Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

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

doi:10.1021/acs.nanolett.7b04818

Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

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

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

^[1]; ^[2]; Londo, Stephen ^[2]; ^[2]

The Ohio State Univ., Columbus, OH (United States); The Ohio State University, Department of chemistry and biochemistry
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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0014051

OSTI ID:: 1594151

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Ultrafast Transient Absorption Studies of Hematite Nanoparticles: The Effect of Particle Shape on Exciton Dynamics Fitzmorris, Bob C.; Patete, Jonathan M.; Smith, Jacqueline ChemSusChem, Vol. 6, Issue 10 https://doi.org/10.1002/cssc.201300571	journal	September 2013
Transient Absorption Spectroscopy of Anatase and Rutile: The Impact of Morphology and Phase on Photocatalytic Activity Wang, Xiuli; Kafizas, Andreas; Li, Xiaoe The Journal of Physical Chemistry C, Vol. 119, Issue 19 https://doi.org/10.1021/acs.jpcc.5b01858	journal	May 2015
Descriptors of Oxygen-Evolution Activity for Oxides: A Statistical Evaluation Hong, Wesley T.; Welsch, Roy E.; Shao-Horn, Yang The Journal of Physical Chemistry C, Vol. 120, Issue 1 https://doi.org/10.1021/acs.jpcc.5b10071	journal	December 2015
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 Vaida, Mihai E.; Leone, Stephen R. The Journal of Physical Chemistry C, Vol. 120, Issue 5 https://doi.org/10.1021/acs.jpcc.5b11161	journal	January 2016
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M _2,3 -Edge Reflection–Absorption of Transition Metal Oxides Cirri, Anthony; Husek, Jakub; Biswas, Somnath The Journal of Physical Chemistry C, Vol. 121, Issue 29 https://doi.org/10.1021/acs.jpcc.7b05127	journal	July 2017
Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO ₂ Sachs, Michael; Pastor, Ernest; Kafizas, Andreas The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01501	journal	September 2016
Auger Recombination in Chemical Vapor Deposition-Grown Monolayer WS ₂ Cunningham, Paul D.; McCreary, Kathleen M.; Jonker, Berend T. The Journal of Physical Chemistry Letters, Vol. 7, Issue 24 https://doi.org/10.1021/acs.jpclett.6b02413	journal	November 2016
Dynamical Excitonic Effects in Doped Two-Dimensional Semiconductors Gao, Shiyuan; Liang, Yufeng; Spataru, Catalin D. Nano Letters, Vol. 16, Issue 9 https://doi.org/10.1021/acs.nanolett.6b02118	journal	August 2016
Ultrafast Carrier Trapping of a Metal-Doped Titanium Dioxide Semiconductor Revealed by Femtosecond Transient Absorption Spectroscopy Sun, Jingya; Yang, Yang; Khan, Jafar I. ACS Applied Materials & Interfaces, Vol. 6, Issue 13 https://doi.org/10.1021/am5026159	journal	June 2014
Perspective on Engineering Transition-Metal Oxides Goodenough, John B. Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm402063u	journal	September 2013
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a013	journal	May 1995
Ultrafast Charge Carrier Recombination and Trapping in Hematite Photoanodes under Applied Bias Pendlebury, Stephanie R.; Wang, Xiuli; Le Formal, Florian Journal of the American Chemical Society, Vol. 136, Issue 28 https://doi.org/10.1021/ja504473e	journal	July 2014
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Ultrafast Elemental and Oxidation-State Mapping of Hematite by 4D Electron Microscopy Su, Zixue; Baskin, J. Spencer; Zhou, Wuzong Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b00906	journal	March 2017
Interfacial Charge Carrier Dynamics of Colloidal Semiconductor Nanoparticles Zhang, Jin Z. The Journal of Physical Chemistry B, Vol. 104, Issue 31 https://doi.org/10.1021/jp000594s	journal	August 2000
Optical Excitations in Hematite (α-Fe ₂ O ₃ ) via Embedded Cluster Models: A CASPT2 Study Liao, Peilin; Carter, Emily A. The Journal of Physical Chemistry C, Vol. 115, Issue 42 https://doi.org/10.1021/jp206991v	journal	October 2011
Observation of Ultrafast Carrier Dynamics and Phonon Relaxation of Graphene from the Deep-Ultraviolet to the Visible Region Oum, Kawon; Lenzer, Thomas; Scholz, Mirko The Journal of Physical Chemistry C, Vol. 118, Issue 12 https://doi.org/10.1021/jp4072197	journal	March 2014
Characterization of Photo-Induced Charge Transfer and Hot Carrier Relaxation Pathways in Spinel Cobalt Oxide (Co ₃ O ₄ ) Jiang, Chang-Ming; Baker, L. Robert; Lucas, J. Matthew The Journal of Physical Chemistry C, Vol. 118, Issue 39 https://doi.org/10.1021/jp5071133	journal	September 2014
Excitation-Dependent Ultrafast Carrier Dynamics of Colloidal TiO ₂ Nanorods in Organic Solvent Triggiani, Leonardo; Brunetti, Adalberto; Aloi, Antonio The Journal of Physical Chemistry C, Vol. 118, Issue 43 https://doi.org/10.1021/jp507383w	journal	October 2014
