2, XeF 2, HCN
H 2CO
　　　　　 CO, NO, H 2, N 2, He, Xe, Kr, O 2
Vibratinally excited-CO 2*, N 2O*, CF 3I*
(molecules marked in black after the 1st RCP, in pink after 2nd RCP)
Neutral Radical Detection- ionization threshold spectroscopy

Table 1. Ionization thresholds

Parent CH4+ CH3+ CH2+ CH+ C+
neutral
CH4 12.6 14.3 15.1 22.2 25

e + CH4 CH3 + H + e CH3 9.8 15.1 17.7 25

CH2 10.3 17.4 20.2

CH 13.0 20.3

C 16.8
e + CH3 CH3 +2e
+
Total Cross Sections of CH3 radicals by Electron Impact
from Higher electronic excitation states in CH 4

present work
CH 4 photoab., Kameta et al.
CH 4 neutral diss., Kameta et al.
1.5
cm )

CH 4 photoab., Au et al.
2
-16

cm )
2
Absolute cross section (10

1.0

-16
0.5

Cross sections (10

0.5

4s Rydberg
Jahn-Teller
0.0 0.0
5 6 7 8 9 10 11 12 13
Impact energy (eV)
Negative ion formations from CH4 by electron impact

CH4 and
and
: Total
:C
-

-
and : CH
-
and : CH2
-
and : CH3

CH 4 + e  CH 4-  CH 3- + H
CH 2- +

Intensity (arb. units)

H2
CH - +
H2 + H
C- + 2
H2
?
gas phase or surface

TOF data is few eV higher

8 10 12 14 16
(Krishnakumar)
Impact energy (eV)
 SiH4 + e  SiH3-
Negative Ion Formation from SiH4 SiH2-
SiH-
Si-

SiH4 SiH4 Total

SiH3-
31
SiH2-
E0 = 8.5 eV SiH-
30 Si-
Intensity (arb. units)

Intensity (arb. units)

29

-
Cl
28
- 32
CN
33

26 28 30 32 34 36 38 7 8 9 10 11 12
Mass Number (amu) Impact energy (eV)
 B.1 Electron Interactions with
Vibrationally -Excited (hot) Molecule

Electron impact total cross section from

vibrationally excited CO2
 Electron impact DCS cross section from
vibrationally excited CO2
CO2* (v≠0) + e

34mm
μ metal
Mo

Cu pipe
mesh

Heater Thermocouple

Geometry of the heating nozzle

H. Kato et al., Chem. Phys. Lett. accepted.

  P000 (T1 ) P010 (T1 )  σ (T ) 
   σ 01   bend 1 
P010 (T2 )       σ bend (T2 ) 
2
Πu shape resonance  P000 (T2 )
 P (T )
 000 3

P010 (T3 )   σ 12   
 σ bend (T3 ) 
B.2 Recent Developments in Electron Collision Experiments

New electron energy loss spectrometer (EELS ll)

Nozzle
filament

Analyzer
Monochromator
Elastic DCS of CH3Cl

HCl@Gote and Ehrhardt J.Phys.B 28 (1995) 3957.

Development for TOF apparatus

Sophia Univ. N2
E0 = 20.0 eV non-calib. o
 = 90
Trajimar et al.
E0 = 19.0 eV
3 1
C u b u

Intensity(arb.unit)
3 + 3 +
E  gD  u
1
a g
3
W u
3 +
A u

Sophia Univ. N2
E0 = 15.5 eV non-calib. o
Trajimar et al.  = 90
E0 = 15.5 eV

View of TOF setup.

0 2 4 6 8 10 12 14
Energy loss (eV)
Cold Collision Experiments
Ar + h  Ar+ + e
- photoelectron source induced by SR -
E  10 meV
E0  30meV
Lenz system Gas
Cell Total cross section of Xe in low en
ergy region (preliminary data )
Detecto
r
Xe

Cross section (cm 2)

Ar
Synchrotron

Schematic view of experimental setup

Research site: Photon Factory at KEK Impact energy (eV)

Xe, Kr, O 2
Summary

A. Electron Collision Cross Section Database for Polyatomic Molecules

Three NIFS reports prepared for elastic scattering DCS, vibtational, and
electronic excitations
B. Electron Interactions with Excited Molecules
Vibrational excitation cross section determined for inelastic and super-
elastic electron scattering in the ground-electronic state in hot CO 2
C. Recent Developments in Electron Collision Experiments
Four new Apparatuses developed recently for EELS, TOF, Negative ion, an
d
Cold Collision

Comprehensive, absolute, and correct cross-section data implemented thro

ugh joint efforts involving
many knowledgeable works and international collaboration
 Group Members

Dr. M. Hoshino (Assist. Prof.)

