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  • 1
    Electronic Resource
    Electronic Resource
    Rate coefficient for the reaction of methyldioxy with nitric oxide at 295 K (1981)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 85 (1981), S. 3136-3138 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j150621a026
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of trifluoromethyl radical with atomic oxygen(3P) and molecular oxygen at 295 K (1982)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 86 (1982), S. 4678-4683 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100221a008
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  • 3
    Electronic Resource
    Electronic Resource
    Gas-phase reactions of CF2 with O(3P) to produce COF: Their significance in plasma processing (1984)
    Springer
    Plasma chemistry and plasma processing 4 (1984), S. 271-283 
    Details
    ISSN: 1572-8986
    Keywords: Plasma etching ; CF2 reactions ; F atom production ; CF4-O2 plasmas ; COF reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Reactions between CF2 and O(3P) have been studied at 295 K in a gas flow reactor sampled by a mass spectrometer. The major reaction for CF2 has been found to be $$CF_2 + O \to COF + F$$ with $$CF_2 + O \to CO + 2F(F_2 )$$ more than a factor of three slower. The rate coefficient for all loss processes for CF2 on reaction with O is (1.8±0.4)×10−11 cm3 s−1. The COF produced in (18) undergoes a fast reaction with O to produce predominantly CO2. $$COF + O \to CO_2 + F$$ It is uncertain from the results whether or not $$COF + O \to CO + FO$$ occurs, but in any event (19) is the major route. The rate coefficient for the loss of COF in this system [i.e., the combined rate coefficients for (19) and (20)] is (9.3±2.1)×10−11 cm3 s−1. Stable product analysis reveals that for each CF2 radical consumed, the following distribution of stable products is obtained: COF2 (0.04±0.02), CO (0.21±0.04), and CO2 (0.75±0.05). Thus COF2, which we assume is produced via $$CF_2 + O \xrightarrow{M} COF_2$$ is a very minor product in this reaction sequence. The measured rate coefficients demonstrate that reactions (18) and (19) are important sources of F atoms in CF4/O2 plasmas.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00568981
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  • 4
    Electronic Resource
    Electronic Resource
    Gas-phase reactions of CF3 and CF2 with atomic and molecular fluorine: Their significance in plasma etching (1986)
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 11-25 
    Details
    ISSN: 1572-8986
    Keywords: Plasma etching ; CF3 reactions ; CF2 reactions ; F atom reactions ; association reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Reaction rate coefficients have been measured at 295 K for both CF3 and CF2 with atomic and molecular fluorine. The reaction between CF3 and F was studied over a gas number density range of (2.4–23)×1016 cm−3 with helium as the bath gas. The measured rate coefficient increased from (1.1–1.7)×10−11 cm3 s−1 as the gas number density increased over this range. In contrast to this relatively small change in rate coefficient with gas number density, the rate coefficient for CF2+F increased from (0.4–2.3)×10−12 cm3 s−1 as the helium gas number density increased from (3.4–28.4)×1016 cm−3. Even for the highest bath gas number density employed, the rate coefficient was still more than an order of magnitude lower than earlier measurements of this coefficient performed at comparable gas number densities. Both these association reactions are examined from the standpoint of the Gorin model for association of radicals and use is made of unimolecular dissociation theory to examine the expected dependence on gas number density. The calculations reveal that CF3+F can be explained satisfactorily in these terms but CF2+F is not well described by the simple Gorin model for association. CF3 was found to react with molecular fluorine with a rate coefficient of (7±2)×10−14 cm3 s−1 whereas only an upper limit of 2×10−15 cm3 s−1 could be placed on the rate coefficient for the reaction between CF2 and F2. The values obtained for this set of reactions mean that the reaction between CF3 and F will play an important role in plasmas containing CF4. The high rate coefficient will mean that, under certain conditions, this particular reaction will control the amount of CF4 consumed. On the other hand, the much lower rate coefficient for reactions between CF2 and F means that CF2 will attain much higher concentrations than CF3 in plasmas where these combination reactions are dominant.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00573818
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  • 5
    Electronic Resource
    Electronic Resource
    Gas-phase reactions in plasmas of SF6 with O2: Reactions of F with SOF2 and SO2 and reactions of O with SOF2 (1989)
