Mediation of chain reactions by propagating radicals during halogenation of H-masked Si(100): implications for atomic-scale lithography and processing.

Scanning tunneling microscopy reveals a free radical-induced surface chain reaction in the chlorination of nanoscale patterns on an otherwise H-passivated (masked) Si(100). While scanning probe methods can be used to pattern active surface regions with single-bond precision, follow-up selective chemical vapor deposition with polyatomic molecules can produce various filling characteristics. On active surface regions, molecular Cl(2) undergoes an atom abstraction reaction in which a Si dangling bond abstracts one atom of the incident Cl(2) molecule while the complementary Cl atom is scattered away from the initial abstraction site either back into the vacuum or to be captured by a second dangling bond and adsorbed there, or to react with a nearby adsorbed H atom to form volatile HCl. In contrast, I(2) undergoes only dissociative adsorption on two immediately neighboring dangling bonds, whereby two I-Si bonds are formed simultaneously upon cleavage of the I(2) bond. The different chemisorption processes of the two model diatomic molecular gases place intrinsic limitations on atomic-scale lithography and processing: Adsorption of Cl(2) results in spillage over the prepatterned regions of active bonds. In contrast, adsorption of I(2) is a pair process and results in under-filling.