Growth of fluorocarbon macromolecules in the gas phase: II. The growth mechanisms of large positive ions observed in the downstream region of Ar/CF4 plasmas

Kenji Furuya, Shinobu Yuktta, Akira Harata

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The mass analysis of positive ions has been carried out at a position 90 cm downstream from the center of the Ar/CF4 plasmagenerating area, the size of which is 5 cm in length and 5 cm in diameter in a cylindrical tube. As a result, it has been found that there are six series of adduct ions, C nF2n+1 + (n = 2-7), Cnp2 n-1 + (n = 3-8), CnF2n-3 + (n = 3-9), CnF2n-5 + (n = 6-10), C nF2n + (n = 2-6), and CnF2 n-2 + (n = 4-6), as well as CF+, CF 2 +, and CF3 + produced by (dissociative) ionization of CF4 and its neutral fragments. The dependence of the intensities of Ar+, CF+, CF2 +, and CF3 + on the CF4 mixing ratio in a range of 0-0.3 agrees very well with that predicted by Kimura and Takai [Jpn. J. Appl. Phys. 43 (2004) 7240] using a global model for an electronegative plasma. This fact demonstrates that various chemical reactions advance even in the downstream region of the plasma. The logarithmic plots of the intensity in CnF2n+1 + at n ≥ 2 with respect to the mass number decrease linearly as the mass number increases. This is the case for CnF2n-1 + at n ≥ 3, and its slope is gentler than that in the CnF2n+1 + case. Quantum chemical calculations with GAUSSIAN 03 have been carried out to estimate the enthalpy change in the various reactions predicted to advance in the downstream region of the plasma. As a result, it has been found that C2F 5 + is produced dominantly by the addition reaction of CF3 + to CF2. No peak is assigned to the C 2F3 + ion in all the observed mass spectra. This finding indicates that the C3F5 + ion must be produced, not by the addition reaction between C2P 3 + and CF2, but by other reactions. C 3F5 + is expected to be produced by the reactions, C3F7 + + CF2 → C 3F5 + + CF4, C2F 5 + + CF → C3P5 + + F, and C3F7 + + CF → C3F 5 + + CF3, judging from the calculated enthalpy changes of these processes. The linearity of the logarithmic plots obtained experimentally can be described by considering the rate equations for the addition reactions of CF2 with CnF2n+1 + at n ≥ 2 and CnF2n-1 + at n ≥ 3 under the steady-state approximation. The difference in the slope between the logarithmic plots of the intensity in the CnF 2n+1 + and CnF2n-1 + series indicates that the formation of CnF2n-1 + at n ≥ 4 is due to the addition reaction of CF2 with Cn-1F2n-3 +. The lowest unoccupied molecular orbitals (LUMOs) of the CnF2n+1 + series are dominantly constructed from the -CF2 + end included commonly in CnF2n+1 +, and those of the C nF2n-1 + series are from the -C 3p4 + end, regardless of the value of n. leading to the difference in the reactivity between CnF 2n+1 + and CnF2n-1 +.

Original languageEnglish
Pages (from-to)5219-5231
Number of pages13
JournalJapanese Journal of Applied Physics, Part 1: Regular Papers and Short Notes and Review Papers
Volume45
Issue number6 A
DOIs
Publication statusPublished - Jun 28 2006

Fingerprint

Addition reactions
Fluorocarbons
fluorocarbons
Macromolecules
Heavy ions
positive ions
macromolecules
Positive ions
vapor phases
Plasmas
Gases
Enthalpy
Ions
plots
Molecular orbitals
Ionization
enthalpy
Chemical reactions
slopes
ions

