summary of electron collision data of c-h &c-f compound molecules for plasma modeling review of...
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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
3rd Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Program 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
2005-2006Electron Collision Data of C-H Compound Moleculesfor Plasma Modeling
2007Electron Collision Data of C-H & C-F Compound Molecules for Plasma Modeling
2008Summary 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 scattere
d 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 oth
er research groups to the database. In the same process, data from our group will be systematically compiled for the more than 30 molecules 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.
-3 -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13
Chemistry
Lepton Pairs&
Electron CaptureControlled
Fusion
Nuclear Explosions
Fission Fragments
Arc Heaters
Combus. MHD Gen. Lamps
Particle Accelerator Technology
X-ray
Laser
Planetary
Atmospheres
Ionosphere, Exci
mer Laser
Reverse Kinematics
High Energy AstrophysicsStarsIntersteller
Medium
Cosmic X-ray SourcesStellar
Photospheres
Solar Corona
Stellar Atoms.
Gaseous Nebulae
.)(log10 eVEnergy
Illustration of a variety of applications wherein cross-section data involving atomic & molecular physical processes are important. Illustration of a variety of applications wherein cross-section data involving atomic & molecular physical processes are important.
Gaseous ElectronicsGaseous Electronics
ITER (International Thermonuclear Reactor)
Electron Collision Cross Section Data Needs for
Carbon impurities (H/D-C molecules) produced by physical and chemical sputtering CH4, C2H2, C2H4, C2H6, C3 H8
Still difficult to measure the cross section of even C2, CH, CH2, CH3, ……. Vibrationally (Hot) excited Molecules H2, D2
A. Electron Collision Cross Section Database for Polyatomic Molecules
B. Developing Electron Collision Cross Sections forPolyatomic-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
1Department of Physics, Sophia University, Tokyo 102-8554, Japan2Center for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Australia
3Center for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia4Department of Physics, Chungnam National University, Daejeon 305-764, Korea
5Graduate School of Sciences, Kyushu University, Fukuoka 812-8581, Japan6National Institute of Fusion Science, Toki 509-5292, Japan
1 Introduction2 Definition of Cross Sections3 Experimental Techniques for Precision Measurement of Elastic DCS4 Benchmark Cross Section for Elastic DCS A. Fusion Plasma-Related Gases B. Processing Plasma-Related Gases C. Environmental Issues-Related Gases 5 Concluding RemarksThis work is supported partially by the IAEA, CUP, MEXT, and ARC
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, C3F6, cyclo-C4F8, C2F4, C6F6, CH3F, CH2F2, CHF3 , CF3I NF3, SF6 SiH4, Si2H6, GeH4.
C. Environmental Issues -Related Gases CF3Cl, CF3Br H2O, CO2, N2O
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.
1Department of Physics, Sophia University, Tokyo 102-8554, Japan.2Centre for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Austr
alia.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 Introduction2 Experimental Techniques for Precision Measurement of EELS and Vibrational
Excitation Functions3 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
1Department of Physics, Sophia University, Tokyo 102-8554, Japan2Center for Antimatter-Matter Studies, Australian National University,
Canberra ACT 0200, Australia3Center for Antimatter-Matter Studies, Flinders University,
Adelaide SA 5001, Australia4Department of Physics, Chungnam National University, Daejeon 305-764,, Korea
5National Institute of Fusion Science, Toki 590-5292, Japan
1 Introduction2 Overviews of the BEf-scaling method theory3 Experimental Techniques for Precision Measurement of integral cross sections.
