. (2015). Size-dependent chemical reactivity of silicon nanocrystals with water and oxygen. The Journal of Physical Chemistry C: Energy Conversion and Storage, Optical and Electronic Devices, Interfaces, Nanomaterials, and Hard Matter, 119 (1), 826-834.
Size-dependent chemical reactivity of silicon nanocrystals with water and oxygen
AbstractA detailed investigation examines how the size of allylbenzene-capped silicon nanocrystals (ncSi:AB) affects their chemical reactivity with gaseous O 2 , H 2 O, and O 2 /H 2 O as probed by in situ luminescence spectroscopy. Specifically, changes in the photoluminescence (PL) of size-separated ncSi:AB are monitored through alterations of their PL absolute quantum yield (AQY) as well as the wavelength and intensity of their PL spectra over time. These experiments, conducted under both continuous and intermittent illumination, help elucidate the roles of O 2 , H 2 O, and mixtures of O 2 /H 2 O, with respect to oxidation of ncSi:AB as a function of their size, providing vital information for any perceived application in advanced materials and biomedical devices.
ABSTRACT:The effects of exposure to dry and controlled humidity oxygenated atmospheres in the dark and light were examined in situ for monodisperse allylbenzene-capped silicon nanocrystals (ncSi:AB). Changes in photoluminescence (PL) intensity as measured by alterations of the PL absolute quantum yields (AQY) and blue shifting of PL spectra were measured over time under continuous and intermittent illumination to help elucidate the roles of O2 and H2O as well as UV irradiation in the oxidation of the ncSi surface. Size-dependent trends were observed for both PL blue shifting and changes in the PL AQY indicating that nanocrystal size plays an important role in how oxygen species react at the nanocrystal surface.
IntroductionSilicon nanocrystals (ncSi) were found to exhibit intense room temperature photoluminescence in 1990, 1 and subsequent study has identified that they possess size-dependant optical and electronic properties, 2a-c similar to other semiconductor nanocrystals composed of heavy metal materials. In particular, quantum and spatial confinement effects result in a widening of the electronic band gap and a blue shift in photoluminescence (PL) as the ncSi particle size decreases. 2a-c,3 Recent studies also report that ncSi show size-dependent PL absolute quantum yields (AQY). 2a,c,4a,b These size-dependent properties as well as a wide PL range that spans the visible to near infrared region, 2c have established ncSi as a promising candidate in optoelectronic and biological imaging applications. 5a-e Currently, there are a variety of methods that exist for the synthesis of ncSi, including the annealing of SiOx powders followed by etching with HF, 6 plasma synthesis, 7 and solution reduction of SiCl4. 8 Colloidal stability of ncSi is easily achieved through a hydrosilylation reaction between surface Si-H groups and terminal alkenes. 9a-c It is well established that surface capping with organic ligands helps to pre...