Hostname: page-component-586b7cd67f-tf8b9 Total loading time: 0 Render date: 2024-11-29T08:16:56.271Z Has data issue: false hasContentIssue false

Quasi-Equilibrium Nucleation and Growth of Diamond and Cubic Boron-Nitride

Published online by Cambridge University Press:  25 February 2011

Y. Bar-Yam
Affiliation:
ECS, 44 Cummington St., Boston University, Boston MA 02215
T. Lei
Affiliation:
ECS, 44 Cummington St., Boston University, Boston MA 02215
T. D. Moustakas
Affiliation:
ECS, 44 Cummington St., Boston University, Boston MA 02215
D. C. Allan
Affiliation:
Applied Process Research, SP-PR-2–2 Corning Inc., Corning NY 14830
M. P. Teter
Affiliation:
Applied Process Research, SP-PR-2–2 Corning Inc., Corning NY 14830
Get access

Abstract

Material growth is an inherently non-equilibrium process. However, thermodynamic considerations often provide important insight into material growth, the structure of grown materials, and process control parameters. In essence, thermodynamic considerations are important when activated processes are either slow or fast on the time scale of the growth. Activated kinetic processes are important when their time scale is the same as that of growth. Realistic ab-initio calculations of material structure and dynamics can provide a microscopic understanding of both thermodynamics and the kinetics of material growth. The primary focus of this article is a recently proposed defect-assisted multiple-regrowth stabilization of cubic phases. in this theory the incorporation of vacancies at the growth face changes the relative binding energy of cubic versus hexagonal phases so that diamond and cubic boron nitride can nucleate and grow. This theory predicts that diamond nucleation and growth is enhanced under electron rich or positive ion conditions. Experimental results on growth of both diamond and cubic boron nitride that motivate and support theoretical predictions are described. Cubic boron-nitride grows under off-stoichiometric conditions. The nucleation rate of diamond is increased by many orders of magnitude when a flux of electrons impinges upon the surface. Raman line broadening and ESR measurements indicate the presence of significant concentrations of point defects. Predictions and experimental evidence for both n and p type doping will be discussed. Ab-initio calculations of key kinetic processes and thermodynamic quantities for diamond and boron nitride growth are described.

Type
Research Article
Copyright
Copyright © Materials Research Society 1992

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1 Bar-Yam, Y. and Moustakas, T. D., Nature 342, 786, 14 December 1989 Google Scholar
2 Bar-Yam, Y. and Moustakas, T. D., Mater. Res. Soc. Symp. Proc. Vol. 162, 201 (1989)Google Scholar
3 Bemholc, J., Antonelli, A., Del Sole, T. M., Bar-Yam, Y. and Pantelides, S. T., Phys. Rev. Lett. 61, 2689 (1988)Google Scholar
4 Davies, G. and Lawson, S., private communication.Google Scholar
5 Kaxiras, E. and Pandey, K. C., Phys. Rev. Lett. 60, 2693 (1988)Google Scholar
6 Spitsyn, B. V., Bouilov, L. L., and Derjaguin, B. V., J. Crysi. Growth 52, 219 (1981)Google Scholar
7 Badzian, A. R., and De Vries, R. C., Material Research Bulletin 23, 181, (1988)Google Scholar
8 It is possible instead to suggest that the etching process itself is able to stabilize the growth of diamond because graphite etches more easily than diamond. However, once dynamical processes become reversible, fast etching is equivalent to fast growth and slow etching becomes equivalent to slow growth. This is the standard result in equilibrium processes which operate in both directions. It is possible, as in Ref. 7, to construct kinetically consistent arguments for the stabilization of diamond growth by different etching rates if the etching process is different from the atom addition process. Then the production of diamond is directly controlled by the kinetic processes of atom addition and removal from diamond and graphite.Google Scholar
9 The “entropy of mixing” term is not included in this expression because for non-equilibrium defect densities it is negligible compared to the terms shown, and it is the same for materials with similar concentrations of defects.Google Scholar
10 Bar-Yam, Y., Adler, D., and Joannopoulos, J. D. Phvs. Rev. Lett. 57, 467 (1986);Google Scholar
Phvsics and Applications of Amorphous Semiconductors I. (ed Demichelis, F.) (World Scientific, 1988). p. 1.Google Scholar
11 Buckley, R. G., Moustakas, T. D., Ye, L. and Varon, J., J. of Appl. Phys. 66, 3595 (1989)Google Scholar
12 Fanciulli, M., and Moustakas, T. D., Diamond and Related Materials (in press) (1992)Google Scholar
13 Moustakas, T. D. in Proceedings of the 20th Int. Conf. on the Physics of Semiconductors, (Anastassakis, E. M., and Joannopoulos, J. D. eds.) (1990) p. 320 Google Scholar
14 Sawabe, A. and Inuzuka, T., Appl. Phys. Lett. 46, 146 (1985)CrossRefGoogle Scholar
15 Kajihara, S. A., Antonelli, A., Bcrnholc, J. and Car, R., Phys. Rev. Lett. 66. 2010 (1991)CrossRefGoogle Scholar
16 Teter, M. P., Payne, M. C., and Allan, D. C., Phys. Rev. B 40, 11357 (1989)CrossRefGoogle Scholar
17 Bar-Yam, Y. and Joannopoulos, J. D., Phys. Rev. Lett, 52, 1129 (1984); J. of Electron. Mater. 14a, 261 (1985)Google Scholar
18 Lei, T., Bar-Yam, Y., Allan, D. C. and Teter, M. P. (unpublished)Google Scholar
19 Moustakas, T. D., et. al. (this volume)Google Scholar
20 Fanciulli, M., and Moustakas, T. D. (this volume)Google Scholar