Tailored Near‐Infrared Photoemission in Fluoride Perovskites through Activator Aggregation and Super‐Exchange between Divalent Manganese Ions

Advanced Science

Enhai Song²  Shi Ye²  Tianhui Liu³  Peipei Du¹  Rui Si¹  Xiping Jing³  Sha Ding²  Mingying Peng²  Qinyuan Zhang² 

[1] Shanghai Institute of Applied Physics, Chinese Academy Sciences, Shanghai Synchrotron Radiation Facility, Shanghai, China;State Key Laboratory of Luminescent Materials and Devices, Institute of Optical Communication Materials, South China University of Technology, Guangzhou, China;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, China

关键词: Mn2+‐aggregation;    near‐infrared emission;    perovskites;    photoluminescence;    super‐exchange;   

DOI  :  10.1002/advs.201500089

来源: Wiley

【 摘 要 】

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 ABF₃ fluoride 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 ABF₃ compound. 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.

【 授权许可】

CC BY   
© 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.