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

Insulator Material Barrier

Atomic and Molecular age

Atomic and Molecular age

Semiconductor Device age

Semiconductor Device age

1995 2000 2005 2010 2015 2020 2025

changeover

High-k Materials

Low-k Materials

Nano-mechanics device

Atomic and Molecular Science and

Technology age

Atomic and Molecular Science and

Technology age

MOS Transistor Barrier

Analysis and Evaluation Barrier

Atomic and Molecular Barrier

year

Heads into the Atomic and Molecular Science and

Technology age

Heads into the Atomic and Molecular Science and

Technology age

Quantum-device

Bio-device

Barriers for The Micro-Processing in the Semiconductors

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