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Title: Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12

Abstract

First-principles studies of electronic structures, excitons, and defects in Li2B12H12 reveal unique photophysical properties of Li2B12H12 and its potential as a neutron scintillator material. We identify the electronic shell structure in (B12H12)2-, which gives rise to strong chemical stability of (B12H12)2- and a large band gap of Li2B12H12. Based on hybrid functional calculations, we show that excitons in Li2B12H12 are strongly self-trapped and predict that the exciton excitation and emission are both in the UV range and are not related to the bright blue emission observed in the experiment. The experimentally observed blue emission in Li2B12H12 is likely due to the emission of excitons bound to hydrogen vacancies. The calculated strong localization and large exciton trapping energy at hydrogen vacancies indicate enhanced radiative recombination, while the calculated large Stokes shift suggests that the self-absorption and the resonance transfer of the excitation energy may be suppressed. These properties should promote efficient defect emission at room temperature. The efficient defect emission, combined with the large thermal neutron capture cross-section by Li and B and the efficient energy transfer between fast neutrons and H, suggests potential applications of Li2B12H12 as a thermal or fast neutron scintillator. Optical characterization of VH may also bemore » used to monitor H and Li concentrations in Li2B12H12-based hydrogen storage materials and solid-state electrolytes in Li batteries.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  2. Key Laboratory of Micro-Nano Measurement-Manipulation and Physics (Ministry of Education); Department of Physics; Beihang University; Beijing 100191; China
  3. Rensselaer Polytechnic Inst., Troy, NY (United States). Dept. of Electrical, Computer and Systems Engineering
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1607243
Alternate Identifier(s):
OSTI ID: 1573509
Grant/Contract Number:  
AC05-00OR22725; SC0002623
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 7; Journal Issue: 45; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Du, Mao-Hua, Shi, Hongliang, and Zhang, S. B. Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12. United States: N. p., 2019. Web. doi:10.1039/c9tc04150h.
Du, Mao-Hua, Shi, Hongliang, & Zhang, S. B. Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12. United States. https://doi.org/10.1039/c9tc04150h
Du, Mao-Hua, Shi, Hongliang, and Zhang, S. B. Wed . "Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12". United States. https://doi.org/10.1039/c9tc04150h. https://www.osti.gov/servlets/purl/1607243.
@article{osti_1607243,
title = {Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12},
author = {Du, Mao-Hua and Shi, Hongliang and Zhang, S. B.},
abstractNote = {First-principles studies of electronic structures, excitons, and defects in Li2B12H12 reveal unique photophysical properties of Li2B12H12 and its potential as a neutron scintillator material. We identify the electronic shell structure in (B12H12)2-, which gives rise to strong chemical stability of (B12H12)2- and a large band gap of Li2B12H12. Based on hybrid functional calculations, we show that excitons in Li2B12H12 are strongly self-trapped and predict that the exciton excitation and emission are both in the UV range and are not related to the bright blue emission observed in the experiment. The experimentally observed blue emission in Li2B12H12 is likely due to the emission of excitons bound to hydrogen vacancies. The calculated strong localization and large exciton trapping energy at hydrogen vacancies indicate enhanced radiative recombination, while the calculated large Stokes shift suggests that the self-absorption and the resonance transfer of the excitation energy may be suppressed. These properties should promote efficient defect emission at room temperature. The efficient defect emission, combined with the large thermal neutron capture cross-section by Li and B and the efficient energy transfer between fast neutrons and H, suggests potential applications of Li2B12H12 as a thermal or fast neutron scintillator. Optical characterization of VH may also be used to monitor H and Li concentrations in Li2B12H12-based hydrogen storage materials and solid-state electrolytes in Li batteries.},
doi = {10.1039/c9tc04150h},
journal = {Journal of Materials Chemistry C},
number = 45,
volume = 7,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: Electronic band structure (a) and density of states (DOS) (b) of Li2B12H12 obtained by the PBE calculation. Note that the band gap is underestimated. The hybrid PBE0 calculation increases the band gap to 7.63 eV. The energy of the valence band maximum is set to zero.

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