Electron Collision Data of C-H Compound Molecules f

or Plasma Modeling Framework for Our Research Proposal 　The IAEA’s Co-ordinated Research Program on

” Atomic and Molecular Data for Plasma Modeling”

　　 Hiroshi Tanaka

　　 Department of Physics

　　 Sophia University, Tokyo, JAPAN

1st 　 Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Program on” Atomic and Molecular Data for Plasma Modeling”

IAEA, Vienna, Austria 26-28 Sep. 2005

RESEARCHER’S INSTITUTE

Department of Physics Sophia UniversityTokyo JAPAN CONTACT DETAILS:Telephone: +81-3-3238-3472Facsimile: +81-3-3238-3341E-mail: h_tanaka@sophia.ac.jp

PROPOSED TITLE OF RESEARCH TOPIC (under Co-ordinated Research Project the research will support)　

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

SUMMARY OF THE PROPOSED RESEARCHTarget Molecules: H-C molecules produced from the internal wall materials of fusion chambers Research directions for three year project: 1st year: compilation and analysis of data already available in literature that

relates to this filed of plasma modeling. 2nd year : analyzing recent data from our collaboration group in conjunction

with related data from other laboratories on cross sections from these molecules.

3rd year: 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.

PROJECT PERSONNEL

Chief Scientific Investigator:

Hiroshi TANAKA (Prof. Sophia Univ. Japan)

Other Supporting Scientific Staff:

Mineo KIMURA (Prof. Kyushu Univ. JAPAN)

Casten MAKOCHEKANWA (Dr. JSPS Fellow JAPAN )

Masamitsu HOSHINO (Dr.Sophia Univ. JAPAN)

Hyuck CHO (Prof. Chungnam Nat’l Univ. South KOREA)

Michael J. BRUNGER(Prof. Flinders Univ. of Southen AU AU)

Stephen J. BUCKMAN(Prof., Australian Nat’l Univ. AU)

 

DESCRIPTION OF RESEARCH OBJECTIVES AND ANTICIPATED OUTCOMES

Main Objectives:

￭ Understanding electron-C-H compound molecule

interactions in the fundamental collision processes

for Fusion and Plasma processing Plasmas

￭ The comprehensive evaluation and analysis of the

previous related cross section data available in

literature from all over the world within the framework

of IAEA International Bulletin on Atomic and Molecular

Data for Fusion.

DESCRIPTION OF RESEARCH OBJECTIVES AND ANTICIPATED OUTCOMES continued

￭ Compilation of new data from our group as well as from other research groups into the database. 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.

￭ Propose new directions for producing missing but necessary experimental and theoretical data for these processes

Currently, from a world wide perspective, the data source for these absolute cross sections are from these Australian, South Korean, and Japanese experimental groups involved in this collaboration. Other possible sources may include the Polish, Danish, Spanish, Brazilian, and Switzerland

WORK PLAN Year 1: 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: 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: Proposal of new directions for producing missing but necessary experimental and th

eoretical data for these processes related to fusion and plasma processing plasmas. 

Brief description of facilities availableOnly limited to measurement of absolute cross sections1) Sophia University (JP): three cross beam spectrometers2) Flinders University of Southern Australia (AU): two cross beam spectrometers3) Australian National University (AU): two cross beam spectrometers4) Chungnam National University (SOK): one cross beam spectrometer5) Kyushu University (JP): data analysis

PROPOSED COMMENCEMENT DATE

1 September 2005

Preliminary stage

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) 

Ongoing Data Collection Network

Data Needs for Electron Interaction with Plasma Data Needs for Electron Interaction with Plasma

Processing and Fusion Plasma GasesProcessing and Fusion Plasma Gases

H.TANAKA , M. HOSHINO, and C. MAKOCHEKANWADepartment of Physics

Sophia UniversityTokyo, Japan

1st 　 Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Program on” Atomic and Molecular Data fror Plasma Modeling”

IAEA, Vienna, Austria 26-28 Sep. 2005

Collaboration

International Chugnam National University ( Prof. Cho S. Korea) Australian National University (Prof. Buckman AU) Flinders University of Southern Australia (Prof. Brunger AU) The Open University (Prof. Mason UK)

Domestic Kyushu University (Prof. Kimura, Collaboration Theoretical) NIFS (Prof. Kato under the Japan-Korea CUP program) JAERI (Dr. Kubo under the Fusion Plasma Project in Japan) Tohoku University(Prof. Ueda, SR experiment at Spring-8) RIKEN (Prof. Yamazaki, Highly Charged Ion Research)

Group Members

Dr. M. Hoshino (Dr. Research Associate)

Dr. C. Makochekanwa (Dr. JSPS Fellow, Kyushu Univ.)

