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Title: First principles study of the structural, electronic, and optical properties of Sn 2+-doped ZnO–P 2O 5 glasses [First principles study of the structural, electronic and optical properties of Sn-doped ZnO-P2O5 glasses]

Abstract

The atomic-structural, electronic, and optical properties of Sn-doped ZnO–P 2O 5 glasses are examined using combined semi-empirical and density functional theory calculations. From model structures for two different ZnO–P 2O 5 glass compositions, it is found that these glasses consist of nearly ideal tetrahedral PO 4 unit and largely distorted ZnO 4 and ZnO 5 units. The concentration of ZnO 5 units is calculated to increase and exceed that of ZnO 4 as the amount of ZnO in the glass is increased. Also, the concentration of terminal oxygen atoms shared by two Zn neighbors is largely increased for 70ZnO:30P 2O 5 (70:30) glass compared to 60:40 glass, which can be rationalized by electrostatic bond strength calculations. Regarding medium-range order, calculations show that Q 1 and Q 2 structures (where Q n refers to structures containing n bridging oxygen atoms on PO 4 tetrahedra) are dominant for the 60:40 glass, while Q 0 and Q 1 prevail for the 70:30 glass, in good agreement with experimental observations. For the Sn-doped ZnO–P 2O 5 glass, various Sn coordination geometries are found, with trigonal pyramidal SnO 3 and largely distorted pyramidal SnO 4 configurations being dominant and a small fraction of two-fold andmore » five-fold coordinated Sn configurations also present. From combined cluster and glass model calculations, two-fold coordinated Sn are found to exhibit slightly smaller optical transition energy than three-fold and four-fold coordinated Sn. However, local variations in coordination structures throughout the glass likely result in a broad singlet transition (S 0→S 1) around 5.4 eV for all the different Sn configurations. Finally, a triplet transition (S 0→T 1) driven by spin-orbit coupling can occur around 4.5 – 4.8 eV, but the magnitude of this transition is predicted to be much smaller than the spin-allowed singlet transition.« less

Authors:
 [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1466955
Report Number(s):
LLNL-JRNL-711877
Journal ID: ISSN 0022-3093; 849404
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Non-Crystalline Solids
Additional Journal Information:
Journal Volume: 492; Journal Issue: C; Journal ID: ISSN 0022-3093
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Glasses; Coordination environment

Citation Formats

Kweon, Kyoung E., and Lordi, Vincenzo. First principles study of the structural, electronic, and optical properties of Sn2+-doped ZnO–P2O5 glasses [First principles study of the structural, electronic and optical properties of Sn-doped ZnO-P2O5 glasses]. United States: N. p., 2018. Web. doi:10.1016/j.jnoncrysol.2018.04.016.
Kweon, Kyoung E., & Lordi, Vincenzo. First principles study of the structural, electronic, and optical properties of Sn2+-doped ZnO–P2O5 glasses [First principles study of the structural, electronic and optical properties of Sn-doped ZnO-P2O5 glasses]. United States. doi:10.1016/j.jnoncrysol.2018.04.016.
Kweon, Kyoung E., and Lordi, Vincenzo. Sun . "First principles study of the structural, electronic, and optical properties of Sn2+-doped ZnO–P2O5 glasses [First principles study of the structural, electronic and optical properties of Sn-doped ZnO-P2O5 glasses]". United States. doi:10.1016/j.jnoncrysol.2018.04.016. https://www.osti.gov/servlets/purl/1466955.
@article{osti_1466955,
title = {First principles study of the structural, electronic, and optical properties of Sn2+-doped ZnO–P2O5 glasses [First principles study of the structural, electronic and optical properties of Sn-doped ZnO-P2O5 glasses]},
author = {Kweon, Kyoung E. and Lordi, Vincenzo},
abstractNote = {The atomic-structural, electronic, and optical properties of Sn-doped ZnO–P2O5 glasses are examined using combined semi-empirical and density functional theory calculations. From model structures for two different ZnO–P2O5 glass compositions, it is found that these glasses consist of nearly ideal tetrahedral PO4 unit and largely distorted ZnO4 and ZnO5 units. The concentration of ZnO5 units is calculated to increase and exceed that of ZnO4 as the amount of ZnO in the glass is increased. Also, the concentration of terminal oxygen atoms shared by two Zn neighbors is largely increased for 70ZnO:30P2O5 (70:30) glass compared to 60:40 glass, which can be rationalized by electrostatic bond strength calculations. Regarding medium-range order, calculations show that Q1 and Q2 structures (where Qn refers to structures containing n bridging oxygen atoms on PO4 tetrahedra) are dominant for the 60:40 glass, while Q0 and Q1 prevail for the 70:30 glass, in good agreement with experimental observations. For the Sn-doped ZnO–P2O5 glass, various Sn coordination geometries are found, with trigonal pyramidal SnO3 and largely distorted pyramidal SnO4 configurations being dominant and a small fraction of two-fold and five-fold coordinated Sn configurations also present. From combined cluster and glass model calculations, two-fold coordinated Sn are found to exhibit slightly smaller optical transition energy than three-fold and four-fold coordinated Sn. However, local variations in coordination structures throughout the glass likely result in a broad singlet transition (S0→S1) around 5.4 eV for all the different Sn configurations. Finally, a triplet transition (S0→T1) driven by spin-orbit coupling can occur around 4.5 – 4.8 eV, but the magnitude of this transition is predicted to be much smaller than the spin-allowed singlet transition.},
doi = {10.1016/j.jnoncrysol.2018.04.016},
journal = {Journal of Non-Crystalline Solids},
number = C,
volume = 492,
place = {United States},
year = {2018},
month = {7}
}

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