We have investigated the photoluminescence and ultrafast dynamics of LaAlO3 crystal. The photoluminescence consists of a broad spectrum and two sharp peaks, which arise from various defect levels within the bandgap. A doublet splitting of roughly 6 nm is seen in these two sharp peaks. An Al displacement of 0.09 Å in a sublattice, which is possible because of twinning, is adequate to explain the spectral splitting. Femtosecond pump probe experiments reveal further that many of these defect levels have a few picosecond decay times while the lowest defect states have decay times longer than nanosecond to the valence band.

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