T. Tanaka (D1)

H.Kato (M2)

K.Nakagawa (M2)

Y.Miyamoto (M2)

K.Oguri (M2)

SPring-8SPring-8

RIKENRIKEN

SophiaSophiaelectronelectron

photonphoton

ionion

scattered electronscattered electron

ejected electronejected electronsecondary-photo secondary-photo -Auger-electron-Auger-electron

positive / negative ion, radicalpositive / negative ion, radical

AtomAtom MoleculeMolecule

Research Sites

SurfaceSurface

Data providers(Atomic physicists) * theory * experiment

Data users in variousapplication fields * fusion science * astrophysics * industrial plasmas * environmental physics * medical (radiotherapy) etc.

Data centers data compilation data evaluation (important but not easy) dissemination and updating of database retrievable online database = easy to access, use, find data

Data requests

Data

need

s

Data provide

Dat

a pr

ovid

e

Data

sear

ch

Hard to find or request data

Data search for check

International A&M data center network IAEA, NIFS, NIST, ORNL, GAPHIOR, etc.

Data provide

feed

back

Views from Database assessed data on electron collision cross sections

Electron Interaction 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

Definition of various Cross Section

・ Differential Cross Section for channel “n”

2

00

0 ),(),(

),(

Ef

k

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

Collision Data for Molecules by Electron Impact

investigated at Sophia University

CH4, C2H6, C3H8, C2H4, C3H4, C3H6

CF4, C2F6, C3F8, C2F4, c-C4F8, C6F6, C3F6

CF3H, CF2H2, CFH3

CF3Cl, CF3Br, CF3I

CF2Cl2, CFCl3

SiH4, Si2H6, SiF4, GeH4

NF3, C60

N2O, CO2, COS, H2O, CS2, XeF2, HCN

F2CO

Activities on Data Compilation

NIFS: Compile the previous related data available in literature but scattered in different places all over JAPAN for Plasma Processing

JAERI: Provide the electron collision data of the C-H double bond compound molecules for Fusion

Our Data Base to be prepared in IAEA,NIFS Report, and AAMOP

On-going and Near -future Measurements EELS:

Elastic Scattering: C3H6 isomers, C3F6

Vibrational Excitation : C3F6, COF2

Electronic Excitation : C3F6, COF2, H2O, DNA bases

Excited Molecular Target: vibratinally excited H2, CO2

QMSS:Radical Detection: CHx (X=31) from CH4

Negative Ion Detection: Gas- and Condensed-PhaseLEED:

Anti-ferromagnetic Surface: NiO, CoO, FeO

Why C3H6, C3F6, and COF2?

Data Base for Alternative Gases in Plasma Etching Process

Data Base for Hydro-carbon Molecules near the Edge Plasma of Fusion Plasma

New trends in processing system design

Two approaches have been introduced:

Vertically integrated computer-aided design for device processing (VicAddress)

(Prof. Makabe’s group, Japan)

Intelligent nano-prosessing technology for nanometer-processing techniques with in-time monitoring and

simulation (System-on chip (SoC) design)

(Prof. Samukawa’s group, Japan)

Plasma Processing will be still in core methodology!

Gas-phaseC + A

A+ + B-

A + AB

Q(ε)

Kj

Feed Gas

Database Governing Equation Source

from T. Makabe

Modeling flows for plasma processing

Gases commonly used for plasma etching

Materials Classification Molecular speciesSi Fluorides CF4, SF6, NF3, SiF4, BF3, CBrF3, XeF2

Chlorofluorides CClF3, CCl2F2, CCl3F, C2ClF5, C2Cl2F4

Chlorides CCl4, SiCl4, PCl3, BCl3, Cl2, HCl

Bromides Br2, HBr

Si dioxide Fluoride/hydrogen CHF3, CF4+H2

Fluorocarbons C2F6, C3F8, C4F8

Al alloys Chlorides CCl4, BCl3, SiCl4, Cl2, HCl

Chlorofluorides CCl2F2, CCl3F

Bromides Br2, BBr3Current database needs to elaborate on the optimum conditions between the device designer and the process engineer.

Green Chemistry

High-performance etching of SiO2 at high efficiency with small amounts of PFC gases

Etching of SiO2 using alternative gases with low GWP value

Cleaning alternative gases for electronics devices with low GWP value

(targets in ASET/ RITE/ Mirai / Projects of NEDO in JAPAN)

In parallel with the trends, more ecologically friendly processing technology is demanded:

(ASET: Association of Super-advanced Electronics Technology)

(RITE: Research Institute of Innovative Technology for the Earth)

(NEDO:New Energy and Industrial Technology Development Organization)

Alternative Candidates compared with feed gases commonly used

GWP: Global Warming Potential NFPA: National Fire Protection Association

ITER (International Thermonuclear Reactor) agreed in June to be built in Cadarache, France

Data Needs for

Carbon impurities (H-C molecules) produced by physical and chemical sputtering CH3, CH4, C2H2, C2H4, C2H6, C3H8