4 Benchmark Cross Section and BEf-scaling model for Optically allowed Electronic Excitation5 Concluding Remarks6 Acknowledgements
Concepts of Yong –ki Kim’s TheoryConcepts of Yong –ki Kim’s Theory
We use the BEf-scaling on Born
(T) σE)B(T
T f
f(T)σ BornBorn
accuBEf
where T = incident energy of the electrons,B = Binding energy, E = Excitation Energy, faccu = accurate optical oscillator strength (OOS) value, fBorn = value of the optical oscillator strength obtained from the same wavefunctions used to calculate Born
CO (A1Π) J. Chem. Phys. 126 (2007) 064307-1-13, H2 ( 1Bu and 1Cu ) Phys. Rev. A (2008)
CO (C1Σ+ + c3Π, E1Π) Phys. Rev. A 77 (2008) 012713(1)-(7) CO2 (1Σ+
u , 1Πu ) J. Phys. B 41 (2008) 085203(1)-(6)
List of Molecules tabulated in this report
CO 、 H2 、 CO2, H2O, ( N2, O2, N2O, CH4, C6H6 )
B. Developing Electron Collision Cross Sections forPolyatomic-Molecules
Collision Processes to be investigated Quantitative Differential Cross Section Measurements1) 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 1st RCP meeting
Collision Data for Molecules Electron Impact
investigated at Sophia University
CH4, C2H6, C3H8, C2H4, C3H4, C3H6
CF4, C2F6, C3F8, C2F4, c-C4F8, C6F6, C3F6
CF3H, CF2H2, CFH3, CH3I, CH3Br, CH3Cl
CF3Cl, CF3Br, CF3I
CF2Cl2, CFCl3, 1,1-C2F2H2
SiH4, Si2H6, SiF4, GeH4
NF3, C60, C6H6, C6H5CH3, C6H5CF3, (CH3)2CO
N2O, CO2, COS, H2O, CS2, XeF2, HCN
H2CO
CO, NO, H2, N2, He, Xe, Kr, O2
Vibratinally excited-CO2*, N2O*, CF3I*
(molecules marked in black after the 1st RCP, in pink after 2nd RCP)
Neutral Radical Detection- ionization threshold spectroscopy
Parent neutral
CH4+ CH3
+ CH2+ CH+ C+
CH4 12.6 14.3 15.1 22.2
25
CH3 9.8 15.1 17.7
25
CH2 10.3 17.4
20.2
CH 13.0
20.3
C 16.8
Table 1. Ionization thresholds
e + CH4 CH3 + H + e
e + CH3 CH3+
+2e
Total Cross Sections of CH3 radicals by Electron Impact from Higher electronic excitation states in CH4
5 6 7 8 9 10 11 12 130.0
0.5
1.0
1.5
0.0
0.5
Cro
ss s
ectio
ns (
10-1
6 c
m2 )
present work A
bsol
ute
cros
s se
ctio
n (1
0-1
6cm
2 )
Impact energy (eV)
CH4 photoab., Kameta et al.
CH4 neutral diss., Kameta et al.
CH4 photoab., Au et al.
Jahn-Teller
4s Rydberg
Negative ion formations from CH4 by electron impact
CH4 + e CH4- CH3
- + H CH2
- + H2
CH- + H2 + H C- + 2H2
?gas phase or surface
TOF data is few eV higher(Krishnakumar)
8 10 12 14 16
and : Total
and : C-
and : CH-
and : CH2
-
and : CH3
-
Inte
nsi
ty (
arb. unit
s)
Impact energy (eV)
CH4
34 36 70 72 74 76 78 80 82
7978
7776
75
74
73
72
71Inte
nsit
y (
arb
. u
nit
s)
Mass Number (amu)
(c) GeH4
E0 = 7.5 eV
70
Cl-
26 28 30 32 34 36 38
Cl-
3332
31
30
29
Inte
nsit
y (
arb
. u
nit
s)
Mass Number (amu)
CN-
28
(b) SiH4
E0 = 8.5 eV
8 9 10 11 12 13 14 15 16 17 18
11
OH-O-
12
13
E0 = 11.5 eV
Inte
nsit
y (
arb
. u
nit
s)
Mass Number (amu)
(a) CH4 14
Negative Ion Formation from SiH4
26 28 30 32 34 36 38
Cl-
3332
31
30
29
Inte
nsi
ty (
arb
. u
nit
s)
Mass Number (amu)
CN-
28
SiH4
E0 = 8.5 eV
7 8 9 10 11 12
Inte
nsi
ty (
arb
. unit
s)
Impact energy (eV)
SiH4 SiH3
-
SiH2-
SiH-
Si-
Total
SiH4 + e SiH3-
SiH2-
SiH-
Si-
Electron impact total cross section from vibrationally excited CO2
B.1 Electron Interactions with Vibrationally -Excited (hot) Molecule
34mm
Moμ metal
Cu pipe
Heater Thermocouple
mesh
Geometry of the heating nozzle
H. Kato et al., Chem. Phys. Lett. accepted.
CO2* (v≠0) + e
Electron impact DCS cross section from vibrationally excited CO2
2Πu shape resonance
)(
)(
)(
)()(
)()(
)()(
3
2
1
12
01
30103000
20102000
10101000
Tσ
Tσ
Tσ
σ
σ
TPTP
TPTP
TPTP
bend
bend
bend
B.2 Recent Developments in Electron Collision Experiments
New electron energy loss spectrometer (EELS ll)
Nozzle
MonochromatorAnalyzer
filament
Elastic DCS of CH3Cl
HCl@Gote and Ehrhardt J.Phys.B 28 (1995) 3957.
Development for TOF apparatus
0 2 4 6 8 10 12 14
N2
Sophia Univ. E
0 = 20.0 eV non-calib.
Trajimar et al. E
0 = 19.0 eV
Inte
nsi
ty(a
rb.u
nit
)
Sophia Univ. E
0 = 15.5 eV non-calib.
