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Title: Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

Abstract

The ability to observe charge localization in photocatalytic materials on the ultrafast time scale promises to reveal important correlations between excited state electronic structure and photochemical energy conversion. Of particular interest is the ability to determine hole localization in the hybridized valence band of transition metal oxide semiconductors. Using femtosecond extreme ultraviolet reflection absorption (XUV-RA) spectroscopy we directly observe the formation of photoexcited electrons and holes in Fe2O3, Co3O4, and NiO occurring within the 100 fs instrument response. In each material, holes localize to the O 2p valence band states as probed at the O L1-edge, while electrons localize to metal 3d conduction band states on this same time scale as probed at the metal M2,3-edge. Chemical shifts at the O L1-edge enable unambiguous comparison of metal–oxygen (M–O) bond covalency. In conclusion, pump flux dependent measurements show that the exciton radius is on the order of a single M–O bond length, revealing a highly localized nature of exciton in each metal oxide studied.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1594151
Grant/Contract Number:  
SC0014051
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Covalency; exciton; metal oxides; X-ray absorption; water splitting

Citation Formats

Biswas, Somnath, Husek, Jakub, Londo, Stephen, and Baker, L. Robert. Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.7b04818.
Biswas, Somnath, Husek, Jakub, Londo, Stephen, & Baker, L. Robert. Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors. United States. https://doi.org/10.1021/acs.nanolett.7b04818
Biswas, Somnath, Husek, Jakub, Londo, Stephen, and Baker, L. Robert. Thu . "Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors". United States. https://doi.org/10.1021/acs.nanolett.7b04818. https://www.osti.gov/servlets/purl/1594151.
@article{osti_1594151,
title = {Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors},
author = {Biswas, Somnath and Husek, Jakub and Londo, Stephen and Baker, L. Robert},
abstractNote = {The ability to observe charge localization in photocatalytic materials on the ultrafast time scale promises to reveal important correlations between excited state electronic structure and photochemical energy conversion. Of particular interest is the ability to determine hole localization in the hybridized valence band of transition metal oxide semiconductors. Using femtosecond extreme ultraviolet reflection absorption (XUV-RA) spectroscopy we directly observe the formation of photoexcited electrons and holes in Fe2O3, Co3O4, and NiO occurring within the 100 fs instrument response. In each material, holes localize to the O 2p valence band states as probed at the O L1-edge, while electrons localize to metal 3d conduction band states on this same time scale as probed at the metal M2,3-edge. Chemical shifts at the O L1-edge enable unambiguous comparison of metal–oxygen (M–O) bond covalency. In conclusion, pump flux dependent measurements show that the exciton radius is on the order of a single M–O bond length, revealing a highly localized nature of exciton in each metal oxide studied.},
doi = {10.1021/acs.nanolett.7b04818},
journal = {Nano Letters},
number = 2,
volume = 18,
place = {United States},
year = {Thu Jan 25 00:00:00 EST 2018},
month = {Thu Jan 25 00:00:00 EST 2018}
}

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Cited by: 45 works
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