Spectroscopic Determination of Electron and Hole Effective Masses in a Nanocrystalline Semiconductor Film Enright, Brendan; Fitzmaurice, Donald The Journal of Physical Chemistry, Vol. 100, Issue 3 https://doi.org/10.1021/jp951142w	journal	January 1996
Ultrafast Studies of Photoexcited Electron Dynamics in γ- and α-Fe ₂ O ₃ Semiconductor Nanoparticles Cherepy, Nerine J.; Liston, Dorion B.; Lovejoy, Jennifer A. The Journal of Physical Chemistry B, Vol. 102, Issue 5 https://doi.org/10.1021/jp973149e	journal	January 1998
Femtosecond M _2,3 -Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe ₂ O ₃ Vura-Weis, Josh; Jiang, Chang-Ming; Liu, Chong The Journal of Physical Chemistry Letters, Vol. 4, Issue 21 https://doi.org/10.1021/jz401997d	journal	October 2013
Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide Sun, Dezheng; Rao, Yi; Reider, Georg A. Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl5021975	journal	September 2014
Time-resolved single dopant charge dynamics in silicon Rashidi, Mohammad; Burgess, Jacob A. J.; Taucer, Marco Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13258	journal	October 2016
Excitons in nanoscale systems Scholes, Gregory D.; Rumbles, Garry Nature Materials, Vol. 5, Issue 9 https://doi.org/10.1038/nmat1710	journal	September 2006
Universal energy-level alignment of molecules on metal oxides Greiner, Mark T.; Helander, Michael G.; Tang, Wing-Man Nature Materials, Vol. 11, Issue 1 https://doi.org/10.1038/nmat3159	journal	November 2011
Elastically driven cooperative response of a molecular material impacted by a laser pulse Bertoni, Roman; Lorenc, Maciej; Cailleau, Hervé Nature Materials, Vol. 15, Issue 6 https://doi.org/10.1038/nmat4606	journal	March 2016
Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3 Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong Nature Materials, Vol. 16, Issue 8 https://doi.org/10.1038/nmat4936	journal	July 2017
Population inversion and giant bandgap renormalization in atomically thin WS2 layers Chernikov, Alexey; Ruppert, Claudia; Hill, Heather M. Nature Photonics, Vol. 9, Issue 7 https://doi.org/10.1038/nphoton.2015.104	journal	June 2015
Exciton–exciton annihilation and relaxation pathways in semiconducting carbon nanotubes Chmeliov, Jevgenij; Narkeliunas, Jonas; Graham, Matt W. Nanoscale, Vol. 8, Issue 3 https://doi.org/10.1039/C5NR06853C	journal	January 2016
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D. Energy & Environmental Science, Vol. 9, Issue 12 https://doi.org/10.1039/C6EE02266A	journal	January 2016
Surface electron dynamics in hematite (α-Fe ₂ O ₃ ): correlation between ultrafast surface electron trapping and small polaron formation Husek, Jakub; Cirri, Anthony; Biswas, Somnath Chemical Science, Vol. 8, Issue 12 https://doi.org/10.1039/C7SC02826A	journal	January 2017
Transition metal oxide alloys as potential solar energy conversion materials Toroker, Maytal Caspary; Carter, Emily A. Journal of Materials Chemistry A, Vol. 1, Issue 7 https://doi.org/10.1039/c2ta00816e	journal	January 2013
Carrier dynamics in α‐Fe2O3 (0001) thin films and single crystals probed by femtosecond transient absorption and reflectivity Joly, Alan G.; Williams, Joshua R.; Chambers, Scott A. Journal of Applied Physics, Vol. 99, Issue 5 https://doi.org/10.1063/1.2177426	journal	March 2006
Electrical Properties of α - Fe 2 O 3 Morin, F. J. Physical Review, Vol. 93, Issue 6 https://doi.org/10.1103/PhysRev.93.1195	journal	March 1954
Electrical Properties of NiO Morin, F. J. Physical Review, Vol. 93, Issue 6 https://doi.org/10.1103/PhysRev.93.1199	journal	March 1954
Oxygen 1 s x-ray-absorption edges of transition-metal oxides de Groot, F. M. F.; Grioni, M.; Fuggle, J. C. Physical Review B, Vol. 40, Issue 8 https://doi.org/10.1103/PhysRevB.40.5715	journal	September 1989
Exciton-exciton annihilation in MoSe 2 monolayers Kumar, Nardeep; Cui, Qiannan; Ceballos, Frank Physical Review B, Vol. 89, Issue 12 https://doi.org/10.1103/PhysRevB.89.125427	journal	March 2014
Carrier Relaxation in Epitaxial Graphene Photoexcited Near the Dirac Point Winnerl, S.; Orlita, M.; Plochocka, P. Physical Review Letters, Vol. 107, Issue 23 https://doi.org/10.1103/PhysRevLett.107.237401	journal	November 2011
Hole localization in Fe 2 O 3 from density functional theory and wave-function-based methods Ansari, Narjes; Ulman, Kanchan; Camellone, Matteo Farnesi Physical Review Materials, Vol. 1, Issue 3 https://doi.org/10.1103/PhysRevMaterials.1.035404	journal	August 2017
Ultrafast Three-Dimensional Imaging of Lattice Dynamics in Individual Gold Nanocrystals Clark, J. N.; Beitra, L.; Xiong, G. Science, Vol. 341, Issue 6141 https://doi.org/10.1126/science.1236034	journal	May 2013

