Photoluminescence of polycrystalline hexagonal boron nitride ͑hBN͒ was measured by means of time-and energy-resolved spectroscopy methods. The observed bands are related to donor-acceptor pair transitions, impurities, and structural defects. The excitation of samples by high-energy photons above 5.4 eV enables a phenomenon of photostimulated luminescence ͑PSL͒, which is due to distantly trapped conduction band electrons and valence band holes. These trapped charges are metastable and their re-excitation with low-energy photons results in anti-Stokes photoluminescence. The comparison of photoluminescence excitation spectra and PSL excitation spectra allows band analysis that supports the hypothesis of Frenkel-type exciton in hBN with a large binding energy.

The processes of intrinsic and extrinsic luminescence excitation by synchrotron radiation of 4-40 eV or electron pulses have been studied in ␣-Al 2 O 3 single crystals at 8 K. The intrinsic A ͑7.6 eV͒ and E emissions ͑3.77 eV͒ can be effectively excited in the region of long-wavelength ͑8.85-9.1 eV͒ and short-wavelength ͑9.1-9.3 eV͒ components of exciton absorption doublet, respectively. Fast ͑ϳ6 and ϳ20 ns͒ and slow ͑ϳ150 ns͒ components of the A emission correspond to the creation of singlet and triplet p 5 s excitons. The efficiency of the A emission in the region of band-to-band transitions is low. The intensity of A emission sharply increases ͑approximately quadratically͒ with a rise of the excitation density by nanosecond electron pulses. In Al 2 O 3 :Sc, the 5.6-eV luminescence is caused by the decay of near-impurity electronic excitations ͑ϳ8.5 eV͒ as well as by the electron recombination with holes localized near Sc 3ϩ centers. The efficiency of 7.6-, 5.6-, and 3.8-eV emission sharply increases at the energy of exciting photons of hϾ25 eV. One photon of 26-29 and 30-37 eV causes the ionization of the 2p 6 or 2s 2 shell of the oxygen ion and provides the creation of two or three electron-hole pairs, respectively. Long-term investigations of ␣-Al 2 O 3 crystals did not lead to the detection of immobile self-trapped holes or electrons. The A emission excited at the direct photocreation of excitons or at the recombination of free electrons and free holes is interpreted by us as the radiative decay of self-shrunk excitons. The theoretical model of Sumi allows the existence of such immobile self-shrunk excitons even if an electron and a hole do not separately undergo the self-trapping. ͓S0163-1829͑99͒01825-1͔

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