Desorption/ionization on porous silicon mass spectrometry (DIOS-MS) is a no
vel method for generating and analyzing gas-phase ions that employs direct
laser vaporization. The structure and physicochemical properties of the por
ous silicon surfaces are crucial to DIGS-MS performance and are controlled
by the selection of silicon and the electrochemical etching conditions. Por
ous silicon generation and DIGS signals were examined as a function of sili
con crystal orientation, resistivity, etching solution, etching current den
sity, etching time, and irradiation. Pre-and postetching conditions were al
so examined for their effect on DIGS signal as were chemical modifications
to examine stability with respect to surface oxidation, Pore size and other
physical characteristics were examined by scanning electron microscopy and
Fourier transform infrared spectroscopy, and correlated with DIGS-MS signa
l. Porous silicon surfaces optimized for DIGS response were examined for th
eir applicability to quantitative analysis, organic reaction monitoring, po
st-source decay mass spectrometry, and chromatography.