Cited By (6)

In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells Pastor, Ernest; Park, Ji-Sang; Steier, Ludmilla Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11767-9	journal	September 2019
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
Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy Biswas, Somnath; Husek, Jakub; Baker, L. Robert Chemical Communications, Vol. 54, Issue 34 https://doi.org/10.1039/c8cc01745j	journal	January 2018
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 Biswas, Somnath; Husek, Jakub; Londo, Stephen Physical Chemistry Chemical Physics, Vol. 20, Issue 38 https://doi.org/10.1039/c8cp04502j	journal	January 2018
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
On the linear geometry of lanthanide hydroxide (Ln-OH, Ln = La–Lu) Harb, Hassan; Thompson, Lee M.; Hratchian, Hrant P. Physical Chemistry Chemical Physics, Vol. 21, Issue 39 https://doi.org/10.1039/c9cp01560d	journal	January 2019

Similar Records

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy

Journal Article · Fri Apr 06 00:00:00 UTC 2018 · ChemComm · OSTI ID:1594152

Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe₂O₃/NiO heterojunction

Journal Article · Wed Sep 05 00:00:00 UTC 2018 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1594155

Microscopic Theory of Resonant Soft-X-Ray Scattering in Materials with Charge Order: The Example of Charge Stripes in High-Temperature Cuprate Superconductors

Journal Article · Tue Mar 26 00:00:00 UTC 2013 · Physical Review Letters · OSTI ID:1958848

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Covalency
X-ray absorption
exciton
metal oxides
water splitting

Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

Citation Formats

References (41)

Cited By (6)

Similar Records

Related Subjects