    Springer
    Plasma chemistry and plasma processing 9 (1989), S. 409-420 
    Details
    ISSN: 1572-8986
    Keywords: Gas flow reactor ; plasma chemistry of SF6/O2 ; rate coefficients ; experimental
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The plasma chemistry of SF6/O2 mixtures is particularly complicated because of the large number of possible reactions. Over a wide range of conditions, products including SF4, SOF4, SOF2, and SO2F2 can be formed but thre is considerable uncertainty about the major reactions which contribute to the formation of these species. In this work reactions of oxygen atoms with SOF2 and fluorine atoms with SOF2 and SO2 have been studied in order to determine the principal sources of SO2F2 in these plasmas. Reactions were studied at 295 K in a gas flow reactor sampled by a mass spectrometer. No reaction could be detected between oxygen atoms and SOF2, which for the conditions employed, means that the upper limit for the reaction rate coefficient is 1×10−14 cm3 sec−1. The reaction of fluorine atoms with SOF2 was studied with the helium bath gas number density ranging from 3.1×1016 to 2.0×1017 cm−3. Within this range the rate coefficient increased with increasing [He] from (4.1 to 10.8)×10−14 cm3 sec−1. SO2 was found to react with fluorine atoms with a rate coefficient which appeared to be independent of the helium bath gas number density over the range given above. The possibility that this reaction occurred entirely on the walls of the reactor is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01083675
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  • 6
    Electronic Resource
    Electronic Resource
    Aspects of the chemistry of SF6/O2 plasmas (1989)
    Springer
    Plasma chemistry and plasma processing 9 (1989), S. 483-496 
    Details
    ISSN: 1572-8986
    Keywords: Low-pressure plasma ; rate coefficients ; analytical/experimental
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The production ofSOF 4 initiated by the reaction of F atoms withSOF 2 has been studied in a gas-flow reactor at 295 K for helium bath gas number densities in the range (3.0–27.0)×1016 cm−3. The effect of O atoms on the formation ofSOF 4 has been analyzed in terms of the competing reactionsSOF 3+F→SOF4 andSOF 3+O→SO 2 F 2+F. This analysis leads to the conclusion that the rate coefficients for these two processes are equal within an uncertainty of about 50%. Furthermore, both experiment and calculations indicate that the rate coefficient for reactions between F atoms andSOF 3 is close to its high-pressure limit under the conditions employed. The experiments set a lower limit on this rate coefficient of 5×10−11 cm3 s−1, while calculations based on unimolecular rate theory suggest that it may be greater than 1×10−10 cm3 s−1. These results make it clear that the two reactions shown above cannot explain the relative abundances ofSOF 4 andSO 2 F 2 which are observed inSF 6/O 2 plasmas. This suggests thatSF 2 is a major precursor in the sequence of reactions following the dissociation ofSF 6.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01023915
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  • 7
    Electronic Resource
    Electronic Resource
    Gas-phase reactions of SF5, SF2, and SOF with O(3 P): Their significance in plasma processing (1986)
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 247-258 
    Details
    ISSN: 1572-8986
    Keywords: Plasma etching ; SF6-O2 plasmas ; SF5 reactions ; SF2 reactions ; plasma chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Reactions of both SF5 and SF2 with O(3 P) and molecular oxygen have been studied at 295 K in a gas flow reactor sampled by a mass spectrometer. For reactions with O(3 P), rate coefficients of (2.0±0.5)×10−11 cm3 s−1 and (10.8±2.0)×10−11 cm3 s−1 were obtained for SF5 and SF2 respectively. The rate coefficients for reactions with O2 are orders of magnitude lower, with an estimated upper limit of 5×10−16 cm3 s−1 for both SF5 and SF2. Reaction of SF2 with O(3 P) leads to the production of SOF which then reacts with O(3 P) with a rate coefficient of (7.9±2.0)×10−11 cm3 s−1. Both SO and SO2 are products in the reaction sequence initiated by reaction between SF2 and O(3 P). Although considerable uncertainty exists for the heat of formation of SOF, it appears that SO arises only from reaction between SOF and O atoms which is also the source of SO2. These results are discussed in terms of a reaction scheme proposed earlier to explain processes occurring during the plasma etching of Si in SF6/O2 plasmas. A comparison between the results obtained here and those reported earlier for reactions of both CF3 and CF2 with O and O2 shows that there is a marked similarity in the free radical chemistry which occurs in SF6/O2 and CF4/O2 plasmas.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00575131
