Porous silicon showing a two-layer structure is studied by stepwise pe
eling the surface layer to clarify the nonuniformity in photoluminesce
nce (PL) emission as a function of depth. The upper layer is amorphous
and luminesces at higher energy and efficiency. The deeper the depth
or the lower the excitation energy E(ex), the lower the PL peak E(p);
but, at a low E(ex), E(p) is not sensitive to the depth. Both intrinsi
c PL emission and the variation of penetration depth with E(ex) contri
bute to the linear dependence of E(p) on E(ex), which is in contrast t
o the cases of a-Si:H and siloxene exhibiting thermalization gaps. The
total PL excitation spectrum, the integrated PL intensities versus E(
ex), saturates rather than exhibiting a peak. Its leading edge profile
is similar to that for the absorption spectrum, unchanged by the dept
h, and described by an Urbach tail with energy of 0.26 eV, which is 4-
5 times larger than that of a-Si:H. The results can be understood base
d on silicon clusters embedded in amorphous silicon incorporating oxyg
en and/or hydrogen.