A Broad Dual Emitter by Codoping Cr3+ (d→d) and Bi3+ (s→p) in Cs2Ag0.6Na0.4InCl6 Halide Double Perovskite.

Sajid Saikia^a

^aPh.D. student at Indian Institute of Science Education and Research (IISER) Pune

Proceedings of International Conference on Emerging Light Emitting Materials (EMLEM23)

Peyia, Cyprus, 2023 November 13th - 15th

Organizers: Grigorios Itskos, Maksym Kovalenko and Maryna Bodnarchuk

Oral, Sajid Saikia, presentation 015
DOI: https://doi.org/10.29363/nanoge.emlem.2023.015
Publication date: 18th August 2023

Materials that emit either white light or near-infrared (NIR) are known for indoor/ outdoor room lighting^[1]or NIR spectroscopic applications like food inspection, remote sensing, bioimaging etc. However, simultaneous white light and broad NIR radiation from a single material can provide both information viz. visual inspection (color/ overall appearance) and early signs of rotting of food products. The broad NIR emission near 1000 nm can effectively absorb by the vibrational overtones of water molecules (-OH) present in food items, providing the non-invasive image contrast to assess the food freshness. Upon single excitation a material that can provide dual emissions covering white light and broad NIR is desired and challenging to design. Here I will be discussing about our recently designed such broad dual emitter, Cr³⁺-Bi³⁺-codoped Cs₂Ag_0.6Na_0.4InCl₆.

Octahedral site of perovskites lattice is suitable for wide range of ions to dope and hence allows to tune optical properties^[2]. Codoping Cr³⁺ and Bi³⁺ in the lattice of Cs₂Ag_0.6Na_0.4InCl₆ halide double perovskitecan simultaneously emit warm white light and broad NIR (λ_max≈1000 nm) radiation with quantum yield 27%. This dual emitter is designed by combining the features of s²-electron (Bi³⁺) and d³-electron (Cr³⁺) doping. Importantly, host lattice Cs₂Ag_0.6Na_0.4InCl₆ provides weak crystal field to Cr³⁺enabling to get broadness in the NIR PL. Other hand, Bi³⁺ via 6s²→6s¹6p¹excitation allows to use a commercial 370 nm ultraviolet light-emitting-diodes (UV-LED), yielding both emissions. A fraction of the excited Bi³⁺ dopants emit warm white light, and the other fraction transfers its energy non-radiatively to codopants Cr³⁺. Then the Cr³⁺ de-excites emitting broad NIR emission. Temperature dependent (6.4–300 K) photoluminescence in combination with Tanabe-Sugano diagram helps to understand the photophysics of the system. It reveals that Cr³⁺ experiences a weak crystal field (Dq∕B=2⋅2), yielding the⁴T₂→ ⁴A₂ (d-d transition) NIR emission. As a proof of concept, we fabricated a panel of 122 phosphor-converted LEDs with dimensions 22 × 17 cm², demonstrating its capability to inspect food products.^[3]

References:

[1] Luo, J.; Wang, X.; Li, S.; Liu, J.; Guo, Y.; Niu, G.; Yao, L.; Fu, Y.; Gao, L.; Dong, Q.; Zhao, C.; Leng, M.; Ma, F.; Liang, W.; Wang, L.; Jin, S.; Han, J.; Zhang, L.; Etheridge, J.; Wang, J.; Yan, Y.; Sargent, E. H.; Tang, J. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature 2018, 563 (7732), 541-545.

[2] Dey, A.; Ye, J.; De, A.; Debroye, E.; Ha, S. K.; Bladt, E.; Kshirsagar, A. S.; Wang, Z.; Yin, J.; Wang, Y.; Quan, L. N.; Yan, F.; Gao, M.; Li, X.; Shamsi, J.; Debnath, T.; Cao, M.; Scheel, M. A.; Kumar, S.; Steele, J. A.; Gerhard, M.; Chouhan, L.; Xu, K.; Wu, X.-g.; Li, Y.; Zhang, Y.; Dutta, A.; Han, C.; Vincon, I.; Rogach, A. L.; Nag, A.; Samanta, A.; Korgel, B. A.; Shih, C.-J.; Gamelin, D. R.; Son, D. H.; Zeng, H.; Zhong, H.; Sun, H.; Demir, H. V.; Scheblykin, I. G.; Mora-Seró, I.; Stolarczyk, J. K.; Zhang, J. Z.; Feldmann, J.; Hofkens, J.; Luther, J. M.; Pérez-Prieto, J.; Li, L.; Manna, L.; Bodnarchuk, M. I.; Kovalenko, M. V.; Roeffaers, M. B. J.; Pradhan, N.; Mohammed, O. F.; Bakr, O. M.; Yang, P.; Müller-Buschbaum, P.; Kamat, P. V.; Bao, Q.; Zhang, Q.; Krahne, R.; Galian, R. E.; Stranks, S. D.; Bals, S.; Biju, V.; Tisdale, W. A.; Yan, Y.; Hoye, R. L. Z.; Polavarapu, L. State of the Art and Prospects for Halide Perovskite Nanocrystals. ACS Nano 2021, 15 (7), 10775-10981.

[3] Saikia, S.; Ghosh, A.; Nag, A. Broad Dual Emission by Codoping Cr(3+) ( d → d ) and Bi(3+) ( s → p ) in Cs(2) Ag(0.6) Na(0.4) InCl(6) Double Perovskite. Angew. Chem. Int. Ed. 2023, e202307689.

Acknowledgements:

I acknowledge Aprajita Joshi and Prof. Surajit Saha from IISER Bhopal for Raman spectroscopy measurements. Also, I acknowledge the Prime Minister's Research Fellowship (PMRF), Ministry of Education, India for research fellowship and contingency.

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