Hydrogen desorption kinetics from monohydride and dihydride species on crystalline-silicon surfaces were measured using transmission Fourier-transform infrared (FTIR) spectroscopy. The FTIR desorption measurements were performed in situ in an ultrahigh-vacuum chamber using high-surface-area porous-silicon samples. The kinetics for hydrogen desorption from the monohydride and dihydride species was monitored using the SiH stretch mode at 2102 ${\mathrm{cm}}^{\mathrm{-}1}$ and the ${\mathrm{SiH}}_2$ scissors mode at 910 ${\mathrm{cm}}^{\mathrm{-}1}$, respectively. Annealing studies revealed that hydrogen from the ${\mathrm{SiH}}_2$ species desorbed between 640 and 700 K, whereas hydrogen from the SiH species desorbed between 720 and 800 K. Isothermal studies revealed second-order hydrogen desorption kinetics for both the monohydride and dihydride surface species. Desorption activation barriers of 65 kcal/mol (2.82 eV) and 43 kcal/mol (1.86 eV) were measured for the monohydride and dihydride species, respectively. These desorption activation barriers yield upper limits of 84.6 kcal/mol (3.67 eV) and 73.6 kcal/mol (3.19 eV) for the Si-H chemical bond energies of the SiH and ${\mathrm{SiH}}_2$ surface species.

• Received 21 December 1987

DOI:https://doi.org/10.1103/PhysRevB.37.8234