  Using first-principles electronic structure calculations we identify the
anion vacancies in II-VI and chalcopyrite Cu-III-VI2 semiconductors as a class
of intrinsic defects that can exhibit metastable behavior. Specifically, we
predict persistent electron photoconductivity (n-type PPC) caused by the oxygen
vacancy VO in n-ZnO, and persistent hole photoconductivity (p-type PPC) caused
by the Se vacancy VSe in p-CuInSe2 and p-CuGaSe2. We find that VSe in the
chalcopyrite materials is amphoteric having two "negative-U" like transitions,
i.e. a double-donor transition e(2+/0) close to the valence band and a
double-acceptor transition e(0/2-) closer to the conduction band. We introduce
a classification scheme that distinguishes two types of defects (e.g., donors):
type-alpha, which have a defect-localized-state (DLS) in the gap, and
type-beta, which have a resonant DLS within the host bands (e.g., conduction
band). In the latter case, the introduced carriers (e.g., electrons) relax to
the band edge where they can occupy a perturbed-host-state (PHS). Type alpha is
non-conducting, whereas type beta is conducting. We identify the neutral anion
vacancy as type-alpha and the doubly positively charged vacancy as type-beta.
We suggest that illumination changes the charge state of the anion vacancy and
leads to a crossover between alpha- and beta-type behavior, resulting in
metastability and PPC. In CuInSe2, the metastable behavior of VSe is carried
over to the (VSe-VCu) complex, which we identify as the physical origin of PPC
observed experimentally. We explain previous puzzling experimental results in
ZnO and CuInSe2 in the light of this model.
