Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy

Porter, Ilana J.; Cushing, Scott K.; Carneiro, Lucas M.; Lee, Angela; Ondry, Justin C.; Dahl, Jakob C.; Chang, Hung -Tzu; Alivisatos, A. Paul; Leone, Stephen R.

doi:10.1021/acs.jpclett.8b01525

Title: Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy

Journal Article · Mon Jul 09 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b01525· OSTI ID:1530368

^[1]; Cushing, Scott K. ^[1]; Carneiro, Lucas M. ^[1];

^[2];

^[1]; Dahl, Jakob C. ^[1];

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

Small polaron formation limits the mobility and lifetimes of photoexcited carriers in metal oxides. As the ligand field strength increases, the carrier mobility decreases, but the effect on the photoexcited small polaron formation is still unknown. Extreme ultraviolet transient absorption spectroscopy is employed to measure small polaron formation rates and probabilities in goethite (α-FeOOH) crystalline nanorods at pump photon energies from 2.2 to 3.1 eV. The measured polaron formation time increases with excitation photon energy from 70 ± 10 fs at 2.2 eV to 350 ± 30 fs at 2.6 eV, whereas the polaron formation probability (85 ± 10%) remains constant. By comparison to hematite (α-Fe₂O₃), an oxide analogue, the role of ligand composition and metal center density in small polaron formation time is discussed. Here, this work suggests that incorporating small changes in ligands and crystal structure could enable the control of photoexcited small polaron formation in metal oxides.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1530368

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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References (28)