Vibrationally (Hot) excited Molecules H2, D2

Electron Collision Cross Section Data

e + C2H4

prototype of double bond H-C

elastic scattering qm vibrationalexcitation qv

electronic excitation qe ionization qi

10- 1 100 101 102 103

10- 2

10- 1

100

101

qi

qe3

qe2

qe1

qv2

qv1

qm

Cro

ss s

ecti

on

(10-1

6 cm2 )

Electron energy (eV)

From M. Hayashi

C3X6 elastic DCS (X = H, F)

1

1

1

1

1

1

10

1

10

0 40 80 120

1

10

1

10

1

10

1

10

0.1

0 40 80 120

100eV

60eV

30eV

20eV

15eV

10eV

9eV

8eV

7eV

6eV

5eV

4eV

3eV

2eV

DC

S(10-

16 c

m2 /

sr)

Scattering Angle (deg)

1.5eV △ ： C3H6

■ ： C3F6

Double bond

X2C2X2

(C2H4,C2F4)

X2C2XCX3

(C3H6, C3F6)

Neutral Radical Detection 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

10 20 30 400

0.5

1

1.5

2

2.5

: present : Moore et al.: Sugai et al.A

bs

olu

te c

ros

s s

ec

tio

n (

10

–16 c

m2 )

Impact energy (eV)

CH3 radical formation cross sections

Table 1. Ionization thresholds

e + CH4 CH3 + H + e

e + CH3 CH3+

+2e

Deduction for unknown DCS

COF2 vibrational excitation

6 8 10 12 14 16 18

0

5

10

15

20

25Electronic Excitation

100eV 5deg 30eV 10deg

DC

S (1

0-18 cm

2 /sr)

Energy Loss (eV)

x15

COF2 Electronic Excitation

-24-

e-

６００℃ １２００℃

２５００℃

Hot Molecular Beam Source

Sheath heater

Electron Bombardment

288 289 290 291 292 293

TIY0o

Inte

nsity

(arb

. uni

ts)

room 430 C

(b)

CO2 C 1s

ground excited

(c)90o TIY

room 430 C

(d)

Photon energy (eV)

ground excited

(a)

532 533 534 535 536 537 538

(a)0o

Inte

nsity

(arb

. uni

ts)

TIY room 430 C

(b)

CO2 O 1s

ground excited

(c)90o TIY

room 430 C

(d)

Photon energy (eV)

ground excited

C 1C 1ss-1-122uu excitation excitation O 1O 1ss-1-122uu excitation excitation

Results Comparison

Outlook EELS:

Elastic Scattering: C3H6 C3F6 COF2

Vibrational Excitation : C3H6 C3F6 COF2

Electronic Excitation : C3F6 COF2 (H2O, DNA bases)

QMSS:Radical Detection: CHx (X = 30) from CH4

Our Data Base to be prepared in IAEA,NIFS Report, and AAMOP

Future Plan

Radical Detection: OH from H2O

Excited Molecular Target: vibratinally excited H2,CO2

Negative Ion Detection: Gas- and Condensed-Phase

H2O vibrational excitation

0

0

0

4 6 8 100

4 6 8 10

0.43 eV

0.46 eV

0.51 eV

0.49 eV

Inte

nsi

ty (

arb

. un

its)

Inte

nsi

ty (

arb

. un

its)

Impact energy (eV)

3

3

3

3

60 deg 90 deg0.45 eV

0.46 eV

0.49 eV

0.51 eV

Impact energy (eV)

-0.2 0.0 0.2 0.4 0.6 0.80

200

400

600

800

1000

DCBA

E0 = 7.5 eV

angle 90 deg

Inten

sity (

arb.

units

)

(010)

(000)

(001)

(100)

Energy loss (eV)

H2O electronic excitation

H2O GOS

No Molecular Formula GWP(100ys) A.L.T (100ys)

1 CF3I negligible negligible

2 ｌ- C4F6 >100 1.7(days)

3 C3F6 >100 >0.01

4 CF3COCF3 unknown <10

5 C5F8 90 0.98

6 (CF3CO)2O 0 0.84

7 CF3OCHFCF3 0.22 11

8 CF3CH2OH unknown 0.5

9 (CF3)2CHOH unknown 0.5

10 C2F5I negligible negligible

11 F(CF2)3I negligible negligible

12 CF3CFICF3 negligible negligible

No Molecular Formula GWP A.L.T(100ys)

1 CO2 1 0.5 2～

2 CF4 6500 500

3 C2F6 9200 100

4 C3F8 7000 26

5 α - C4F8 8700 32

6 CHF3 11700 2.64

7 SF6 23900 32

8 NF3 8000 7

Alternative Candidates Feed Gases commonly used

GWP: Global Warming Potential A.L.T: Atmospheric Life Time