The hysteresis and kinetics of capillary condensation of N2 and Ar in linear mesopores, produced by etching of Si wafers, have been studied for different pore shapes, including the ink bottle geometry. Pore blocking has been observed in the solid state of the pore fillings, but not in the liquid state. We conclude that individual local geometries such as the pore mouth, a blind end, or a single constriction have no effect on the shape of sorption isotherms, that the pore space should be regarded as a statistical ensemble of pore segments with a lot of quenched disorder.
We report new types of heterogeneous hydrogen-oxygen and silicon-oxygen branched chain reactions which have been found to proceed explosively after the filling of pores of hydrogen-terminated porous silicon (Si) by condensed or liquid oxygen in the temperature range of 4.2-90 K. Infrared vibrational absorption spectroscopy shows that, while initially Si nanocrystals assembling the layers have hydrogen-terminated surfaces, the final products of the reaction are SiO2 and H2O. Time-resolved optical experiments show that the explosive reaction develops in a time scale of 10(-6) s. We emphasize the remarkable structural properties of porous Si layers which are crucial for the strong explosive interaction.
We demonstrate efficient resonant energy transfer from excitons confined in silicon nanocrystals to molecular oxygen (MO). Quenching of photoluminescence (PL) of silicon nanocrystals by MO physisorbed on their surface is found to be most efficient when the energy of excitons coincides with triplet-singlet splitting energy of oxygen molecules. The dependence of PL quenching efficiency on nanocrystal surface termination is consistent with short-range resonant electron exchange mechanism of energy transfer. A highly developed surface of silicon nanocrystal assemblies and a long radiative lifetime of excitons are favorable for achieving a high efficiency of this process.
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