title: Tailored Near-Infrared Photoemission in Fluoride Perovskites through Activator Aggregation and Super-Exchange between Divalent Manganese Ions.
abstract: Biomedical imaging and labeling through luminescence microscopy requires materials that are active in the near-infrared spectral range, i.e., within the transparency window of biological tissue. For this purpose, tailoring of Mn2+-Mn2+activator aggregation is demonstrated within the ABF3fluoride perovskites. Such tailoring promotes distinct near-infrared photoluminescence through antiferromagnetic super-exchange across effective dimers. The crossover dopant concentrations for the occurrence of Mn2+interaction within the first and second coordination shells comply well with experimental observations of concentration quenching of photoluminescence from isolated Mn2+and from Mn2+-Mn2+effective dimers, respectively. Tailoring of this procedure is achieved via adjusting the Mn-F-Mn angle and the Mn-F distance through substitution of the A+and/or the B2+species in the ABF3compound. Computational simulation and X-ray absorption spectroscopy are employed to confirm this. The principle is applied to produce pure anti-Stokes near-infrared emission within the spectral range of ≈760-830 nm from codoped ABF3:Yb3+,Mn2+upon excitation with a 976 nm laser diode, challenging the classical viewpoint where Mn2+is used only for visible photoluminescence: in the present case, intense and tunable near-infrared emission is generated. This approach is highly promising for future applications in biomedical imaging and labeling.
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices Institute of Optical Communication Materials South China University of Technology Guangzhou 510640 China.
authors.forename: Enhai
authors.initials: E
authors.lastname: Song
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices Institute of Optical Communication Materials South China University of Technology Guangzhou 510640 China.
authors.forename: Shi
authors.initials: S
authors.lastname: Ye
authors.affiliation: Beijing National Laboratory for Molecular Sciences State Key Laboratory of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering Peking University Beijing 100871 China.
authors.forename: Tianhui
authors.initials: T
authors.lastname: Liu
authors.affiliation: Shanghai Institute of Applied Physics Chinese Academy Sciences Shanghai Synchrotron Radiation Facility Shanghai 201204 China.
authors.forename: Peipei
authors.initials: P
authors.lastname: Du
authors.affiliation: Shanghai Institute of Applied Physics Chinese Academy Sciences Shanghai Synchrotron Radiation Facility Shanghai 201204 China.
authors.forename: Rui
authors.initials: R
authors.lastname: Si
authors.affiliation: Beijing National Laboratory for Molecular Sciences State Key Laboratory of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering Peking University Beijing 100871 China.
authors.forename: Xiping
authors.initials: X
authors.lastname: Jing
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices Institute of Optical Communication Materials South China University of Technology Guangzhou 510640 China.
authors.forename: Sha
authors.initials: S
authors.lastname: Ding
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices Institute of Optical Communication Materials South China University of Technology Guangzhou 510640 China.
authors.forename: Mingying
authors.initials: M
authors.lastname: Peng
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices Institute of Optical Communication Materials South China University of Technology Guangzhou 510640 China.
authors.forename: Qinyuan
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: Otto Schott Institute of Materials Research University of Jena 07743 Jena Germany.
authors.forename: Lothar
authors.initials: L
authors.lastname: Wondraczek
keywords: Mn2+‐aggregation; near‐infrared emission; perovskites; photoluminescence; super‐exchange