H. Kato (D3) : EELS I, II, SR Experiment
H. Kawahara (M2) : EELS I, II, SR Experiment
Y. Nagai (M2) : EELS I
S. Kobayashi (M2) : Threshold Electron Spectroscopy by TOF
D. Tomida (M2) : Positron Experiment
　 Y. Kanazawa (M2) : Capillary Experiment on Highly Charged Ion
　 T. Shishimoto(M1): Negative Ion Experiment
H. Masui (M1): EELS I
T. Asahina (M1) : EELS II, SR Experiment
 PROJECT PERSONNEL

Chief Scientific Investigator:

Hiroshi TANAKA (Prof. Sophia Univ. JAPAN)

Other Supporting Scientific Staff:

　 Masamitsu HOSHINO (Dr. Sophia Univ. JAPAN)
Mineo KIMURA (Prof. Kyushu Univ. JAPAN, deceased)
　 Michael J. BRUNGER (Prof. Flinders Univ. AUSTRALIA)
　 Stephen J. BUCKMAN (Prof., Australian Nat’l Univ. AUSTRALIA)
Casten MAKOCHEKANWA (Dr. Australian Nat’l Univ. AUSTRALIA )
Hyuck CHO (Prof. Chungnam Nat’l Univ. South KOREA)

Many thanks to the IAEA- RCP for this collaboration ( 2005-2008 )

 IAEA
Role of NIFS NETWORK
Platform for Worldwide Database
NIST, NIFS, APAN, etc

Research Institute University

Research Society Industry

Individual
 Measurements of electron collision-cross sections
Definition of various Transmission experiment
Cross Section

Crossed beam method

I  I 0 e QT Nl
QT   qn
n
( n  m)

※Upper limit of cross sections

・ Differential Cross Section for
channel “n”
dqn ( E0 , ) k f 2
σn ( E0 , )   f n ( E0 , )
d ki

・ Integral and Momentum transfer

Cross Section

qM ( E0 )     0 ( E0 , )(1  cos ) sin dd Boltzmann equation

2 
f t  v   X f  ( F m)   v f  [f t ]c
qn ( E0 )   
0 0
n ( E0 , ) sin dd

・ Total Cross Section

Q T ( E0 )   q n ( E0 )
Swarm experiment
n
Molecules investigated
A. Fusion Plasma-Related Gases
CH 4, C 2H 6, C 3H 8, C 2H 4, C 3H 6, isomer- C 3H 4

B. Processing Plasma-Related Gases

CF 4, C 2F 6, C 3F 8, C3F6 cyclo -C 4F 8, C 2F 4, C 6F 6,
CH 3F, CH 2F 2, CHF 3 NF 3, (SF 6 )
SiH 4, Si 2H 6, GeH 4, SiF 4
F 2CO
C. Environmental Issues -Related Gases
CF 3Cl, CF 3Br,
CF 3I, CF 2Cl 2, CFCl 3
CO 2, N 2O,( H 2O), OCS, CS 2 H 2CO,
C 6H 5X(X=H,CH 3,CF 3), (CH 3) 2O, CH 3I
Results (publication list related to IAEA)

