The effect of room-temperature plastic deformation in darkness on the photoluminescence properties of ZnS

Inorganic semiconductors have been considered to be brittle at room temperature generally, but recently zinc sulfide (ZnS), a II-VI compound semiconductor, was found to exhibit extraordinarily large plasticity even at room temperature if it was deformed in darkness. Room-temperature plastic deformation can achieve high density of glide dislocations in the crystal without significantly changing the point defect structure, and these dislocations themselves have a potential to provide unique functional properties different from those of the bulk. In this study, therefore, undoped ZnS crystals were plastically deformed at room temperature in darkness to generate only a large number of dislocations, and the changes in luminescence properties resulting from this process were investigated for the first time. As a result, we found that ZnS deformed in darkness exhibits characteristic photoluminescence and persistent luminescence emissions with a visible green color. SEM-CL analyses also identified the emissions from the dislocations. Theoretical calculations indicated that individual dislocations in ZnS have the ability to trap photo-excited carriers. Such changes in luminescence properties due to room temperature plastic deformation in darkness can be considered to originate from dislocations rather than point defects. In other words, the dislocations themselves serve as the significant recombination centers, realizing visible light emission.