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Kinetic and Surface Mechanisms to Growth of Hexagonal Boron Nitride

Published online by Cambridge University Press:  11 February 2011

Patrícia R. R. Barreto ,
Alan E. Kull  and
Mark A. Cappelli
Patrícia R. R. Barreto
Affiliation:
Laboratório Associado de Plasma, Instituto Nacional de Pesquisas Espaciais, São José dos Campos, SP, CP 515, 12201–970, Brazil
Alan E. Kull
Affiliation:
Mechanical Engineering Department, Stanford University, Stanford, CA 94305–3032, USA
Mark A. Cappelli
Affiliation:
Mechanical Engineering Department, Stanford University, Stanford, CA 94305–3032, USA
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Abstract

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 BF3, H2 and N2. 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 H2, BF3 and NF3 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 BFx, 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.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 750: Symposium Y – Surface Engineering 2002–Synthesis, Characterization and Applications , 2002 , Y5.13
Copyright
Copyright © Materials Research Society 2003

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References

REFERENCES

1. Kalss, W., Haubner, R., and Lux, B., Diamond and Related Materials, 7, 369, (1998).Google Scholar
2. Dugne, O., Prouhet, S., Guette, A., and Naslain, R., J. of Alloy and Compounds, 176, 187, (1991).Google Scholar
3. Hannache, H., Naslain, R., Bernard, C., and Heraud, L., Proc. Forth European Conference on Chemical Vapour Deposition, 305, (1983).Google Scholar
4. Matsumoto, S., Nishida, N., Akashi, K., and Sugai, K., J. Mat. Sci., 31, 713, (1996).Google Scholar
5. Hannache, H., Naslain, R., and Bernard, C., J. Less-Common Met., 95, 221, (1983).Google Scholar
6. McDaniel, H. and Allendorf, M. D., J. Phys. Chem. A, 102, 7804, (1998).Google Scholar
7. Allendorf, M. D. and Melius, C. F., J. Phys. Chem. A, 101, 2670, (1997).Google Scholar
8. Barreto, P. R. P. and Cappelli, M. A. (private communication).Google Scholar
9. Prouhet, S., Langlais, F., Guette, A., and Naslain, R.. Eur. J. Solid State Inorg. Chem., 30: 953, 1993.Google Scholar
10. Prouhet, S., Vignoles, G., Langlais, F., Guette, A., and Naslain, R.. Eur. J. Solid State Inorg. Chem., 30: 971, 1993.Google Scholar
11. Barreto, P. R. P., Cappelli, M. A. and Matsumoto, S., International Conference on Plasma Physics, Quebec City, CA, (2000).Google Scholar
12. Barreto, P. R. P., Kull, A.E., Cappelli, M.A., 6° Encontro Brasileiro de Física dos Plasmas, 31, Campos do Jordão, SP, Brazil, Dez. 2000.Google Scholar
13. Barreto, P. R. P., 6° Encontro Brasileiro de Física dos Plasma, 30, Campos do Jordão, SP, Brazil, Dez. 2000.Google Scholar
14. Barreto, P. R. P. (INPE - internal report).Google Scholar
15. Harris, S. J. and Weiner, A. M.., Appl. Phys. Lett., 53, 1605 (1988).Google Scholar
16. Harris, S. J., J. Appl. Phys. 65, 3044 (1989).Google Scholar
17. Goodwin, D. G. and Gavillet, G. G., J. Appl. Phys. 68, 6393 (1990).Google Scholar
18. Kee, R. J., Rupley, F. M., and Miller, J. A., Technical Report SAND89–8009, Sandia National Laboratories (1990).Google Scholar
19. Reynolds, Wn.C., (private communication).Google Scholar
20. Frenklack, M. and Spear, K.E., J. Material Research 3, 133 (1988).Google Scholar