Abstract

We report on a study of the adsorption and decomposition of arsine molecules on clean Si(100) 2\ifmmode\times\else\texttimes\fi{}1 surfaces using photoemission and scanning tunneling microscopy (STM). Arsine decomposition depends on the substrate temperature and occurs in five regimes: (i) Below 100 \ifmmode^\circ\else\textdegree\fi{}C the arsine dissociatively adsorbs most likely into As-H and Si-H. At these temperatures there is negligible surface diffusion and the saturation arsenic coverage is 20% because the remaining Si sites do not have enough unoccupied near neighbors to provide four bonds for ${\mathrm{AsH}}_{3}$ adsorption. (ii) Between 100 \ifmmode^\circ\else\textdegree\fi{}C and 400 \ifmmode^\circ\else\textdegree\fi{}C the onset of surface diffusion increases the saturation coverage of As to 25% (i.e., one arsenic per four silicon atoms), As-As dimers form and coalesce into short chains. (iii) Above 400 \ifmmode^\circ\else\textdegree\fi{}C the hydrogen starts to desorb significantly thereby allowing larger As coverages. (iv) This process reaches an extremum at about 575 \ifmmode^\circ\else\textdegree\fi{}C where all hydrogen is desorbed resulting in nearly 100% As coverage. (v) Near 650 \ifmmode^\circ\else\textdegree\fi{}C the As desorption rate becomes significant. The STM images recorded in these regimes reveal a wide variety of surface structures which are due to different relative rates of ${\mathrm{AsH}}_{3}$ adsorption, H and As desorption, and H, As, and Si surface diffusion. The ${\mathrm{AsH}}_{3}$ adsorption and H and As desorption processes are discussed in the context of a kinetic model.

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