Trajimar et al. E
0 = 15.5 eV
b1u
a1g
C3u
D3+
uE3+
g
W3u
A3+
u
= 90o
N2
= 90o
Energy loss (eV)
View of TOF setup.
Cold Collision Experiments - photoelectron source induced by SR -
Lenz system Gas Cell
Detector
SynchrotronAr
Cro
ss s
ectio
n (c
m2 )
Impact energy (eV)
Xe
Schematic view of experimental setup
Total cross section of Xe in low energy region (preliminary data )
Research site: Photon Factory at KEK
Ar + h Ar+ + e
Xe, Kr, O2
E 10 meVE0 30meV
Summary
A. Electron Collision Cross Section Database for Polyatomic Molecules Three NIFS reports prepared for elastic scattering DCS, vibtational, and electronic excitationsB. Electron Interactions with Excited Molecules Vibrational excitation cross section determined for inelastic and super- elastic electron scattering in the ground-electronic state in hot CO2
C. Recent Developments in Electron Collision Experiments Four new Apparatuses developed recently for EELS, TOF, Negative ion, and Cold Collision
Comprehensive, absolute, and correct cross-section data implemented through 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 )
Role of NIFS NETWORKIAEA
Platform for Worldwide DatabaseNIST, NIFS, APAN, etc
Research Institute
Industry
University
Research Society
Individual
Definition of various Cross Section
・ Differential Cross Section for channel “n”
2
00
0 ),(),(
),(
Efk
k
d
EdqE n
i
fnnσ
・ Integral and Momentum transfer Cross Section
Crossed beam method
ddEEq nn sin),()(2
0 0
00
ddEEqM sin)cos1(),()( 000
・ Total Cross Section
n
n EqEQ T )()( 00
Transmission experiment
NlQTeII 0
n
nT qQ)( mn
Swarm experiment
※Upper limit of cross sections
cvX tffmFfvtf ][)(
Boltzmann equation
Measurements of electron collision-cross sections
Molecules investigated
A. Fusion Plasma-Related GasesCH4, C2H6, C3H8, C2H4, C3H6, isomer- C3H4
B. Processing Plasma-Related Gases CF4, C2F6, C3F8, C3F6 cyclo-C4F8, C2F4, C6F6,
CH3F, CH2F2, CHF3 NF3, (SF6 ) SiH4, Si2H6, GeH4, SiF4 F2COC. Environmental Issues -Related Gases CF3Cl, CF3Br,
CF3I, CF2Cl2, CFCl3 CO2, N2O,( H2O), OCS, CS2 H2CO,C6H5X(X=H,CH3,CF3), (CH3)2O, CH3I
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 DCSResonant Phenomena in Vibrational ExcitationElectronic 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) 14. 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: CH4, 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 C2, 3Hy and C2, 3Hy Hydrocarbons with electrons and Protons R. K .Janev and D. Reiter, Phys. Plasma 11 (2004) 7808. 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
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 fusion- and plasma processing- plasmas (proposed 2005)
Furthermore, being proposed as follows:Experimental Verification for BEf - Scaling Law in Electron-Molecule Collision
continued
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changeover
High-k Materials
Low-k Materials
Nano-mechanics device
Atomic and Molecular Science and
Technology age
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Technology age
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Heads into the Atomic and Molecular Science and
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Bottom Down tech. Bottom Up tech.
Research Sites
SPring-8SPring-8
RIKENRIKEN
SophiaSophiaelectronelectronpositronpositron
photonphoton
ionion
scattered electronscattered electron
ejected electronejected electronsecondary-photo secondary-photo -Auger-electron-Auger-electron
positive / negative ion, radicalpositive / negative ion, radical
AtomAtom MoleculeMolecule
SurfaceSurface
Science Univ. of TokyoPhoton Factory
Y.-K. Kim and M. E. Rudd, Phys. Rev. A 50, 3954 (1994)
BEf -scaling proposed by Yong-ki Kim
Deduction of unavailable data
1. Ionization cross section
2max0
2min0
)(
)( 20
200
20
20
)(
)(
/
)(4)(
4 Ka
KaPWBPWB Ka
Kad
RE
KF
T
RaTF
T
Ra
PWBPWB
accurBEf f
f
EBT
T
2. Optically allowed electronic excitation for Atom
BEf -scaling proposed by Yong-ki Kim 3. Electronic excitation cross sections in CO
0 20 40 60 80 1000.1
1
10
100
Impact Energy 50eV Sophia's Data Flinder's Data Flinder's Data (80%)
A1 (=2) ← X1+
DC
S (
10-1
8 cm2 /s
r)
angle (deg)
DCS for v =2 of the A state in CO
10- 3 10- 2 10- 1 100 101 1020.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
A1 (=2) ← X1+
100 eV 200 eV
OOS=0.03886
GO
S (
a. u. )
K2 (a. u. )
GOS of v =2 of the A state in CO