Microscopic understanding of the photoetching of semiconductors on a m
olecular scale by halogens is essential in terms of defining initially
the role of substitutional defects, charged carriers and band bending
at the surface. Creation of charged carriers at high doping levels by
photodionization coupled with field-induced transport introduces new
reaction channels into the surface chemistry. This paper focusess on h
eavily doped Si(111) and Si(100) in the quantum mechanical regime at l
ow laser fluences and surface temperatures where desorption is dominat
ed by electron excitations [6]. Substantial alteration of the etching
mechanism occurs when the atomic processes are driven quantum mechanic
ally rather than thermally. Fundamental aspects are presented for this
reaction regime where the surface chemistry is primarily electron-exc
ited in terms of: (1) the influence of substitutional electron defects
on the microetching and surface chemistry of heavily p- and n-doped S
i(100) and Si(111) and, (2) photoexcited velocity distribution results
at low laser fluences and temperatures. Some implications for the ext
ension of these studies to energetic mechanisms for photodesorption ar
e discussed.