ABSTRACT Piezoelectric materials with strain‐induced polarization and rapid stimulus responsiveness hold immense promise for intelligent sensing and high‐security information systems. However, integrating sensitive temperature sensing, intense mechanoluminescence (ML), and stable multimodal luminescence into a single material system remains challenging due to functional/environmental trade‐offs. Herein, we report an integrated design strategy combining matrix engineering, ion synergy, and heterojunction interface modulation. Leveraging the dual cationic sites (Zn 2+ /Ba 2+ ) in BaZnOS for selective Mn 2+ /Er 3+ codoping, dual emission centers with enhanced luminescence are constructed: Mn 2+ ‐derived orange luminescence and Er 3+ ‐dominated red emission, enabled by efficient Mn 2+ ‐Er 3+ energy transfer. The BaZnOS:Mn,Er exhibits reliable thermometric performance with a maximum relative sensitivity of 1.02% K −1 over 303–563 K, alongside Mn 2+ ‐centered ML under mechanical stimulation. To overcome the intrinsic ML intensity limitation of single‐phase materials, we rationally engineer a heterojunction by integrating BaTiO 3 nanosheets with BaZnOS:Mn,Er microcrystals, achieving a remarkable 134% ML intensity enhancement (at 5 N) via piezoelectric polarization and interfacial coupling. These advances enable the fabrication of a dynamic multimodal luminescence platform, applicable for unclonable anti‐counterfeiting, tamper‐evident electronic signatures, and forgery‐proof information encryption. This work establishes a versatile design paradigm for multifunctional piezoelectric luminescent materials, thereby paving the way for next‐generation intelligent sensing devices and high‐security information systems.
Wáng et al. (Mon,) studied this question.