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Title: Orbital controlled band gap engineering of tetragonal BiFeO 3 for optoelectronic applications

Abstract

Bismuth ferrite BiFeO 3 (BFO) is an important ferroelectric material for thin-film optoelectronic sensing and potential photovoltaic applications. Its relatively large band gap, however, limits the conversion efficiency of BFO absorber-based PV devices. In this study, based on density functional theory calculations we demonstrate that with well-designed Fe-site elemental substitution, tetragonal BFO can exhibit a much lower fundamental band gap than conventional rhombohedral BFO without forming in-gap electronic states and unravel the underlying mechanisms. Cation atomic size, electronegativity, and crystallographic symmetry are evidenced as critical parameters to tailor the metal 3d – oxygen 2p orbital interactions and thus intrinsically modify electronic structure, particularly, the shape and character of the valence and conduction band edges. With reduced band gap, improved mobility, and uncompromised ferroelectric and magnetic ground states, the present results provide a new strategy of designing high symmetry BFO for efficient optoelectronic applications.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [2];  [6]
  1. Univ. of Electronic Science and Technology of China, Chengdu (China). School of Physics; Univ. of Manchester (United Kingdom). School of Materials; Univ. of New South Wales, Sydney, NSW (Australia). School of Materials
  2. Univ. of Electronic Science and Technology of China, Chengdu (China). School of Physics
  3. Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
  4. Xiamen Univ., Xiamen (China). College of Chemistry and Chemical Engineering; Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Engineering
  5. Lanzhou City Univ., Lanzhou (China). Dept. of Physics
  6. Univ. of New South Wales, Sydney, NSW (Australia). School of Materials
Publication Date:
Research Org.:
Univ. of Missouri, Columbia, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1419252
Grant/Contract Number:  
SC0014607; U1530129; 11774044
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 33 ADVANCED PROPULSION SYSTEMS; 36 MATERIALS SCIENCE; Band gap engineering; Optical absorption; BiFeO3; DFT+U

Citation Formats

Qiao, L., Zhang, S., Xiao, H. Y., Singh, D. J., Zhang, K. H. L., Liu, Z. J., Zu, X. T., and Li, S. Orbital controlled band gap engineering of tetragonal BiFeO 3 for optoelectronic applications. United States: N. p., 2018. Web. doi:10.1039/c7tc04160h.
Qiao, L., Zhang, S., Xiao, H. Y., Singh, D. J., Zhang, K. H. L., Liu, Z. J., Zu, X. T., & Li, S. Orbital controlled band gap engineering of tetragonal BiFeO 3 for optoelectronic applications. United States. doi:10.1039/c7tc04160h.
Qiao, L., Zhang, S., Xiao, H. Y., Singh, D. J., Zhang, K. H. L., Liu, Z. J., Zu, X. T., and Li, S. Mon . "Orbital controlled band gap engineering of tetragonal BiFeO 3 for optoelectronic applications". United States. doi:10.1039/c7tc04160h. https://www.osti.gov/servlets/purl/1419252.
@article{osti_1419252,
title = {Orbital controlled band gap engineering of tetragonal BiFeO 3 for optoelectronic applications},
author = {Qiao, L. and Zhang, S. and Xiao, H. Y. and Singh, D. J. and Zhang, K. H. L. and Liu, Z. J. and Zu, X. T. and Li, S.},
abstractNote = {Bismuth ferrite BiFeO3 (BFO) is an important ferroelectric material for thin-film optoelectronic sensing and potential photovoltaic applications. Its relatively large band gap, however, limits the conversion efficiency of BFO absorber-based PV devices. In this study, based on density functional theory calculations we demonstrate that with well-designed Fe-site elemental substitution, tetragonal BFO can exhibit a much lower fundamental band gap than conventional rhombohedral BFO without forming in-gap electronic states and unravel the underlying mechanisms. Cation atomic size, electronegativity, and crystallographic symmetry are evidenced as critical parameters to tailor the metal 3d – oxygen 2p orbital interactions and thus intrinsically modify electronic structure, particularly, the shape and character of the valence and conduction band edges. With reduced band gap, improved mobility, and uncompromised ferroelectric and magnetic ground states, the present results provide a new strategy of designing high symmetry BFO for efficient optoelectronic applications.},
doi = {10.1039/c7tc04160h},
journal = {Journal of Materials Chemistry C},
number = 5,
volume = 6,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
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Cited by: 4 works
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Figures / Tables:

Fig. 1 Fig. 1: Schematic view of tetragonal BiFeO3 with (a) G-AFM arrangement of Fe atoms and spins and (b) C-AFM arrangement of Fe atoms and spins.The purple, brown and red spheres represent Bi, Fe and O atoms, respectively.

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