The function of common, positive tone photoresist
materials is based on radiation-induced
modulation of the dissolution rate of phenolic polymer films in aqueous
base. The process through which
novolac and other low molecular weight phenolic polymers undergo
dissolution is examined from a new
perspective in which the “average degree of ionization” of the
polymer is regarded as the principal factor
that determines the rate of dissolution rather than a diffusive,
transport process. This perspective has
been coupled with a probabilistic model that provides an explanation
for the dependence of the dissolution
rate on molecular weight, base concentration, added salts, residual
casting solvent, and the addition of
“dissolution inhibitors”. It predicts the observed minimum
base concentration below which dissolution
is no longer observed, and it predicts a molecular weight dependence of
that phenomenon. A series of
experiments was designed to test this predicted molecular weight
response. The results of these
experiments are in good agreement with the predicted
response.