We demonstrate that the electronic structure of mesoporous silicon is
affected by adsorption of nitro-based explosive molecules in a
compound-selective manner. This selective response is demonstrated by probing
the adsorption of two nitro-based molecular explosives (trinitrotoluene and
cyclotrimethylenetrinitramine) and a nonexplosive nitro-based arematic molecule
(nitrotoluene) on mesoporous silicon using soft X-ray spec- troscopy. The Si
atoms strongly interact with adsorbed molecules to form Si-O and Si-N bonds, as
evident from the large shifts in emission energy present in the Si L2,3 X-ray
emission spectroscopy (XES) measurements. Furthermore, we find that the energy
gap of mesoporous silicon changes depending on the adsorbant, as estimated from
the Si L2,3 XES and 2p X-ray absorption spectroscopy (XAS) measurements. Our ab
initio molecular dynamics calculations of model compounds suggest that these
changes are due to spontaneous breaking of the nitro groups upon contacting
surface Si atoms. This compound-selective change in electronic structure may
provide a powerful tool for the detection and identification of trace
quantities of airborne explosive molecules.Comment: 27 pages, 9 figure