Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

Biswas, Somnath; Husek, Jakub; Londo, Stephen; Baker, L. Robert

doi:10.1021/acs.nanolett.7b04818

Title: Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

Journal Article · Thu Jan 25 00:00:00 EST 2018 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b04818· OSTI ID:1594151

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^[1]; Londo, Stephen ^[1];

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The Ohio State Univ., Columbus, OH (United States)

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 M_2,3-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.

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Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0014051

OSTI ID:: 1594151

Journal Information:: Nano Letters, Vol. 18, Issue 2; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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Three applications of ultrafast transient absorption spectroscopy of semiconductor thin films: spectroelectrochemistry, microscopy, and identification of thermal contributions Knowles, Kathryn E.; Koch, Melissa D.; Shelton, Jacob L. Journal of Materials Chemistry C, Vol. 6, Issue 44 https://doi.org/10.1039/c8tc02977f	journal	January 2018
Effect of Doping and Excitation Wavelength on Charge Carrier Dynamics in Hematite by Time‐Resolved Microwave and Terahertz Photoconductivity Kay, Asaf; Fiegenbaum‐Raz, Mor; Müller, Sönke Advanced Functional Materials, Vol. 30, Issue 18 https://doi.org/10.1002/adfm.201901590	journal	May 2019
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

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