<i>Ab initio</i>studies of silane decomposition on Si(100)

Abstract

The mechanism of silane decomposition on the Si(100)-(2\ifmmode\times\else\texttimes\fi{}1) surface is investigated in the context of a many-electron theory that permits the accurate computation of molecule-solid surface interactions at an ab initio configuration-interaction level. The adsorbate and local surface region are treated as embedded in the remainder of the lattice electronic distribution, which is modeled as a three-layer, 19-Si--plus--21-H cluster. A possible energetic pathway is found for the reaction ${\mathrm{SiH}}_{4}$\ensuremath{\rightarrow}${\mathrm{SiH}}_{3}$+H on the surface. It involves two separate steps: (1) scission of one Si-H bond; (2) formation of two bonds to ${\mathrm{SiH}}_{3}$ and H from two surface dangling bonds. The energy barrier, which is calculated to be 9 kcal/mol, occurs in the first step at a distance of 3.6 \AA{} from the Si in ${\mathrm{SiH}}_{4}$ to a Si surface atom with a Si-H bond aligned with a surface dangling-bond direction. The overall dissociation process ${\mathrm{SiH}}_{4}$\ensuremath{\rightarrow}${\mathrm{SiH}}_{3}$+H on the surface is found to be 2.8 eV exothermic. Quantum tunneling is found to play an important role in the process at room temperature. A symmetrical Eckart potential is used to estimate the quantum tunneling effect and the reaction probability is calculated to be small (on the order of ${10}^{\mathrm{\ensuremath{-}}5}$) and relatively insensitive to the silane temperature.