Kinetics of the thermal decomposition of alkyl derivatives of Group III and V elements

Yablokov, V. A.; Yablokova, N. V.

doi:10.1070/rc1995v064n10abeh000187

Cited by 6 publications

(7 citation statements)

References 95 publications

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“…Interestingly, the value of E eff at θ = 0 agrees with the 35 kJ/mol previously reported for the low-temperature pyrolysis of TMA . The origin of that result remains controversial, but it has been suggested to have been caused by a surface process …”

Section: Discussionsupporting

confidence: 89%

“…78 The origin of that result remains controversial, but it has been suggested to have been caused by a surface process. 79 We have suggested the cooperative effect of neighboring CH 3 * groups as being one possible explanation for the coverage-dependent activation energy, but this is not the only interpretation. With E eff having a linear dependence on θ, the reaction probability obtained by equating eqs 8 and 10 is which has a functional form that resembles "type B" adsorption in the classification outlined by Morris, Bowker, and King.…”

Section: ■ Discussionmentioning

confidence: 92%

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Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

2020

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Atomic layer deposition (ALD) of Al 2 O 3 using trimethylaluminum and H 2 O is known to proceed through sequential surface reactions that leave the surface alternately terminated with AlCH 3 and OH groups. Using in situ reflection− absorption infrared spectroscopy in a flow reactor, we monitor the consumption of AlCH 3 groups by brief pulses of H 2 O at temperatures between 105 and 300 °C. At low temperatures, the surface reactions occur by what appears to be two stages that can be fit to a biexponential decay. Rate laws based on species of AlCH 3 groups that also predict a biexponential decay are found to depend on unrealistic activation energies for their constituent reactions when applied to the data. However, a model in which the effective activation energy changes linearly with AlCH 3 coverage does adequately fit the data. This model produces the apparent biexponential decay at low temperatures, and it confirms prior suggestions of a coverage dependence in the rate constant. The decrease in the effective activation energy with increasing coverage can be interpreted in terms of a cooperative effect between adjacent AlCH 3 groups. These findings may provide a framework for further studies, and both the kinetic model and parametric fits to the data may be useful in the construction of models of this important ALD process.

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Section: Discussionsupporting

confidence: 89%

Section: ■ Discussionmentioning

confidence: 92%

Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

2020

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“…The aim of this work is to evaluate chemical constants of the reactive mechanisms concerning Al-containing species (see Table 1). Thermal decomposition of aluminium compounds is the simplest reactive path; these reactions become fundamental as temperature grows, but the first two methyl losses start to be significant already in the low-temperature zone of the reactor (Al(CH 3 ) 3 -Al(CH 3 ) 2 +CH 3 is important for temperatures greater than 100 1C [4]). AlCH 3 is therefore the most stable methyl species inside the reactor.…”

Section: Resultsmentioning

confidence: 99%

p-doping mechanism in HTCVD silicon carbide

Fiorucci

Moscatelli

Masi

2007

Journal of Crystal Growth

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“…A special feature of our mechanism is the assumption that the Me 3 SiO radicals can only abstract hydrogen from Me 3 SiH or combine with Me 3 Si radicals. Self-combination is not taking place: neither the combination product Me 3 SiOOSiMe 3 nor Me 3 SiOSiMe 2 OMe, which emerges quantitatively by thermal rearrangement of the peroxide, , was found.…”

Section: Discussionmentioning

confidence: 94%

Oxidation of Trimethylsilyl Radicals by N₂O: A Mechanistic Study

and¹,

Potzinger²

2000

Organometallics

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The reaction of Me 3 Si (MetCH 3 ) radicals with N 2 O has been studied by analysis of the end products of the mercury-sensitized photolysis of N 2 O with Me 3 SiH. The main products found were N 2 , Me 3 SiSiMe 3 , Me 3 SiOSiMe 3 , and Me 3 SiOH. The influence on both major and minor products of reactant pressure, different scavenger and quencher molecules, temperature, and the reactor surface permits the derivation of a reaction mechanism and identification of the intermediates involved. The most important steps comprising the mechanism are oxygen abstraction from N 2 O by Me 3 Si with formation of Me 3 SiO and a chain propagation step, the reaction of Me 3 SiO and Me 3 SiH with formation of Me 3 SiOH and Me 3 -Si. Although the precise nature of the last step is unknown, it is a multistep reaction. Me 3 -SiO radicals also undergo combination with Me 3 Si radicals. Self-combination under formation of a peroxide does not occur. Vibrationally excited species emerge in Si-O bond-forming processes, and a number of minor products stem from unimolecular decomposition of these excited species. The rate constant of O atom abstraction from N 2 O (reaction 5) relative to Me 3 Si radical combination (reaction 4) is given by k 5 /k 4 1/2 ) (6.5 ( 1.3) × 10 -12 cm 3/2 s -1/2 at room temperature. An activation energy of E A (5) ) 23 ( 1 kJ mol -1 is obtained from experiments in the temperature range 295-520 K.

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Kinetics of the thermal decomposition of alkyl derivatives of Group III and V elements

Cited by 6 publications

References 95 publications

Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

p-doping mechanism in HTCVD silicon carbide

Oxidation of Trimethylsilyl Radicals by N₂O: A Mechanistic Study

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Kinetics of the thermal decomposition of alkyl derivatives of Group III and V elements

Cited by 6 publications

References 95 publications

Atomic Layer Deposition of Al2O3Using Trimethylaluminum and H2O: The Kinetics of the H2O Half-Cycle

Atomic Layer Deposition of Al2O3Using Trimethylaluminum and H2O: The Kinetics of the H2O Half-Cycle

p-doping mechanism in HTCVD silicon carbide

Oxidation of Trimethylsilyl Radicals by N2O: A Mechanistic Study

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Product

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Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

Atomic Layer Deposition of Al₂O₃Using Trimethylaluminum and H₂O: The Kinetics of the H₂O Half-Cycle

Oxidation of Trimethylsilyl Radicals by N₂O: A Mechanistic Study