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The assembly of thin films (TFs) having long-lasting luminescence can be expected to play an important role in the development of new-generation smart sensors, anti-counterfeiting materials, and information-encryption systems. However, such films are limited compared with their powder and solution counterparts. In this study, by exploiting the self-organization of phosphors in the two-dimensional (2D) galleries between clay nanosheets, we developed a method for the ordered assembly of long-afterglow TFs by utilizing a hydrogen-bonding layer-by-layer (LBL) process. Compared with the pristine powder, the TFs exhibit high polarization and up-conversion room-temperature phosphorescence (RTP), as well as enhanced quantum yields and luminescence lifetimes, allowing them to be used as room-temperature phosphorescent sensors for humidity and oxygen. Moreover, modified clay-based hybrids with multicolor RTP can serve as anti-counterfeiting marks and triple-mode 2D barcode displays. We anticipate that the LBL assembly process can be extended to the fabrication of other inorganic–organic room-temperature phosphorescent hybrids with smart luminescent sensor and antiforgery applications.
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