Molecular Dynamics Studies of Elementary Surface Reactions of C2H2 and C2H in Low Pressure Diamond Film Formation

James Peploski, Donald L. Thompson and Lionel M. Raff

J. Phys. Chem. 96, 8538 (1992)

Abstract

Molecular dynamics studies of some of the important elementary reactions involved in the low-pressure synthesis of diamond films are reported. The C(111) surface is modelled with an ensemble of 127 atoms and a velocity reset procedure to incorporate the thermal effects of the bulk. The hydrocarbon potential developed by Brenner [Phys. Rev. B 1990, 42, 9458] is employed in all calculations for both the surface and the incident gas-phase molecules. The principal results are (1) the sticking coefficients for acetylene on a clean C(111) surface lie in the range 0.25-0.33 for incident translational energies between 1.5-2.0 eV with surface temperatures in the range 1000 - 1500 K. (2) Chemisorption of acetylene most frequently involves the formation of two C(s)-C single bonds to adjacent adsorption sites on the C(111) surface. (3) Surface chemisorption of acetylene via the formation of one C(s)-C single bond to yield an ethenyl radical is observed and the subsequent desorption of this species from a clean C(111) surface does not appear to be a high probability process. (4) The addition of a second acetylene molecule to form an ethenyl radical is a very low probability process for all surface structures investigated. When such chemisorption does occur, the probability of subsequent desorption is large unless the ethenyl radical is able to subsequently form a second C-C bond. (5) Addition of a .CºCH radical to a chemisorbed acetylene group proceeds with a much higher probability than is the case for C2H2. The ethynyl radical is also chemisorbed readily to other surface structures with a low probability of subsequent desorption. It therefore appears likely that C2H is an important diamond-growth species even in experiments where its concentration is one or two orders of magnitude less than that of acetylene.