Cathodoluminescence and electrostatic techniques were used to study the nanoscale spatial evolution of native defects, crystallinity and work function in Ga2O3 across different morphological regions in laser induced periodic surface structures generated by an ultrafast laser. An emergent ~2.4 eV emission, likely related to oxygen interstitials or divacancy complexes, inversely correlates with the crystallinity of these regions. A contrast in work functions between the rims and troughs of the LIPSS, indicative of periodic differences in defect concentration, correlates with a reduction of crystallinity in the rim region relative to the trough region, suggesting an increased concentration of relatively shallow defects.
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