1) Experimental and theoretical elastic cross sections for electron collisions

with the C3H6 isomers, C. Makochekanwa et al,
J. Chem. Phys. 124 024323-1 (2006)
2) Experimental observation of neutral radical formation from CH4 by electron
impact in the threshold region, C. Makochekanwa et al,
Phys. Rev. A 74 042705 (2006)
3) Low energy electron energy-loss spectroscopy of CF3X (X=Cl, Br), M. Hoshino et al,
J. Chem. Phys. 126 024303 (2007)
4) Electron and positron scattering from 1,1-C2F2H2, C. Makochekanwa et al,
J. Chem. Phys. 126 164309-1 (2007)
5) Electron-impact excitation of the 1Bu and 1Cu electronic states of H2, H. Kato et al,
Phys. Rev. A (2008)
6) Vibrationaaly excitation functions for inelastic and superelastic electron scattering
from the ground-electronic state in hot CO2, H. Kato et al,
Chem. Phys. Letter (2008)
 Electron Interactions with Molecule
Collision Processes of Interest
Quantitative Differential Cross Section Measurements
Electron Energy-loss Spectroscopy (EELS):
Elastic Scattering DCS
Resonant Phenomena in Vibrational Excitation
Electronic Excitation Process, GOS
Quadra- Pole- Mass Spectroscopy (QMSS)
Non-radiative Dissociation Products
(Threshold Ionization Spectroscopy)
Dissociative Attachment Processes
Low Energy Electron Diffraction (LEED)
Surface and Phase Transition
(previously presented in 2005)
Review Articles previously published
Review articles after 1990,
1. International Bulletin on Atomic and Molecular Data for Fusion, 42(1992)-58(2000)
published by IAEA,
2. Collision Data Involving Hydro-Carbon Molecules, H. Tawara, Y. Itikawa, H. Nishimura,
H. Tanaka, and Y. Nakamura, NIFS-DATA-6 July (1990)
3. Atomic Data and Nuclear Data Tables 76 (2000) 1
4. One Century of Experiments on Electron-Atom and Molecule Scattering: a Critical
Review of Integral Cross-sections Ⅱ-Polyatomic Moecules,Ⅲ-Hydrocarbons and
Halides, G. P. Karwasz, R. S. Brusa, and A. Zecca,
La Rivista del Nuvo Cimento 24 (1) (4) 2001
5. Analytic Cross Sections for Electron Collisions with Hydrocarbons: CH 4, C2H6, C2H4,
C2H2, C3H8, and C3H6, T. Shirai, T. Tabata, H. Tawara, and Y. Itikawa, Atomic Data and
Nuclear Data Tables 80, 147-204 (2002)
6. Interaction of Photons and Electrons with Molecules, M.J.Brunger and S.J.Buckman,
Photon and Electron Interactions with Atoms, Molecules, and Ions, vilI/17, sub-volume
C ed Y. Itikawa, Landorf-Beurnstein (2003, Berlin: Springer) p6-118
7. Collision Processes of C 2, 3Hy and C2, 3Hy Hydrocarbons with electrons and Protons
R. K .Janev and D. Reiter, Phys. Plasma 11 (2004) 780
8. Vibrational Excitation of Polyatomic Molecules by Electron Collisions
Y. Itikawa, J. Phys. B: At. Mol. Opt. Phys 37 R1-24 (2004)
Recent Cross-section Data
　 summarized in
“ Molecular Processes in Plasma-Collision of Charged Particles with Molecules-”
(Springer Berlin Heidelberg New York 2007) by Itikawa as follows:

Data Compilations in Printed Form

Journals Exclusively Focused on Atomic and Molecular Data
Online Database
Review Papers
Conference
continued
Research directions for 2008 and in future:
2008: propose directions for experimentalists and theorists to come
up with new cross section data that would make the database for each
molecule as complete as feasible as relates to the application to the fu
sion- and plasma processing- plasmas (proposed 2005)

Furthermore, being proposed as follows:

Experimental Verification for BEf - Scaling Law in Electron-Molecule C
ollision
 Barriers for The Micro-Processing in the Semiconductors
Semiconductor Atomic
Atomic and
and
Semiconductor changeover
Device Molecular
Molecular age
Device age
age age
1995 2000 2005 2010 2015 2020 2025
year

High-k Materials
Insulator Material Barrier Low-k Materials

Quantum-device

MOS Transistor Barrier Bio-device Nano-mechanics devic

e
Analysis and Evaluation Barrier Atomic
Atomicand
andMolecular
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Science
Scienceand
and
Technology
Technologyage
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Atomic and Molecular Barrier
Heads
Headsinto
intothe
theAtomic
Atomicand
and
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and
Bottom Down tech. Technology
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 Research Sites
Sophia
electron
positron Atom
Molecule scattered electron

photon
ejected electron
secondary-photo
SPring-8 Surface -Auger-electron

ion

positive / negative ion, radical

Science Univ. of Tokyo

RIKEN Photon Factory
BEf -scaling proposed by Yong-ki Kim
1. Ionization cross section

Deduction of unavailable data

Y.-K. Kim and M. E. Rudd, Phys. Rev. A 50, 3954 (1994)

2. Optically allowed electronic excitation for Atom
T f accur
 BEf    PWB
T  B  E f PWB

4a02 R 4a02 R ( Ka0 ) 2max F0 ( K ) d ( Ka0 ) 2

T ( Ka0 ) 2min E / R ( Ka0 ) 2
 PWB  FPWB (T ) 
T
BEf -scaling proposed by Yong-ki Kim
3. Electronic excitation cross sections in CO
DCS for v =2 of the A state in CO

100 1 1 +
A  ( =2) ← X 
Impact Energy 50eV
Sophia's Data
Flinder's Data
Flinder's Data (80%)
DCS (10 cm /sr)
10
2
-18

0.1
0 20 40 60 80 100
angle (deg)
 GOS of v =2 of the A state in CO

0.050
0.045 A1 (=2) ← X1+
OOS=0 .0 3 8 8 6
G O S (a . u . )
0.040
0.035 100 eV
200 eV
0.030
0.025
0.020
0.015
0.010
0.005
0.000 -3
10 10-2 10-1 100 101 102
2
K (a. u. )