Cation-defect-induced self-reduction towards efficient mechanoluminescence in Mn²⁺-activated perovskites

Mechanoluminescent (ML) materials have shown promising prospects for various applications, e.g. in stress sensing, information anti-counterfeiting and bio stress imaging fields. However, the development of trap-controlled ML materials is still limited, because the trap formation mechanism is not always clear. Here, inspired by a defect-induced Mn⁴⁺ → Mn²⁺ self-reduction process in suitable host crystal structures, a cation vacancy model is creatively proposed to determine the potential trap-controlled ML mechanism. Combined with the theoretical prediction and experimental results, both the self-reduction process and ML mechanism are clarified in detail, where the contribution of and defects dominates the ML luminescent process. Electrons/holes are mainly captured by the anionic/cationic defects, followed by the combination of electrons and holes to transfer energy to the Mn²⁺ 3d states under mechanical stimuli. Based on the multi-mode luminescent features excited by X-ray, 980 nm laser and 254 nm UV lamp, together with the excellent persistent luminescence and ML, a potential application in advanced anti-counterfeiting is demonstrated. These results will deepen the understanding of the defect-controlled ML mechanism, and inspire more defect-engineering strategies to develop more high-performance ML phosphors for practical application.