Issue 32, 2021

Mechanisms of bismuth-activated near-infrared photoluminescence – a first-principles study on the MXCl3 series

Abstract

Bismuth dopants have attracted intensive studies experimentally for their extremely broad near-infrared luminescence. Here we performed first-principles calculations to investigate the site occupancy and valence state by taking the condition of synthesis into consideration, and then calculated the excited states and various transitions of the bismuth ions by focusing on the targeted valent state Bi+ in a variety of ternary chloride MXCl3 (M = K, Rb, Cs; X = Mg, Cd) hosts. The results on formation energies and charge transition levels show that vacant defects play an important role in the charge compensation for the bismuth dopants, and a lower chemical potential of chlorine benefits the stabilization of Bi+ at monovalent M sites. The multi-configurational quantum-chemical method and the constrained occupancy approach together confirm the near-infrared photoluminescence of Bi+, and the spontaneous emission rates due to electric–dipole and magnetic–dipole contributions are evaluated and analyzed in terms of transition selection rules, to affirm the Bi+ nature of the long lifetime luminescence. Our results show that the mechanisms revealed in this study, and the combination of density-functional calculations for defect formation energies with the wave-function based calculations for optical transitions, are effective in exploring the luminescence of bismuth dopants in solids.

Graphical abstract: Mechanisms of bismuth-activated near-infrared photoluminescence – a first-principles study on the MXCl3 series

Supplementary files

Article information

Article type
Paper
Submitted
15 Apr 2021
Accepted
20 Jul 2021
First published
20 Jul 2021

Phys. Chem. Chem. Phys., 2021,23, 17420-17429

Mechanisms of bismuth-activated near-infrared photoluminescence – a first-principles study on the MXCl3 series

Q. Chen, W. Jing, Y. Yeung, M. Yin and C. Duan, Phys. Chem. Chem. Phys., 2021, 23, 17420 DOI: 10.1039/D1CP01632F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements