electron collision data of c-h compound molecules for plasma modeling framework for our research...
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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: [email protected]
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
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)
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
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
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)
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