Kevin Summers, N. Kemp, Nathan J. Paris
Mar 15, 2007
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Journal
Surface Science
Abstract
Abstract The surface reactions of 2-iodopropane ((CH 3 ) 2 CHI) on gallium-rich GaAs(1 0 0)-(4 × 1), was studied by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). CH 3 CHICH 3 adsorbs molecularly at 120 K but dissociates below room temperature to form chemisorbed 2-propyl ((CH 3 ) 2 CH ) and iodide (I ) species. Thermal activation causes desorption of the molecular species at 240 K, and this occurs in competition with the further reactions of the (CH 3 ) 2 CH and I chemisorbed species. Self-coupling of the (CH 3 ) 2 CH results in the formation of 2,3-dimethylbutane ((CH 3 ) 2 CH–CH(CH 3 ) 2 ) at 290 K. β-Hydride elimination in (CH 3 ) 2 CH yields gaseous propene (CH 3 CH CH 2 ) at 550 K while reductive elimination reactions of (CH 3 ) 2 CH with surface hydrogen yields propane (CH 3 CH 2 CH 3 ) at 560 K. Recombinative desorption of the adsorbed hydrogen as H 2 also occurs at 560 K. We observe that the activation barrier to carbon–carbon bond formation with 2-propyls on GaAs(1 0 0) is much lower than that in our previous investigations involving ethyl and 1,1,1-trifluoroethyl species where the β-elimination process was more facile. The difference in the surface chemistry in the case of 2-propyl species is attributable to its rigid structure resulting from the bonding to the surface via the second carbon atom, which causes the methyl groups to be further away from the surface than in the case of linear ethyl and 1,1,1-trifluoroethyl species. The β-hydride and reductive elimination processes in the adsorbed 2-propyl species thus occurs at higher temperatures, and a consequence of this is that GaI desorption, which is expected to occur in the temperature range 550–560 K becomes suppressed, and the chemisorbed iodine leaves the surface as atomic iodine.