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 Program on” Atomic and Molecular Data for Plasma Modeling” IAEA, Vienna, Austria Nov. 2008

TITLES OF RESEARCH TOPIC presented under the CRP, 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 scattered 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 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 experimental and theoretical data for these processes related to fusion.

Chemistry Lepton Pairs & Electron Capture Controlled Fusion Nuclear Explosions Fission Fragments Arc Heaters Combus. MHD Gen. Lamps Particle Accelerator Technology X-ray Laser Planetary Atmospheres Ionosphere, Excimer Laser Reverse Kinematics High Energy Astrophysics Stars Intersteller Medium Cosmic X-ray Sources Stellar Photospheres Solar Corona Stellar Atoms. Gaseous Nebulae 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 Electronics

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 2 H 2, C 2 H 4, C 2 H 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 ( ) 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 Polyatomic Molecules (NIFS report, submitted 2008) 3. Electron-impact Excitation Cross Sections of Electronic States in Polyatomic Molecules (NIFS report, to be submitted, 2009) Target Molecules: H-C Molecules produced from the internal wall materials of fusion chambers 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. Hoshino 1, H. Kato 1, C. Makochekanwa 1, 2, S.J. Buckman 2, M. J. Brunger 3, H. Cho 4, M. Kimura 5, D. Kato 6, I. Murakami 6, T. Kato 6, and H. Tanaka 1 1 Department of Physics, Sophia University, Tokyo , 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 , Korea 5 Graduate School of Sciences, Kyushu University, Fukuoka , Japan 6 National Institute of Fusion Science, Toki , 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 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, isomers- C 3 H 4 B. Processing Plasma-Related Gases CF 4, C 2 F 6, C 3 F 8, C 3 F 6, cyclo -C 4 F 8, C 2 F 4, C 6 F 6, CH 3 F, CH 2 F 2, CHF 3, CF 3 I NF 3, SF 6 SiH 4, Si 2 H 6, GeH 4. C. Environmental Issues -Related Gases CF 3 Cl, CF 3 Br H 2 O, CO 2, N 2 O

IAEA & NIFS Report (2008) Cross Sections of Electron-induced Resonant Vibrational Excitations in Polyatomic Molecules H. Kato 1, M. Hoshino 1, H. Kawahara 1, C. Makochekanwa 1,2, S. J.Buckman 2, M.J. Brunger 3, H. Cho 4, M. Kimura 5, D. Kato 6, I. Murakami 6, T. Kato 6 and H. Tanaka 1. 1 Department of Physics, Sophia University, Tokyo , Japan. 2 Centre for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Australia. 3 Centre for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia 4 Department of Physics, Chungnam National University, Daejeon , Korea. 5 Graduate School of Sciences, Kyushu University, Fukuoka , Japan. 6 National Institute of Fusion Science, Toki , 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. Kawahara 1, H. Kato 1,M. Hoshino 1, M. C. Garcia 1#, S. J. Buckman 2, M. J.Brunger 3, H. Cho 4, Yong-Ki Kim †, D. Kato 5, I. Murakami 5, T. Kato 5, and H. Tanaka 1 1 Department of Physics, Sophia University, Tokyo , 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 ,, Korea 5National Institute of Fusion Science, Toki , 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

Concepts of Yong –ki Kim’s Theory We use the BEf -scaling on  Born 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 1 Π) J. Chem. Phys. 126 (2007) , H 2 （ 1Bu and 1Cu ） Phys. Rev. A (2008) CO (C 1 Σ + + c 3 Π, E 1 Π) Phys. Rev. A 77 (2008) (1)-(7) CO 2 ( 1 Σ + u, 1 Π u ) J. Phys. B 41 (2008) (1)-(6) List of Molecules tabulated in this report CO 、 H 2 、 CO 2, H 2 O, ( N 2, O 2, N 2 O, CH 4, C 6 H 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 2 H 6, C 3 H 8, C 2 H 4, C 3 H 4, C 3 H 6 CF 4, C 2 F 6, C 3 F 8, C 2 F 4, c-C 4 F 8, C 6 F 6, C 3 F 6 CF 3 H, CF 2 H 2, CFH 3, CH 3 I, CH 3 Br, CH 3 Cl CF 3 Cl, CF 3 Br, CF 3 I CF 2 Cl 2, CFCl 3, 1,1-C 2 F 2 H 2 SiH 4, Si 2 H 6, SiF 4, GeH 4 NF 3, C 60, C 6 H 6, C 6 H 5 CH 3, C 6 H 5 CF 3, (CH 3 ) 2 CO N 2 O, CO 2, COS, H 2 O, CS 2, XeF 2, HCN H 2 CO CO, NO, H 2, N 2, He, Xe, Kr, O 2 Vibratinally excited-CO 2 *, N 2 O*, CF 3 I* (molecules marked in black after the 1 st RCP, in pink after 2 nd RCP)

Neutral Radical Detection- ionization threshold spectroscopy Parent neutral CH 4 + CH 3 + CH 2 + CH + C+C+ CH CH CH CH C16.8 Table 1. Ionization thresholds e + CH 4 CH 3 + H + e e + CH 3 CH e

