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:
-
- 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}
}
Web of Science
Works referenced in this record:
Perspective on Engineering Transition-Metal Oxides
journal, September 2013
- Goodenough, John B.
- Chemistry of Materials, Vol. 26, Issue 1
Transition metal oxide alloys as potential solar energy conversion materials
journal, January 2013
- Toroker, Maytal Caspary; Carter, Emily A.
- Journal of Materials Chemistry A, Vol. 1, Issue 7
Universal energy-level alignment of molecules on metal oxides
journal, November 2011
- Greiner, Mark T.; Helander, Michael G.; Tang, Wing-Man
- Nature Materials, Vol. 11, Issue 1
Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989
- de Groot, F. M. F.; Grioni, M.; Fuggle, J. C.
- Physical Review B, Vol. 40, Issue 8
Hole localization in from density functional theory and wave-function-based methods
journal, August 2017
- Ansari, Narjes; Ulman, Kanchan; Camellone, Matteo Farnesi
- Physical Review Materials, Vol. 1, Issue 3
Ultrafast Elemental and Oxidation-State Mapping of Hematite by 4D Electron Microscopy
journal, March 2017
- Su, Zixue; Baskin, J. Spencer; Zhou, Wuzong
- Journal of the American Chemical Society, Vol. 139, Issue 13
Optical Excitations in Hematite (α-Fe 2 O 3 ) via Embedded Cluster Models: A CASPT2 Study
journal, October 2011
- Liao, Peilin; Carter, Emily A.
- The Journal of Physical Chemistry C, Vol. 115, Issue 42
Characterization of Photo-Induced Charge Transfer and Hot Carrier Relaxation Pathways in Spinel Cobalt Oxide (Co 3 O 4 )
journal, September 2014
- Jiang, Chang-Ming; Baker, L. Robert; Lucas, J. Matthew
- The Journal of Physical Chemistry C, Vol. 118, Issue 39
Transient Absorption Spectroscopy of Anatase and Rutile: The Impact of Morphology and Phase on Photocatalytic Activity
journal, May 2015
- Wang, Xiuli; Kafizas, Andreas; Li, Xiaoe
- The Journal of Physical Chemistry C, Vol. 119, Issue 19
Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO 2
journal, September 2016
- Sachs, Michael; Pastor, Ernest; Kafizas, Andreas
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
Ultrafast Carrier Trapping of a Metal-Doped Titanium Dioxide Semiconductor Revealed by Femtosecond Transient Absorption Spectroscopy
journal, June 2014
- Sun, Jingya; Yang, Yang; Khan, Jafar I.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 13
Time-resolved single dopant charge dynamics in silicon
journal, October 2016
- Rashidi, Mohammad; Burgess, Jacob A. J.; Taucer, Marco
- Nature Communications, Vol. 7, Issue 1
Excitation-Dependent Ultrafast Carrier Dynamics of Colloidal TiO 2 Nanorods in Organic Solvent
journal, October 2014
- Triggiani, Leonardo; Brunetti, Adalberto; Aloi, Antonio
- The Journal of Physical Chemistry C, Vol. 118, Issue 43
Femtosecond Extreme Ultraviolet Photoemission Spectroscopy: Observation of Ultrafast Charge Transfer at the n-TiO 2 /p-Si(100) Interface with Controlled TiO 2 Oxygen Vacancies
journal, January 2016
- Vaida, Mihai E.; Leone, Stephen R.
- The Journal of Physical Chemistry C, Vol. 120, Issue 5
Ultrafast Transient Absorption Studies of Hematite Nanoparticles: The Effect of Particle Shape on Exciton Dynamics
journal, September 2013
- Fitzmorris, Bob C.; Patete, Jonathan M.; Smith, Jacqueline
- ChemSusChem, Vol. 6, Issue 10
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results
journal, May 1995
- Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T.
- Chemical Reviews, Vol. 95, Issue 3
Ultrafast Studies of Photoexcited Electron Dynamics in γ- and α-Fe 2 O 3 Semiconductor Nanoparticles
journal, January 1998
- Cherepy, Nerine J.; Liston, Dorion B.; Lovejoy, Jennifer A.
- The Journal of Physical Chemistry B, Vol. 102, Issue 5
Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3
journal, July 2017
- Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong
- Nature Materials, Vol. 16, Issue 8
Femtosecond M 2,3 -Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe 2 O 3
journal, October 2013
- Vura-Weis, Josh; Jiang, Chang-Ming; Liu, Chong
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M 2,3 -Edge Reflection–Absorption of Transition Metal Oxides
journal, July 2017
- Cirri, Anthony; Husek, Jakub; Biswas, Somnath
- The Journal of Physical Chemistry C, Vol. 121, Issue 29
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance
journal, January 2016
- Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.
- Energy & Environmental Science, Vol. 9, Issue 12
Observation of Ultrafast Carrier Dynamics and Phonon Relaxation of Graphene from the Deep-Ultraviolet to the Visible Region
journal, March 2014
- Oum, Kawon; Lenzer, Thomas; Scholz, Mirko
- The Journal of Physical Chemistry C, Vol. 118, Issue 12
Carrier Relaxation in Epitaxial Graphene Photoexcited Near the Dirac Point
journal, November 2011
- Winnerl, S.; Orlita, M.; Plochocka, P.