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

@article{4de92135a98f46c1b6ba43ee74b2ae09,
title = "Growth of fluorocarbon macromolecules in the gas phase: II. The growth mechanisms of large positive ions observed in the downstream region of Ar/CF4 plasmas",
abstract = "The mass analysis of positive ions has been carried out at a position 90 cm downstream from the center of the Ar/CF4 plasmagenerating area, the size of which is 5 cm in length and 5 cm in diameter in a cylindrical tube. As a result, it has been found that there are six series of adduct ions, C nF2n+1 + (n = 2-7), Cnp2 n-1 + (n = 3-8), CnF2n-3 + (n = 3-9), CnF2n-5 + (n = 6-10), C nF2n + (n = 2-6), and CnF2 n-2 + (n = 4-6), as well as CF+, CF 2 +, and CF3 + produced by (dissociative) ionization of CF4 and its neutral fragments. The dependence of the intensities of Ar+, CF+, CF2 +, and CF3 + on the CF4 mixing ratio in a range of 0-0.3 agrees very well with that predicted by Kimura and Takai [Jpn. J. Appl. Phys. 43 (2004) 7240] using a global model for an electronegative plasma. This fact demonstrates that various chemical reactions advance even in the downstream region of the plasma. The logarithmic plots of the intensity in CnF2n+1 + at n ≥ 2 with respect to the mass number decrease linearly as the mass number increases. This is the case for CnF2n-1 + at n ≥ 3, and its slope is gentler than that in the CnF2n+1 + case. Quantum chemical calculations with GAUSSIAN 03 have been carried out to estimate the enthalpy change in the various reactions predicted to advance in the downstream region of the plasma. As a result, it has been found that C2F 5 + is produced dominantly by the addition reaction of CF3 + to CF2. No peak is assigned to the C 2F3 + ion in all the observed mass spectra. This finding indicates that the C3F5 + ion must be produced, not by the addition reaction between C2P 3 + and CF2, but by other reactions. C 3F5 + is expected to be produced by the reactions, C3F7 + + CF2 → C 3F5 + + CF4, C2F 5 + + CF → C3P5 + + F, and C3F7 + + CF → C3F 5 + + CF3, judging from the calculated enthalpy changes of these processes. The linearity of the logarithmic plots obtained experimentally can be described by considering the rate equations for the addition reactions of CF2 with CnF2n+1 + at n ≥ 2 and CnF2n-1 + at n ≥ 3 under the steady-state approximation. The difference in the slope between the logarithmic plots of the intensity in the CnF 2n+1 + and CnF2n-1 + series indicates that the formation of CnF2n-1 + at n ≥ 4 is due to the addition reaction of CF2 with Cn-1F2n-3 +. The lowest unoccupied molecular orbitals (LUMOs) of the CnF2n+1 + series are dominantly constructed from the -CF2 + end included commonly in CnF2n+1 +, and those of the C nF2n-1 + series are from the -C 3p4 + end, regardless of the value of n. leading to the difference in the reactivity between CnF 2n+1 + and CnF2n-1 +.",
author = "Kenji Furuya and Shinobu Yuktta and Akira Harata",
year = "2006",
month = "6",
day = "28",
doi = "10.1143/JJAP.45.5219",
language = "English",
volume = "45",
pages = "5219--5231",
journal = "Japanese Journal of Applied Physics, Part 1: Regular Papers & Short Notes",
issn = "0021-4922",
publisher = "Institute of Physics",
number = "6 A",

}

TY - JOUR

T1 - Growth of fluorocarbon macromolecules in the gas phase

T2 - II. The growth mechanisms of large positive ions observed in the downstream region of Ar/CF4 plasmas

AU - Furuya, Kenji

AU - Yuktta, Shinobu

AU - Harata, Akira

PY - 2006/6/28

Y1 - 2006/6/28

N2 - The mass analysis of positive ions has been carried out at a position 90 cm downstream from the center of the Ar/CF4 plasmagenerating area, the size of which is 5 cm in length and 5 cm in diameter in a cylindrical tube. As a result, it has been found that there are six series of adduct ions, C nF2n+1 + (n = 2-7), Cnp2 n-1 + (n = 3-8), CnF2n-3 + (n = 3-9), CnF2n-5 + (n = 6-10), C nF2n + (n = 2-6), and CnF2 n-2 + (n = 4-6), as well as CF+, CF 2 +, and CF3 + produced by (dissociative) ionization of CF4 and its neutral fragments. The dependence of the intensities of Ar+, CF+, CF2 +, and CF3 + on the CF4 mixing ratio in a range of 0-0.3 agrees very well with that predicted by Kimura and Takai [Jpn. J. Appl. Phys. 43 (2004) 7240] using a global model for an electronegative plasma. This fact demonstrates that various chemical reactions advance even in the downstream region of the plasma. The logarithmic plots of the intensity in CnF2n+1 + at n ≥ 2 with respect to the mass number decrease linearly as the mass number increases. This is the case for CnF2n-1 + at n ≥ 3, and its slope is gentler than that in the CnF2n+1 + case. Quantum chemical calculations with GAUSSIAN 03 have been carried out to estimate the enthalpy change in the various reactions predicted to advance in the downstream region of the plasma. As a result, it has been found that C2F 5 + is produced dominantly by the addition reaction of CF3 + to CF2. No peak is assigned to the C 2F3 + ion in all the observed mass spectra. This finding indicates that the C3F5 + ion must be produced, not by the addition reaction between C2P 3 + and CF2, but by other reactions. C 3F5 + is expected to be produced by the reactions, C3F7 + + CF2 → C 3F5 + + CF4, C2F 5 + + CF → C3P5 + + F, and C3F7 + + CF → C3F 5 + + CF3, judging from the calculated enthalpy changes of these processes. The linearity of the logarithmic plots obtained experimentally can be described by considering the rate equations for the addition reactions of CF2 with CnF2n+1 + at n ≥ 2 and CnF2n-1 + at n ≥ 3 under the steady-state approximation. The difference in the slope between the logarithmic plots of the intensity in the CnF 2n+1 + and CnF2n-1 + series indicates that the formation of CnF2n-1 + at n ≥ 4 is due to the addition reaction of CF2 with Cn-1F2n-3 +. The lowest unoccupied molecular orbitals (LUMOs) of the CnF2n+1 + series are dominantly constructed from the -CF2 + end included commonly in CnF2n+1 +, and those of the C nF2n-1 + series are from the -C 3p4 + end, regardless of the value of n. leading to the difference in the reactivity between CnF 2n+1 + and CnF2n-1 +.

