Reactions of Silicon Atoms and Silylenes

Tang, Yingjie

doi:10.1007/978-1-4613-3192-6_4

Cited by 33 publications

(3 citation statements)

References 182 publications

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“…SiH 2 is an important intermediate in the chemistry of silicon hydrides and organosilicon compounds. 19,20 It plays a major role in thermally initiated chemical vapour deposition (CVD) processes used for generating high quality films of amorphous Si, SiO, or SiN. 21,22 The kinetics of numerous elementary reactions of SiH 2 have been comprehensively reviewed by Jasinski, Becerra, and Walsh.…”

Section: Introductionmentioning

confidence: 99%

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

Guo

Fikri

Friedrichs

et al. 2003

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

Guo

Fikri

Friedrichs

et al. 2003

Phys. Chem. Chem. Phys.

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“…Heating and optical irradiation of hydrosilane results in cleavage of the relatively weak intrachain Si–Si bond, thereby leading to silylene‐type radicals . The radicals are ground‐state singlets, and their characteristic reactions include insertion into Si–H bonds and π‐type addition across C=C and C≡C bonds . In the present case, these generated radicals react with unsaturated bonds in 1‐hexyne and a Si–H bond in CPS.…”

Section: Resultsmentioning

confidence: 78%

Properties of Phosphorus‐Doped Silicon‐Rich Amorphous Silicon Carbide Film Prepared by a Solution Process

et al. 2016

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Using a polymeric precursor synthesized from a mixture of cyclopentasilane, white phosphorus, and 1‐hexyne, we deposited phosphorus‐doped silicon‐rich amorphous silicon carbide (a‐SiC) films via a solution‐based process. Unlike conventional polymeric precursors, this polymer requires neither catalysts nor oxidation for its synthesis and cross‐linkage. Therefore, the polymeric precursor is sufficiently pure for effective doping and fabricating semiconducting a‐SiC. This study presents the results of a detailed study of the effect of carbon and phosphorus concentrations on the structural, optical, and electrical properties of a‐SiC films. The lowest activation energy for these films is 0.39 eV, which leads to an optical gap and a dark conductivity of 2.1 eV and 109 Ω cm, respectively. Moreover, these films satisfy the Meyer–Neldel rule for thermally activated conductivity, which indicates that white‐phosphorus doping of solution‐processed a‐SiC produces films with the same characteristics as phosphine‐doped vacuum‐processed a‐SiC.

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“…SiH 2 radicals are important intermediates in the chemistry of silicon hydrides and organosilicon compounds, and the reactions of SiH 2 with saturated and unsaturated hydrocarbons have practical significance for modeling chemical vapor deposition (CVD) processes. – In contrast to CH 2 , for which the chemistry is complicated by the interplay of a less reactive triplet ground state and an energetically low-lying reactive singlet state, SiH 2 reactions are dominated by its singlet ground state ( 1 A 1 ) . A considerable set of SiH 2 reaction rate constants, mostly based on time-resolved measurements of SiH 2 concentration profiles, already exist and have been reviewed by Walsh and co-workers , and more recently were updated and compared with available data for other heavy carbenes by Becerra and Walsh .…”

Section: Introductionmentioning

confidence: 99%

Time-Resolved Cavity Ringdown Measurements and Kinetic Modeling of the Pressure Dependences of the Recombination Reactions of SiH₂ with the Alkenes C₂H₄, C₃H₆, and t-C₄H₈

et al. 2008

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Room-temperature rate constants for the pressure-dependent reactions SiH2 + ethene, propene, and t-butene have been determined at total pressures of 3.3 mbar < or = p < or = 300 mbar with Ar as buffer gas. SiH2 was detected by means of time-resolved cavity ringdown spectroscopy (CRDS), and the deconvolution of ringdown, kinetics, and laser bandwidth effect was accomplished with the extended simultaneous kinetics and ringdown model (eSKaR). In this way, pseudofirst-order rate constants could be extracted from nonexponential ringdown profiles. The recombination reactions, including the reaction SiH2 + i-butene, have been modeled based on the simplified statistical adiabatic channel model (SACM) and weak collision energy-grained master equation (ME) simulations. The influence of an interfering fast isomerization channel was investigated based on the Rice, Ramsperger, Kassel, Marcus theory (RRKM) and was found to be only important for the C2H4 reaction. Using ab initio energies (G3) and structures (MP2/6-311G(d,p)) as input parameters for the kinetic models, a consistent description of the pressure and temperature dependences of all four reactions was possible. In the temperature range 295 K < or = T < or = 600 K, the extrapolated limiting high-pressure rate constants, k(infinity)(C2H4)/(cm(3) x mol(-1) x s(-1)) = 1.9 x 10(14) (T/K)(-0.065), k(infinity)(C3H6)/(cm(3) x mol(-1) x s(-1)) = 1.3 x 10(14) (T/K)(0.075), k(infinity)(i-C4H8) = 1.8 x 10(14) cm(3) x mol(-1) x s(-1), and k(infinity)(t-C4H8)/(cm(3) x mol(-1) x s(-1)) = 4.6 x 10(13) (T/K)(0.21), are close to the collision number and are more or less temperature independent. In the case of ethene, probably due to the approximate treatment of rotational effects and/or the interfering isomerization process, the applied model slightly underestimates the falloff and thus yields too high extrapolated rate constants at p < 10 mbar.

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Reactions of Silicon Atoms and Silylenes

Cited by 33 publications

References 182 publications

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

Properties of Phosphorus‐Doped Silicon‐Rich Amorphous Silicon Carbide Film Prepared by a Solution Process

Time-Resolved Cavity Ringdown Measurements and Kinetic Modeling of the Pressure Dependences of the Recombination Reactions of SiH₂ with the Alkenes C₂H₄, C₃H₆, and t-C₄H₈

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Reactions of Silicon Atoms and Silylenes

Cited by 33 publications

References 182 publications

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH2 + O2

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH2 + O2

Properties of Phosphorus‐Doped Silicon‐Rich Amorphous Silicon Carbide Film Prepared by a Solution Process

Time-Resolved Cavity Ringdown Measurements and Kinetic Modeling of the Pressure Dependences of the Recombination Reactions of SiH2 with the Alkenes C2H4, C3H6, and t-C4H8

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An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

An extended simultaneous kinetics and ringdown model: Determination of the rate constant for the reaction SiH₂ + O₂

Time-Resolved Cavity Ringdown Measurements and Kinetic Modeling of the Pressure Dependences of the Recombination Reactions of SiH₂ with the Alkenes C₂H₄, C₃H₆, and t-C₄H₈