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  • 8
    Electronic Resource
    Electronic Resource
    A model of the chemical processes occurring in CF4/O2 discharges used in plasma etching (1986)
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 205-230 
    Details
    ISSN: 1572-8986
    Keywords: Plasma etching ; gas-phase reactions ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A model has been developed in an attempt to explain the chemistry which occurs in plasmas produced in mixtures of CF4 and O2. Emphasis is placed on gas-phase free radical reactions, and the predictions of the model are compared with experimental results. Dissociation rates following electron impact are deduced mainly from experimental observations although relative dissociation rates have been calculated. An important assumption of the model is that CF2 can be produced as a primary dissociation product following electron impact. Furthermore, this process is favored over that producing CF3 by more than a factor of 2. Experimental evidence is presented to support this assumption. Although the model agrees well with experiment on the total amount of fluorine produced, some discrepancy exists between the predicted and measured values of [F2]. It is suggested that the higher concentrations detected in the experiments resulted from recombination of F atoms in the sampling region. The agreement for concentrations of CO2, CO, and COF2 is generally better than a factor of 2 over a wide range of experimental conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00575129
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  • 9
    Electronic Resource
    Electronic Resource
    A model for the etching of Si in CF4 plasmas: Comparison with experimental measurements (1986)
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 231-246 
    Details
    ISSN: 1572-8986
    Keywords: Plasma etching ; CF4 chemistry ; modelling ; comparison with experiments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A model has been developed to describe the chemistry which occurs in CF4 plasmas and the etching of Si both in the plasma and downstream. One very important feature of this model is that for discharge residence times which vary by more than an order of magnitude, the amount of CF4 consumed is low and relatively constant. This is because the gas-phase combination reactions between F and both CF3 and CF2 lead to the rapid reforming of CF4. The model predicts that CF2 is a major species in the gas phase and that the [F] detected as a sample point downstream is a very sensitive function of [CF2]/[F] in the discharge. Even though the calculations show that [F] in the discharge varies only slightly over the wide range of experimental conditions considered, large variations in [F] at the sample point occur because the [CF2]/[F] ratio in the discharge changes. The concentrations of C2F6 and SiF4 are predicted to within a factor of 2 over a very wide range of experimental conditions. This confirms the importance of gas-phase free radical reactions in the etching of Si.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00575130
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  • 10
    Electronic Resource
    Electronic Resource
    Gas-phase reactions in plasmas of SF6 with O2 in He (1988)
    Springer
    Plasma chemistry and plasma processing 8 (1988), S. 263-280 
    Details
    ISSN: 1572-8986
    Keywords: Microwave plasma ; gas-phase reactions ; mass spectrometer sampling ; discharge chemistry of SF6 with O2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Processes which occur in microwave discharges of dilute mixtures of SF6 and O2 in He have been examined using a flow reactor sampled by a mass spectrometer. Two classes of experiments were performed. In the first set of experiments, mixtures containing 6×1011 cm−3 SF6, 6×1016 cm−3 He, and O2 in the range (0–3.6)×1013 cm−3 were passed through a 20-W 2450-MHz microwave discharge. The gas mixtures arriving at a sample point downstream from the discharge were examined for SF6, SF4, SOF2, SOF4, SO2F2, SO2, F, and O. In the second class of experiments, rate coefficients were measured for the reactions of SF4 with O and O2 and for the reaction of SF with O. The rate coefficient for the reaction of SF with O was found to be (4.2±1.5)×10−11 cm−3 s−1. SF4 was found to react so slowly with both oxygen atoms and oxygen molecules that only upper limits could be placed on the rate coefficients for these reactions. These values were 2×10−14 cm3 s−1 and 5×10−15 cm3 s−1 for reactions with O and O2 respectively. The observed distribution of products from the discharged mixtures is discussed in terms of the measured rate coefficients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01020406
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