- Physical Review Letters, Vol. 107, Issue 23
Elastically driven cooperative response of a molecular material impacted by a laser pulse
journal, March 2016
- Bertoni, Roman; Lorenc, Maciej; Cailleau, Hervé
- Nature Materials, Vol. 15, Issue 6
Ultrafast Three-Dimensional Imaging of Lattice Dynamics in Individual Gold Nanocrystals
journal, May 2013
- Clark, J. N.; Beitra, L.; Xiong, G.
- Science, Vol. 341, Issue 6141
Carrier dynamics in α‐Fe2O3 (0001) thin films and single crystals probed by femtosecond transient absorption and reflectivity
journal, March 2006
- Joly, Alan G.; Williams, Joshua R.; Chambers, Scott A.
- Journal of Applied Physics, Vol. 99, Issue 5
Ultrafast Charge Carrier Recombination and Trapping in Hematite Photoanodes under Applied Bias
journal, July 2014
- Pendlebury, Stephanie R.; Wang, Xiuli; Le Formal, Florian
- Journal of the American Chemical Society, Vol. 136, Issue 28
Descriptors of Oxygen-Evolution Activity for Oxides: A Statistical Evaluation
journal, December 2015
- Hong, Wesley T.; Welsch, Roy E.; Shao-Horn, Yang
- The Journal of Physical Chemistry C, Vol. 120, Issue 1
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices
journal, March 2015
- McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M.
- Journal of the American Chemical Society, Vol. 137, Issue 13
Exciton–exciton annihilation and relaxation pathways in semiconducting carbon nanotubes
journal, January 2016
- Chmeliov, Jevgenij; Narkeliunas, Jonas; Graham, Matt W.
- Nanoscale, Vol. 8, Issue 3
Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide
journal, September 2014
- Sun, Dezheng; Rao, Yi; Reider, Georg A.
- Nano Letters, Vol. 14, Issue 10
Interfacial Charge Carrier Dynamics of Colloidal Semiconductor Nanoparticles
journal, August 2000
- Zhang, Jin Z.
- The Journal of Physical Chemistry B, Vol. 104, Issue 31
Population inversion and giant bandgap renormalization in atomically thin WS2 layers
journal, June 2015
- Chernikov, Alexey; Ruppert, Claudia; Hill, Heather M.
- Nature Photonics, Vol. 9, Issue 7
Dynamical Excitonic Effects in Doped Two-Dimensional Semiconductors
journal, August 2016
- Gao, Shiyuan; Liang, Yufeng; Spataru, Catalin D.
- Nano Letters, Vol. 16, Issue 9
Auger Recombination in Chemical Vapor Deposition-Grown Monolayer WS 2
journal, November 2016
- Cunningham, Paul D.; McCreary, Kathleen M.; Jonker, Berend T.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 24
Exciton-exciton annihilation in MoSe monolayers
journal, March 2014
- Kumar, Nardeep; Cui, Qiannan; Ceballos, Frank
- Physical Review B, Vol. 89, Issue 12
Spectroscopic Determination of Electron and Hole Effective Masses in a Nanocrystalline Semiconductor Film
journal, January 1996
- Enright, Brendan; Fitzmaurice, Donald
- The Journal of Physical Chemistry, Vol. 100, Issue 3
Excitons in nanoscale systems
journal, September 2006
- Scholes, Gregory D.; Rumbles, Garry
- Nature Materials, Vol. 5, Issue 9
Works referencing / citing this record:
Three applications of ultrafast transient absorption spectroscopy of semiconductor thin films: spectroelectrochemistry, microscopy, and identification of thermal contributions
journal, January 2018
- Knowles, Kathryn E.; Koch, Melissa D.; Shelton, Jacob L.
- Journal of Materials Chemistry C, Vol. 6, Issue 44
Effect of Doping and Excitation Wavelength on Charge Carrier Dynamics in Hematite by Time‐Resolved Microwave and Terahertz Photoconductivity
journal, May 2019
- Kay, Asaf; Fiegenbaum‐Raz, Mor; Müller, Sönke
- Advanced Functional Materials, Vol. 30, Issue 18
Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe 2 O 3 /NiO heterojunction
journal, January 2018
- Biswas, Somnath; Husek, Jakub; Londo, Stephen
- Physical Chemistry Chemical Physics, Vol. 20, Issue 38
Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy
journal, January 2018
- Biswas, Somnath; Husek, Jakub; Baker, L. Robert
- Chemical Communications, Vol. 54, Issue 34
In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells
journal, September 2019
- Pastor, Ernest; Park, Ji-Sang; Steier, Ludmilla
- Nature Communications, Vol. 10, Issue 1
On the linear geometry of lanthanide hydroxide (Ln-OH, Ln = La–Lu)
journal, January 2019
- Harb, Hassan; Thompson, Lee M.; Hratchian, Hrant P.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 39
In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells
journal, September 2019
- Pastor, Ernest; Park, Ji-Sang; Steier, Ludmilla
- Nature Communications, Vol. 10, Issue 1