Total Cross Sections of CH 3 radicals by Electron Impact from Higher electronic excitation states in CH 4 Jahn-Telle r 4s Rydberg

Negative ion formations from CH 4 by electron impact CH 4 + e  CH 4 -  CH H CH H 2 CH - + H 2 + H C - + 2H 2 ? gas phase or surface TOF data is few eV higher (Krishnakumar)

Negative Ion Formation from SiH 4 SiH 3 - SiH 2 - SiH - Si - Total SiH 4 + e  SiH 3 - SiH 2 - SiH - Si -

Electron impact total cross section from vibrationally excited CO 2 B.1 Electron Interactions with Vibrationally -Excited (hot) Molecule

34mm Mo μmetal Cu pipe HeaterThermocouple mesh Geometry of the heating nozzle H. Kato et al., Chem. Phys. Lett. accepted. CO 2 * (v≠0) + e Electron impact DCS cross section from vibrationally excited CO 2

2 Π u shape resonance

B.2 Recent Developments in Electron Collision Experiments New electron energy loss spectrometer (EELS ll) Nozzle Monochromator Analyzer filament

Elastic DCS of CH 3 Cl and Ehrhardt J.Phys.B 28 (1995) 3957.

Development for TOF apparatus View of TOF setup.

Cold Collision Experiments - photoelectron source induced by SR - Lenz systemGas Cell Detecto r Synchrotron Ar Cross section (cm 2 ) 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, O 2  E  10 meV E 0  30meV

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, 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 ( )

Role of NIFS NETWORK IAEA Platform for Worldwide Database NIST, NIFS, APAN, etc Research Institute Industry University Research Society Individual

Definition of various Cross Section ・ Differential Cross Section for channel “n” ・ Integral and Momentum transfer Cross Section Crossed beam method ・ Total Cross Section Transmission experiment Swarm experiment ※ Upper limit of cross sections Boltzmann equation Measurements of electron collision-cross sections

Molecules investigated A. Fusion Plasma-Related Gases CH 4, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, isomer- C 3 H 4 B. Processing Plasma-Related Gases CF 4, C 2 F 6, C 3 F 8, C 3 F 6 cyclo -C 4 F 8, C 2 F 4, C 6 F 6, CH 3 F, CH 2 F 2, CHF 3 NF 3, (SF 6 ) SiH 4, Si 2 H 6, GeH 4, SiF 4 F 2 CO C. Environmental Issues -Related Gases CF 3 Cl, CF 3 Br, CF 3 I, CF 2 Cl 2, CFCl 3 CO 2, N 2 O,( H 2 O), OCS, CS 2 H 2 CO, C 6 H 5 X(X=H,CH 3,CF 3 ), (CH 3 ) 2 O, CH 3 I

Results (publication list related to IAEA) 1) Experimental and theoretical elastic cross sections for electron collisions with the C 3 H 6 isomers, C. Makochekanwa et al, J. Chem. Phys (2006) 2) Experimental observation of neutral radical formation from CH 4 by electron impact in the threshold region, C. Makochekanwa et al, Phys. Rev. A (2006) 3) Low energy electron energy-loss spectroscopy of CF 3 X (X=Cl, Br), M. Hoshino et al, J. Chem. Phys (2007) 4) Electron and positron scattering from 1,1-C 2 F 2 H 2, C. Makochekanwa et al, J. Chem. Phys (2007) 5) Electron-impact excitation of the 1 B u and 1 C u electronic states of H 2, 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 CO 2, 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) Analytic Cross Sections for Electron Collisions with Hydrocarbons: CH 4, C 2 H 6, C 2 H 4, C 2 H 2, C 3 H 8, and C 3 H 6, T. Shirai, T. Tabata, H. Tawara, and Y. Itikawa, Atomic Data and Nuclear Data Tables 80, (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) p Collision Processes of C 2, 3 H y and C 2, 3 H y Hydrocarbons with electrons and Protons R. K.Janev and D. Reiter, Phys. Plasma 11 (2004) 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 Semiconductor Device age changeover High-k Materials Low-k Materials Nano-mechanics device 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 Quantum-device Bio-device Barriers for The Micro-Processing in the Semiconductors Bottom Down tech. Bottom Up tech.

Research Sites SPring-8 RIKEN Sophia electronpositron photon ion scattered electron ejected electron secondary-photo -Auger-electron positive / negative ion, radical Atom Atom Molecule Molecule Surface Surface Science Univ. of Tokyo Photon Factory

Y.-K. Kim and M. E. Rudd, Phys. Rev. A 50, 3954 (1994) BE f -scaling proposed by Yong-ki Kim Deduction of unavailable data 1. Ionization cross section

2. Optically allowed electronic excitation for Atom

BE f -scaling proposed by Yong-ki Kim 3. Electronic excitation cross sections in CO

DCS for v =2 of the A state in CO

GOS of v =2 of the A state in CO