Reversible Mn valence state switching in submicron α-Al₂O₃:Mn by soft X-rays and blue light - a potential pathway...

The generation of Mn⁴⁺ in α-Al₂O₃:Mn³⁺ by soft X-ray exposure is demonstrated with a large dynamic range of the X-ray generated Mn⁴⁺ luminescence signal, indicating the potential use of α-Al₂O₃:Mn³⁺ for multilevel optical data storage. Samples with a range of Mn concentrations (0.05, 0.1, 0.2, 0.4, 0.6 and 1.2 atom%) were prepared via a facile combustion method and the sample with 0.4 atom% was found to display the highest luminescence intensity. The stored information can be read out via the R-lines (²E → ⁴A₂) under ∼470 nm (⁴A₂ → ⁴T₂), or ∼630 nm (⁴A₂ → ²T₁) excitation with the latter being preferred since photobleaching is minimized. Interestingly, the Mn⁴⁺ valence state can be fully switched back to Mn³⁺ by blue light exposure (e.g., 462 nm laser diode). The stored information could be repeatedly written and erased, showing no significant deterioration over five consecutive cycles, with less than 5% uncertainty.