We elucidate here the nature of the emissive states in Rb7Sb3Cl16 nanocrystals (NCs) for which we report a synthesis. These NCs have a crystal structure comprising both isolated [SbCl6]3- octahedra and isolated [Sb2Cl10]4- dimers of octahedra. The optical properties of Rb7Sb3Cl16 NCs are compared with those of Sb-doped Rb3InCl6 NCs, the latter containing only isolated [SbCl6]3- octahedra. The remarkably similar behaviors of the two systems indicate that the optical emission in both materials originates from the isolated octahedra. Density functional theory calculations suggest that the [SbCl6]3- octahedra are optically active in emission because the local arrangement of the Rb+ ions around the octahedra limits the elongation of the Sb-Cl bonds upon excitation, helping to confine the self-trapped exciton in them. Conversely, in the [Sb2Cl10]4- dimers the constraining effect of the surrounding Rb+ ions is less marked and the Sb-Cl bonds fully break upon photoexcitation, opening up an efficient nonradiative channel for the self-trapped excitons.

Zhang, B., Pinchetti, V., Zito, J., Ray, A., Melcherts, A., Ghini, M., et al. (2021). Isolated [SbCl6]3– Octahedra Are the Only Active Emitters in Rb7Sb3Cl16 Nanocrystals. ACS ENERGY LETTERS, 6(11), 3952-3959 [10.1021/acsenergylett.1c01662].

Isolated [SbCl6]3– Octahedra Are the Only Active Emitters in Rb7Sb3Cl16 Nanocrystals

Pinchetti, Valerio
Co-primo
;
Pianetti, Andrea;Brovelli, Sergio
;
2021

Abstract

We elucidate here the nature of the emissive states in Rb7Sb3Cl16 nanocrystals (NCs) for which we report a synthesis. These NCs have a crystal structure comprising both isolated [SbCl6]3- octahedra and isolated [Sb2Cl10]4- dimers of octahedra. The optical properties of Rb7Sb3Cl16 NCs are compared with those of Sb-doped Rb3InCl6 NCs, the latter containing only isolated [SbCl6]3- octahedra. The remarkably similar behaviors of the two systems indicate that the optical emission in both materials originates from the isolated octahedra. Density functional theory calculations suggest that the [SbCl6]3- octahedra are optically active in emission because the local arrangement of the Rb+ ions around the octahedra limits the elongation of the Sb-Cl bonds upon excitation, helping to confine the self-trapped exciton in them. Conversely, in the [Sb2Cl10]4- dimers the constraining effect of the surrounding Rb+ ions is less marked and the Sb-Cl bonds fully break upon photoexcitation, opening up an efficient nonradiative channel for the self-trapped excitons.
Articolo in rivista - Articolo scientifico
perovskite nanocrystals, optical spectroscopy, colloidal synthesis, DFT;
English
21-ott-2021
2021
6
11
3952
3959
reserved
Zhang, B., Pinchetti, V., Zito, J., Ray, A., Melcherts, A., Ghini, M., et al. (2021). Isolated [SbCl6]3– Octahedra Are the Only Active Emitters in Rb7Sb3Cl16 Nanocrystals. ACS ENERGY LETTERS, 6(11), 3952-3959 [10.1021/acsenergylett.1c01662].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/332427
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