Experimental and theoretical investigation of BCl3 decomposition in H2

Reinisch, Guillaume; Leyssale, Jean‐Marc; Bertrand, Nathalie; Chollon, Georges; Langlais, F.; Vignoles, Gérard L.

doi:10.1016/j.surfcoat.2008.04.086

Cited by 11 publications

(8 citation statements)

References 16 publications

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“…An experiment has been carried out without ammonia and with a reduced gas flow rate (Qtot = 200 sccm), in order to replicate the reactor inlet conditions encountered upstream from the NH3 injection point (at about 700 °C), when the reactor is run in BN deposition conditions. BHCl2 was previously detected by FTIR by Reinisch et al in a similar experiment using the BCl3−H2 system at a temperature of 500 °C and a pressure of 1 kPa [25]. Here, from the same BCl3−H2 gas mixture, BHCl2 is only detected above 650 °C, i.e.…”

Section: Nh3-free Systemsupporting

confidence: 57%

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Carminati

Buffeteau²,

Daugey³

et al. 2018

Thin Solid Films

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The structural and morphological characteristics of flat BN coatings processed by chemical vapour deposition, using BCl3−NH3−H2 gas mixtures at low pressure (P < 1 kPa), have been investigated as a function of the deposition temperature (ranging from 900 °C to 1400 °C) and the total gas flow rate. The resulting BN coatings are mainly turbostratic but with heterogeneous microstructures, i.e. mixtures of poorly and highly organized domains. The structural homogeneity and the degree of crystallization depend notably on the nature of the dilution gas (either H2 or Ar) and the depletion of gas species. The decrease of the apparent activation energy from 80 kJ.mol -1 below 1200 °C to 40 kJ.mol -1 above 1200 °C reflects a change in the deposition regime. Ex situ Fourier transform infrared analysis of the residual gas mixture allowed intermediate species leading to poorly or highly organized BN to be tracked and then connected with the main reaction paths leading to the different BN coatings.

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Section: Nh3-free Systemsupporting

confidence: 57%

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Carminati

Buffeteau²,

Daugey³

et al. 2018

Thin Solid Films

Self Cite

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show abstract

“…Note that the direct Cl abstraction reactions in the Harris mechanism are not considered here, since the A/E scheme is actually much more efficient. Then, we have added three molecular reactions: 19,24 BCl…”

Section: Table 2 Arrheniusàkooij Rate Parameters Of the 10 Additionàe...mentioning

confidence: 99%

Reaction Mechanism for the Thermal Decomposition of BCl₃/CH₄/H₂ Gas Mixtures

2011

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This paper presents an ab initio study of the B/C/Cl/H gas phase mechanism, featuring 10 addition-elimination reactions involving BH(i)Cl(j) (i + j ≤ 3) species and a first description of the chemical interaction between the carbon-containing and boron-containing subsystems through the three reactions BCl(3) + CH(4) ⇌ BCl(2)CH(3) + HCl, BHCl(2) + CH(4) ⇌ BCl(2)CH(3) + H(2), and BCl(2) + CH(4) ⇌ BHCl(2) + CH(3). A reaction mechanism is then proposed and used to perform some illustrative equilibrium and kinetic calculations in the context of chemical vapor deposition (CVD) of boron carbide. Our results show that the new addition-elimination reaction paths play a crucial role by lowering considerably the activation barrier with respect to previous theoretical evaluations; they also confirm that BCl(2)CH(3) is an important species in the mechanism.

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“…Some theoretical work, using ab initio calculations, has been achieved in that area. − However, those studies are somehow contradictory, and even whether the first decomposition reaction of BCl 3 is of molecular (BCl 3 + H 2 ) or radical (BCl 3 + H) nature is not definitely established. Although the kinetics of the molecular reaction BCl 3 + H 2 → BHCl 2 + HCl is now well-identified, , there is still doubt on its radical counterpart.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Decomposition of BCl₃ Induced by a H Radical

2011

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We report on a theoretical study of the gas-phase decomposition of boron trichloride in the presence of hydrogen radicals using ab initio energetic calculations coupled to TST, RRKM, and VTST-VRC kinetic calculations. In particular, we present an addition-elimination mechanism (BCl(3) + H → BHCl(2) + Cl) allowing for a much more rapid consumption of BCl(3) than the direct abstraction reaction (BCl(3) + H → BCl(2) + HCl) considered up to now. At low temperatures, T ≤ 800 K, our results show that a weakly stabilized complex BHCl(3) is formed with a kinetic law compatible with the consumption rate measured in the former experiments. At higher temperatures, this complex is not stable and then easily eliminates a chlorine atom. Our work also shows that a very similar mechanism, involving the same intermediate and sharing the same transition state, allows for the elimination of HCl. A dividing coefficient between these two elimination pathways is obtained from both a potential energy surface based statistical analysis and an ab initio molecular dynamics transition path sampling simulation. It finally allows partitioning of the global consumption rate of BCl(3) in terms of the formation of (i) BHCl(3), (ii) BHCl(2) + Cl through a H addition/Cl elimination mechanism, (iii) BCl(2) + HCl through a H addition/HCl elimination mechanism, and (iv) BCl(2) + HCl through direct abstraction.

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Experimental and theoretical investigation of BCl3 decomposition in H2

Cited by 11 publications

References 16 publications

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Reaction Mechanism for the Thermal Decomposition of BCl₃/CH₄/H₂ Gas Mixtures

Theoretical Study of the Decomposition of BCl₃ Induced by a H Radical

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Experimental and theoretical investigation of BCl3 decomposition in H2

Cited by 11 publications

References 16 publications

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Low pressure chemical vapour deposition of BN: Relationship between gas phase chemistry and coating microstructure

Reaction Mechanism for the Thermal Decomposition of BCl3/CH4/H2 Gas Mixtures

Theoretical Study of the Decomposition of BCl3 Induced by a H Radical

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Reaction Mechanism for the Thermal Decomposition of BCl₃/CH₄/H₂ Gas Mixtures

Theoretical Study of the Decomposition of BCl₃ Induced by a H Radical