Mn4+-activated luminescent materials exhibit high color purity red light emission, but their limited water resistance hinders practical applications. In this study, citric and oxalic acids are innovatively employed for surface modification, resulting in luminescent materials with enhanced water resistance while preserving their luminescent intensity. This enhancement provides a prerequisite for their application in anti-counterfeiting films and aqueous fluorescent inks. Furthermore, the potential for optical information storage is successfully demonstrated by utilizing the photochromic fluorescent properties of polyvinyl alcohol films deposited on oxalic acid-modified K2SiF6:Mn4+. Exploiting the 3 ms day time difference between equivalently and non-equivalently doped Mn4+ fluoride, a millisecond information encryption mode is proposed by combining oxalic acid-modified K2SiF6:Mn4+ (long decay time, τ = 8.99 ms) and K3AlF6:Mn4+ (short decay time, τ = 5.31 ms). This mode can be effectively decoded using digital cameras and editing software, achieving high-level anti-counterfeiting capabilities. This work advances the application of highly efficient Mn4+-activated red phosphors in the realm of information security.
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