posted on 2017-12-06, 00:00authored byPitsiri Sukkaew, Emil Kalered, Erik Janzén, Olof Kordina, Örjan Danielsson, Lars Ojamäe
Silicon carbide is a wide bandgap
semiconductor ideally suitable
for high temperature and high power applications. An active SiC layer
is usually fabricated using halide-assisted chemical vapor deposition
(CVD). In this work, we use quantum chemical density functional theory
(B3LYP and M06-2X) and transition state theory to study adsorptions
of active Si species in the CVD process on both the Si face and the
C face of 4H-SiC. We show that adsorptions of SiCl, SiCl2, SiHCl, SiH, and SiH2 on the Si face likely occur on
a methylene site, CH2(ads), but the processes are thermodynamically
less favorable than their reverse or desorptions. Nevertheless, the
adsorbed products become stabilized with the help of subsequent surface
reactions to form a larger cluster. These cluster formation reactions
happen with rates that are fast enough to compete with the desorption
processes. On the C face, the adsorptions likely occur on a surface
site terminated by a dangling bond, *(ads), and produce the products
which are thermodynamically stable. Lastly, we present the Gibbs free
energies of adsorptions of Si atoms, SiX, SiX2, and SiHX,
for X being F and Br. Adsorptions of Si atoms are shown to be the
most thermodynamically favorable among all the species in the study.
Among the halide-containing species, the Gibbs free energies (ΔRG°) from smallest to largest are observed
in the adsorptions of SiX, SiHX, and SiX2, for X being
the halides. The results in this study suggest that the major Si contributors
in the SiC–CVD process are Si atoms, SiX (for X being the halide)
and SiH.