• Journal of Industrial Technology
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• v.25 no.A
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• pp.141-149
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• 2005

We investigated numerically the evolutions of several chemical species which are important for film growth and particle generation in the pulsed $SiH_4$ plasmas. During the plasma-on, the $SiH_x$ concentration increases with time mainly by the generation reaction from $SiH_4$, but, during the plasma-off, decreases because of the hydrogen adsorption reaction. During the plasma-on, the concentrations of negative ions increase with time by the polymerization reactions of negative ions and those become almost zero in the sheath regions because of the electrostatic repulsion. During the plasma-off, the concentrations of negative ions decrease with time by the neutralization reactions with positive ions and some negative ions can diffuse toward the sheath regions because there is no electric field inside the reactor. The polymerized negative ions of higher mass can be reduced successfully by using the pulsed plasma process.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.636-644
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• 1991

The cationic polymerization of substituted oxethanes which have pendant energetic groups such as methoxy, azido, and nitrato are investigated theoretically using the semiempirical MINDO/3, MNDO, and AM1 methods. The nucleophilicity and basicity of substituted oxethanes can be explained by the negative charge on oxygen atom of oxetanes. The reactivity of propagation in the polymerization of oxetanes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxetanes. The reaction of the energetic cyclic oxonium ion forms to the open chain carbenium ion forms is expected by computational stability energy of the oxonium and carbenium ion (about 10~20 kcal/mole) favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on clauclation that the prepolymer propagation step SN1 mechanism will be at least as fast as that for SN2 mechanism.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.461-468
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• 1991

The cationic polymerizations of substituted oxiranes which have pendant energetic groups such as azido, and nitrato, are investigated theoretically using the semiempirical MNDO, and $AM_1$ methods. The nucleophilicity and basicity of substituted oxiranes can be explained by the negative charge on oxygen atom of oxiranes. The reactivity of propagation in the polymerization of oxiranes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxiranes. Ring opening of the complexed cyclic oxonium ion to the open chain carbenium ion is expected computational stability of the oxonium and carbenium ion by 30∼40 kcal/mol favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions will be a major determinant of mechanism. The chain growth $SN_1$, mechanism will be at least as fast as that for $SN_2$ mechanism.