Unravelling Small-Polaron Transport in Metal Oxide Photoelectrodes Rettie, Alexander J. E.; Chemelewski, William D.; Emin, David The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02143	journal	January 2016
Semiconducting materials for photoelectrochemical energy conversion Sivula, Kevin; van de Krol, Roel Nature Reviews Materials, Vol. 1, Issue 2 https://doi.org/10.1038/natrevmats.2015.10	journal	January 2016
Ab initio modeling of Fe( ii ) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces Alexandrov, Vitaly; Rosso, Kevin M. Physical Chemistry Chemical Physics, Vol. 17, Issue 22 https://doi.org/10.1039/C5CP00921A	journal	January 2015
An ab initio model of electron transport in hematite (α-Fe₂O₃) basal planes Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel The Journal of Chemical Physics, Vol. 118, Issue 14, p. 6455-6466 https://doi.org/10.1063/1.1558534	journal	April 2003
Charge transport in metal oxides: A theoretical study of hematite α-Fe2O3 Iordanova, N.; Dupuis, M.; Rosso, K. M. The Journal of Chemical Physics, Vol. 122, Issue 14 https://doi.org/10.1063/1.1869492	journal	April 2005
Electron transport in pure and substituted iron oxyhydroxides by small-polaron migration Alexandrov, Vitaly; Rosso, Kevin M. The Journal of Chemical Physics, Vol. 140, Issue 23 https://doi.org/10.1063/1.4882065	journal	June 2014
Femtosecond Studies of Electron Dynamics at Interfaces Ge, Nien-Hui; Wong, Chung M.; Harris, Charles B. Accounts of Chemical Research, Vol. 33, Issue 2 https://doi.org/10.1021/ar980138a	journal	February 2000
Exploring the impact of semicore level electronic relaxation on polaron dynamics: An adiabatic ab initio study of ${FePO}_{4}$ Wang, Zi; Bevan, Kirk H. Physical Review B, Vol. 93, Issue 2 https://doi.org/10.1103/PhysRevB.93.024303	journal	January 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
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
Tunable Fröhlich polarons in organic single-crystal transistors Hulea, I. N.; Fratini, S.; Xie, H. Nature Materials, Vol. 5, Issue 12 https://doi.org/10.1038/nmat1774	journal	November 2006
Investigating nanoscale mineral compositions: Iron L ₃ -edge spectroscopic evaluation of iron oxide and oxy-hydroxide coordination von der Heyden, Bjorn P.; Roychoudhury, Alakendra N.; Tyliszczak, Tolek American Mineralogist, Vol. 102, Issue 3 https://doi.org/10.2138/am-2017-5805	journal	March 2017
Raman spectroscopy of Fe ₂ O ₃ to 62 GPa Shim, Sang-Heon; Duffy, Thomas S. American Mineralogist, Vol. 87, Issue 2-3 https://doi.org/10.2138/am-2002-2-314	journal	February 2002
Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin Films Produced by Vapor Deposition Jubb, Aaron M.; Allen, Heather C. ACS Applied Materials & Interfaces, Vol. 2, Issue 10 https://doi.org/10.1021/am1004943	journal	September 2010
Infrared spectroscopic properties of goethite: anharmonic broadening, long-range electrostatic effects and Al substitution Blanchard, Marc; Balan, Etienne; Giura, Paola Physics and Chemistry of Minerals, Vol. 41, Issue 4 https://doi.org/10.1007/s00269-013-0648-7	journal	December 2013
Theoretical study of electronic, magnetic, and structural properties of α- ${Fe}_{2}$ $O_{3}$ (hematite) Catti, M.; Valerio, G.; Dovesi, R. Physical Review B, Vol. 51, Issue 12 https://doi.org/10.1103/PhysRevB.51.7441	journal	March 1995
In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction Gualtieri, Alessandro F.; Venturelli, Paolo American Mineralogist, Vol. 84, Issue 5-6 https://doi.org/10.2138/am-1999-5-624	journal	June 1999
Variation of hydrogen bonded O…O distances in goethite at high pressure Nagai, Takaya; Kagi, Hiroyuki; Yamanaka, Takamitsu American Mineralogist, Vol. 88, Issue 10 https://doi.org/10.2138/am-2003-1005	journal	October 2003
Goethite, α-FeO(OH), from single-crystal data Yang, Hexiong; Lu, Ren; Downs, Robert T. Acta Crystallographica Section E Structure Reports Online, Vol. 62, Issue 12 https://doi.org/10.1107/S1600536806047258	journal	November 2006
Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes Sivula, Kevin; Le Formal, Florian; Grätzel, Michael ChemSusChem, Vol. 4, Issue 4 https://doi.org/10.1002/cssc.201000416	journal	March 2011
Visible Light Induced Photocatalytic Degradation of Rhodamine B on One-Dimensional Iron Oxide Particles Zhou, Xuemei; Yang, Hongchao; Wang, Chenxuan The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp103816e	journal	July 2010
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
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges Stavitski, Eli; de Groot, Frank M. F. Micron, Vol. 41, Issue 7 https://doi.org/10.1016/j.micron.2010.06.005	journal	October 2010
Diffuse Reflectance Spectra of Al Substituted Goethite: A Ligand Field Approach Scheinost, Andreas C. Clays and Clay Minerals, Vol. 47, Issue 2 https://doi.org/10.1346/CCMN.1999.0470205	journal	January 1999
The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy Miedema, Piter S.; de Groot, Frank M. F. Journal of Electron Spectroscopy and Related Phenomena, Vol. 187 https://doi.org/10.1016/j.elspec.2013.03.005	journal	April 2013
Origin of Stretched Exponential Relaxation for Hopping-Transport Models Sturman, B.; Podivilov, E.; Gorkunov, M. Physical Review Letters, Vol. 91, Issue 17 https://doi.org/10.1103/PhysRevLett.91.176602	journal	October 2003
Kinetic Monte Carlo model of charge transport in hematite (α-Fe2O3) Kerisit, Sebastien; Rosso, Kevin M. The Journal of Chemical Physics, Vol. 127, Issue 12 https://doi.org/10.1063/1.2768522	journal	September 2007
Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations Smart, Tyler J.; Ping, Yuan Journal of Physics: Condensed Matter, Vol. 29, Issue 39 https://doi.org/10.1088/1361-648X/aa7e3d	journal	August 2017

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Synthesis and Characterization of Ti-Fe Oxide Nanomaterials for Lead Removal Abebe, Buzuayehu; Ananda Murthy, H. C. Journal of Nanomaterials, Vol. 2018 https://doi.org/10.1155/2018/9651039	journal	November 2018
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
Transient absorption spectroscopy using high harmonic generation: a review of ultrafast X-ray dynamics in molecules and solids Geneaux, Romain; Marroux, Hugo J. B.; Guggenmos, Alexander Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145 https://doi.org/10.1098/rsta.2017.0463	journal	April 2019
Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy Biswas, Somnath; Wallentine, Spencer; Bandaranayake, Savini The Journal of Chemical Physics, Vol. 151, Issue 10 https://doi.org/10.1063/1.5115163	journal	September 2019

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