Mechanism of the thermally induced gas-phase decomposition of silane: a revisitation

Ring, M. A.; O’Neal, H. E.

doi:10.1021/j100205a046

Cited by 64 publications

(62 citation statements)

References 3 publications

(3 reference statements)

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“…For example, there is no consensus on the cause of initial acceleration of silane consumption and hydrogen, disilane, and trisilane formation. Thus, in [23] this acceleration was attributed to the onset of a surface initiation promoted by (SiH 2 ) x product depositions. In ref.…”

Section: Introductionmentioning

confidence: 94%

“…However, there is no common point of view on the mechanism of solid product formation during thermal decomposition of silane. Species such as Si and Si 2 [25 -27], SiH 2 [28], Si 2 H 4 [29], silylenes Si n H 2n [30], SiH 4 [24], and higher silanes like Si 3 H 8 [14,23] were considered as gaseous precursors for the solid phase. Nevertheless, the mechanism of solid-phase formation is uncertain.…”

Section: Introductionmentioning

confidence: 99%

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Studying of silane thermal decomposition mechanism

Onischuk

Strunin

Ushakova

et al. 1998

Int. J. Chem. Kinet.

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The mechanism of silane thermal decomposition is investigated in a flow reactor. The time dependencies of silane consumption and disilane formation were compared with those parameters of solid product (aerosol particles) such as concentration, total hydrogen content in solid product, and fraction of hydrogen contained in solid product as polyhydride groups (SiH 2 ) n . Silane loss and gaseous product formation were analyzed using a mass spectrometer. The hydrogen content in solid product was analyzed by the methods of IR-spectroscopy and hydrogen evolution. Based on a simple kinetic scheme we qualitatively explained the experimental dependencies of silane conversion and disilane formation, the effective activation energy of the decomposition process, and the amount of polyhydride groups in the solid product on reaction time and initial silane concentration.

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Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Studying of silane thermal decomposition mechanism

Onischuk

Strunin

Ushakova

et al. 1998

Int. J. Chem. Kinet.

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show abstract

“…The only molecule with double functionality that was allowed to form in the system was Si 2 H 2 , which was suggested to be the key component in the formation of silicon nanoparticles in the thermal CVD of silicon via silane. 29,30 It has been reported that Si 2 H 2 forms through the elimination of molecular hydrogen from disilene, H 2 SidSiH 2 , and it can insert into Si-H or H-H bonds in the same manner as silylenes. 31,32 Three isomers of Si 2 H 2 were found, and the most stable structure of Si 2 H 2 is reported to be Si(H 2 )Si.…”

Section: Model Developmentmentioning

confidence: 99%

Detailed Kinetic Modeling of Silicon Nanoparticle Formation Chemistry via Automated Mechanism Generation

Wong

Swihart

et al. 2004

J. Phys. Chem. A

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Thermal decomposition of silane can be used to produce silicon nanoparticles, which have attracted great interest in recent years because of their novel optical and electronic properties. However, these silicon nanoparticles are also an important source of particulate contamination leading to yield loss in conventional semiconductor processing. In both cases, a fundamental knowledge of the reaction kinetics of particle formation is needed to understand and control the nucleation of silicon particles. In this work, detailed kinetic modeling of silicon nanoparticle formation chemistry was carried out using automated reaction mechanism generation. Literature values, linear free-energy relationships (LFERs), and a group additivity approach were incorporated to specify the rate parameters and thermochemical properties of the species in the system. New criteria for terminating the mechanisms generated were also developed and compared, and their suitability for handling an unbounded system was evaluated. Four different reaction conditions were analyzed, and the models predicted that the critical particle sizes were Si 5 for an initial H 2 /SiH 4 molar ratio of 90:10 at 1023 K and Si 4 for the same initial composition at 1200 K. For an initial H 2 /SiH 4 molar ratio of 99:1, the critical particle size was larger than or equal to Si 7 for both temperatures, but it was not possible to determine the exact critical particle size because of limitations in computational resources. Finally, the reaction pathways leading to the formation of nanoparticles up to the critical size were analyzed, and the important species in the pathways were elucidated.

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“…[1][2][3][4][5][6][7] There is also a substantial body of work on the kinetics of gas-phase reactions of small silicon hydrides. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] On the basis of this body of research, models of thermal CVD of silicon from silane can now predict film growth rates and precursor utilization with reasonable accuracy and reliability, at least under conditions where particle formation is negligible. However, understanding of the processes that lead to gas-phase particle nucleation is still quite limited, and models for nucleation and growth of particles in this system do not have the level of predictive capability that has been achieved in modeling film growth rates and gas-phase chemical composition.…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

1998

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Product contamination by particles nucleated within the processing environment often limits the deposition rate during chemical vapor deposition processes. A fundamental understanding of how these particles nucleate could allow higher growth rates while minimizing particle contamination. Here we present an extensive chemical kinetic mechanism for silicon hydride cluster formation during silane pyrolysis. This mechanism includes detailed chemical information about the relative stability and reactivity of different possible silicon hydride clusters. It provides a means of calculating a particle nucleation rate that can be used as the nucleation source term in aerosol dynamics models that predict particle formation, growth, and transport. A group additivity method was developed to estimate thermochemical properties of the silicon hydride clusters. Reactivity rules for the silicon hydride clusters were proposed based on the group additivity estimates for the reaction thermochemistry and the analogous reactions of smaller silicon hydrides. These rules were used to generate a reaction mechanism consisting of reversible reactions among silicon hydrides containing up to 10 silicon atoms and irreversible formation of silicon hydrides containing 11-20 silicon atoms. The resulting mechanism was used in kinetic simulations of clustering during silane pyrolysis in the absence of any surface reactions. Results of those simulations are presented, along with reaction path analyses in which key reaction paths and rate-limiting steps are identified and discussed.

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Mechanism of the thermally induced gas-phase decomposition of silane: a revisitation

Cited by 64 publications

References 3 publications

Studying of silane thermal decomposition mechanism

Studying of silane thermal decomposition mechanism

Detailed Kinetic Modeling of Silicon Nanoparticle Formation Chemistry via Automated Mechanism Generation

Thermochemistry and Kinetics of Silicon Hydride Cluster Formation during Thermal Decomposition of Silane

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