The origin of the photoluminescence (PL) of porous silicon is being ex
tensively investigated. In this letter, we offer detailed analyses of
the PL spectra, of which about 3%-5% show small extrema that superimpo
se the larger main peak. Spacing between these smaller maxima is repro
ducible and independent of the main peak energy and sample history, wh
ile energy steps between them correlate with differences in the excito
n energies due to changing the sizes of the quantum wires by complete
monolayers of atoms.