Preparation of BN films by r.f. thermal plasma chemical vapour deposition

Matsumoto, Shinya; Nishida, Naoki; Akashi, Kazuo; Sugai, Kazumi

doi:10.1007/bf00367890

Cited by 31 publications

(24 citation statements)

References 12 publications

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“…Kobayashi [8] proposed that the formation of cBN under high temperature and high pressure could be facilitated by adding fluorides. Kalss and Matsumoto [9][10][11][12][13] reported that fluorides played an important role in promoting the deposition of cBN films. Zhang et al [14] simulated the selective etching of graphite and diamond, and investigated the fluorination-induced etching to hBN and cBN.…”

Section: Introductionmentioning

confidence: 99%

“…However, the experimental process became too complex; hence, a facile and effective method is urgently needed to synthesize cBN under mild conditions. The effect of halide species in the deposition of cBN films [8][9][10][11][12][13][14] reveals that the formation process of cBN in hydrothermal solutions might also be promoted by introducing halide species into the reaction solutions. In this work, the inducing effect of halide ions in hydrothermal solutions has been intensively investigated, and the mechanism is briefly discussed.…”

Section: Introductionmentioning

confidence: 99%

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Inducing effect of halide species in the hydrothermal synthesis of cubic boron nitride

Lian

Zhang

Zhu

et al. 2009

Journal of Crystal Growth

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Inducing effect of halide species in the hydrothermal synthesis of cubic boron nitride

Lian

Zhang

Zhu

et al. 2009

Journal of Crystal Growth

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“…The resulting analytical expression for the growth rate for hexagonal boron nitride is [8,11,12,14]: (4) where k x is the rate coefficient for the x-th surface reaction showed in -3 ] and, for hBN, the total concentration of surface sites is [S] = 7.9 10 9 mol cm -2 . The rate constants, k x -in the Arrhenius form, were estimated to obtain good fits assuming either BF 3 , BF 2, or BF as possible precursors, and are then examined here for their ability to also capture the trends seen in the arcjet studies.…”

Section: Surface Mechanismmentioning

confidence: 99%

“…Theoretical research found in the literature includes thermodynamic equilibrium calculations for mixtures involving B/F/N/H [1][2][3][4][5] and B/Cl/N/H [4,5], as well as limited kinetics studies of the reactions between BCl 3 and NH 3 [6,7].…”

Section: Introductionmentioning

confidence: 99%

Kinetic and Surface Mechanisms to Growth of Hexagonal Boron Nitride

2002

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A mechanism is presented for the gas-phase chemistry and surface reactions describing the growth of boron nitride films. The gas phase mechanism includes 33 species and 216 elementary reactions. Rate parameters for 117 elementary reactions were obtained from published experimental/theoretical data and those for the other 99 were determined using transition state theory. The mechanism examined here is an extension and update of a previous mechanism that contained 26 species and 67 elementary reactions. Standard reaction flux/pathway and gradient sensitivity analysis techniques are used to identify important reaction pathways. The calculations were handled through the use of the ChemKin software package. The model was applied to the growth of hexagonal boron nitride in an arcjet plasma source operating on mixture of BF 3 , H 2 and N 2 . From the growth rate and experimental conditions for such reactors, this work demonstrates that species with mole fractions in the range of 1 10 -10 -2 10 -4 (easily generated by gas-phase conditions) can account for the measured growth rate. A comparison of the predicted mole fractions of the gas-phase species present for the experimental residence times with those required to account for the measured film growth rates allows us to identify possible growth precursors. At the experimental settings, it is found that the residence time of the reacting species does not allow the flow to reach the chemical equilibrium, and that many radicals other than the source gases can account for the measured BN growth rate. The gas-phase is shown to be removed from thermodynamic equilibrium. For comparison, the equilibrium mole fractions were also calculated using an available equilibrium chemistry solver, STANJAN. Growth rates of 10 -9 to 10 -6 kg m -1 s -1 were measured for a wide range of H 2 , BF 3 and NF 3 flux. Both the finite-rate kinetics and equilibrium calculations confirm the importance of added hydrogen to facilitate boron nitride condensation from the gas phase. A simple surface mechanism with 7 steps is proposed with rate constants chosen to best fit the experimental growth kinetics. The results of the model, with surface rate coefficients determined from analogous gas-phase reactions, tuned slightly to agree with the experimental growth rates for BF x , x = 1, 2 or 3, as the rate-limiting growth precursor. It is also shown that the hydrogen atom has a great influence in the growth rate and that fluorine atom etches the hBN films.

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“…Kobayashi [15] proposed that the formation of cBN under HTHP could be facilitated by adding fluorides. Kalss and Matsumoto [16][17][18][19][20] reported that fluorides played an important role in promoting the deposition of cBN films. Zhang et al [21] simulated the selective etching of graphite and diamond, and investigated the fluorination-induced etching to hexagonal boron nitride (hBN) and cBN.…”

mentioning

confidence: 99%