Measuring the site-specific reactivity of impurities: The pronounced effect of dissolved oxygen on silicon etching
The reactivity of dissolved O2, a ubiquitous impurity in aqueous solutions, with H-terminated Si(111) surfaces was quantified using a new technique that exploits kinetic competition between an impurity and an etchant to produce impurity-concentration-dependent changes in the steady-state etch morphology. This method is applicable to any impurity that alters the etch morphology. The impurity-induced changes are quantified using scanning tunneling microscopy measurements and atomistic, concentration-dependent kinetic Monte Carlo simulations. The site-specific reactivity of O2(aq) is surprisingly anisotropic. Oxidation of the highly strained dihydride step site is 4 times faster than oxidation of the relatively unstrained monohydride step site. Both steps are 104times more reactive than terrace sites. The observed site-specific reaction rates are highly correlated to local strain. FTIR measurements of the Si−H stretch vibration showed that dissolved O2 inserts O atoms into surface Si−Si back-bonds without removing the H-termination. Dissolved O2 does not attack Si−H bonds, because neither Si−H consumption nor silanol production is observed.
Garcia, Simon; Bao, Hailing; Manimaran, Muthiah; and Hines, Melissa, "Measuring the site-specific reactivity of impurities: The pronounced effect of dissolved oxygen on silicon etching" (2002). Journal of Physical Chemistry B 106(33): 8258-8264. Faculty Publications. Paper 63.
Journal of Physical Chemistry B