AB - The mass analysis of positive ions has been carried out at a position 90 cm downstream from the center of the Ar/CF4 plasmagenerating area, the size of which is 5 cm in length and 5 cm in diameter in a cylindrical tube. As a result, it has been found that there are six series of adduct ions, C nF2n+1 + (n = 2-7), Cnp2 n-1 + (n = 3-8), CnF2n-3 + (n = 3-9), CnF2n-5 + (n = 6-10), C nF2n + (n = 2-6), and CnF2 n-2 + (n = 4-6), as well as CF+, CF 2 +, and CF3 + produced by (dissociative) ionization of CF4 and its neutral fragments. The dependence of the intensities of Ar+, CF+, CF2 +, and CF3 + on the CF4 mixing ratio in a range of 0-0.3 agrees very well with that predicted by Kimura and Takai [Jpn. J. Appl. Phys. 43 (2004) 7240] using a global model for an electronegative plasma. This fact demonstrates that various chemical reactions advance even in the downstream region of the plasma. The logarithmic plots of the intensity in CnF2n+1 + at n ≥ 2 with respect to the mass number decrease linearly as the mass number increases. This is the case for CnF2n-1 + at n ≥ 3, and its slope is gentler than that in the CnF2n+1 + case. Quantum chemical calculations with GAUSSIAN 03 have been carried out to estimate the enthalpy change in the various reactions predicted to advance in the downstream region of the plasma. As a result, it has been found that C2F 5 + is produced dominantly by the addition reaction of CF3 + to CF2. No peak is assigned to the C 2F3 + ion in all the observed mass spectra. This finding indicates that the C3F5 + ion must be produced, not by the addition reaction between C2P 3 + and CF2, but by other reactions. C 3F5 + is expected to be produced by the reactions, C3F7 + + CF2 → C 3F5 + + CF4, C2F 5 + + CF → C3P5 + + F, and C3F7 + + CF → C3F 5 + + CF3, judging from the calculated enthalpy changes of these processes. The linearity of the logarithmic plots obtained experimentally can be described by considering the rate equations for the addition reactions of CF2 with CnF2n+1 + at n ≥ 2 and CnF2n-1 + at n ≥ 3 under the steady-state approximation. The difference in the slope between the logarithmic plots of the intensity in the CnF 2n+1 + and CnF2n-1 + series indicates that the formation of CnF2n-1 + at n ≥ 4 is due to the addition reaction of CF2 with Cn-1F2n-3 +. The lowest unoccupied molecular orbitals (LUMOs) of the CnF2n+1 + series are dominantly constructed from the -CF2 + end included commonly in CnF2n+1 +, and those of the C nF2n-1 + series are from the -C 3p4 + end, regardless of the value of n. leading to the difference in the reactivity between CnF 2n+1 + and CnF2n-1 +.

UR - http://www.scopus.com/inward/record.url?scp=33745255676&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33745255676&partnerID=8YFLogxK

U2 - 10.1143/JJAP.45.5219

DO - 10.1143/JJAP.45.5219

M3 - Article

AN - SCOPUS:33745255676

VL - 45

SP - 5219

EP - 5231

JO - Japanese Journal of Applied Physics, Part 1: Regular Papers & Short Notes

JF - Japanese Journal of Applied Physics, Part 1: Regular Papers & Short Notes

SN - 0021-4922

IS - 6 A

ER -