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

Abstract

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.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
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
OSTI Identifier:
1530368
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 14; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Porter, Ilana J., Cushing, Scott K., Carneiro, Lucas M., Lee, Angela, Ondry, Justin C., Dahl, Jakob C., Chang, Hung -Tzu, Alivisatos, A. Paul, and Leone, Stephen R. Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b01525.
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. Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy. United States. https://doi.org/10.1021/acs.jpclett.8b01525
Porter, Ilana J., Cushing, Scott K., Carneiro, Lucas M., Lee, Angela, Ondry, Justin C., Dahl, Jakob C., Chang, Hung -Tzu, Alivisatos, A. Paul, and Leone, Stephen R. Mon . "Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy". United States. https://doi.org/10.1021/acs.jpclett.8b01525. https://www.osti.gov/servlets/purl/1530368.
@article{osti_1530368,
title = {Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy},
author = {Porter, Ilana J. and Cushing, Scott K. and Carneiro, Lucas M. and Lee, Angela and Ondry, Justin C. and Dahl, Jakob C. and Chang, Hung -Tzu and Alivisatos, A. Paul and Leone, Stephen R.},
abstractNote = {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.},
doi = {10.1021/acs.jpclett.8b01525},
journal = {Journal of Physical Chemistry Letters},
number = 14,
volume = 9,
place = {United States},
year = {Mon Jul 09 00:00:00 EDT 2018},
month = {Mon Jul 09 00:00:00 EDT 2018}
}

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Cited by: 21 works
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Figures / Tables:

Figure 1 Figure 1: (a) The ground state XUV absorption spectrum of goethite nanorods (black) and the spectrum simulated using the CTM4XAS software (red). Input parameters for the charge transfer multiplet calculation are summarized in the text. (b) A TEM image of the goethite nanorod distribution, confirming the size and the rod-likemore » shape of the particles. (c) An HRTEM image of a single nanorod reveals that the entire rod is a single crystal. (d) Powder XRD of the sample (black) compared to the stick spectrum of goethite from Gualtieri et al. (red), which confirms that the sample is in the goethite phase.« less

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Works referenced in this record:

Unravelling Small-Polaron Transport in Metal Oxide Photoelectrodes
journal, January 2016

  • Rettie, Alexander J. E.; Chemelewski, William D.; Emin, David
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
  • DOI: 10.1021/acs.jpclett.5b02143

Semiconducting materials for photoelectrochemical energy conversion
journal, January 2016


Ab initio modeling of Fe( ii ) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces
journal, January 2015

  • Alexandrov, Vitaly; Rosso, Kevin M.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 22
  • DOI: 10.1039/C5CP00921A

An ab initio model of electron transport in hematite (α-Fe2O3) basal planes
journal, April 2003

  • Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel
  • The Journal of Chemical Physics, Vol. 118, Issue 14, p. 6455-6466
  • DOI: 10.1063/1.1558534

Charge transport in metal oxides: A theoretical study of hematite α-Fe2O3
journal, April 2005

  • Iordanova, N.; Dupuis, M.; Rosso, K. M.
  • The Journal of Chemical Physics, Vol. 122, Issue 14
  • DOI: 10.1063/1.1869492

Electron transport in pure and substituted iron oxyhydroxides by small-polaron migration
journal, June 2014

  • Alexandrov, Vitaly; Rosso, Kevin M.
  • The Journal of Chemical Physics, Vol. 140, Issue 23
  • DOI: 10.1063/1.4882065

Femtosecond Studies of Electron Dynamics at Interfaces
journal, February 2000

  • Ge, Nien-Hui; Wong, Chung M.; Harris, Charles B.
  • Accounts of Chemical Research, Vol. 33, Issue 2
  • DOI: 10.1021/ar980138a

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
  • DOI: 10.1038/nmat4936

Surface electron dynamics in hematite (α-Fe 2 O 3 ): correlation between ultrafast surface electron trapping and small polaron formation
journal, January 2017

  • Husek, Jakub; Cirri, Anthony; Biswas, Somnath
  • Chemical Science, Vol. 8, Issue 12
  • DOI: 10.1039/C7SC02826A

Tunable Fröhlich polarons in organic single-crystal transistors
journal, November 2006

  • Hulea, I. N.; Fratini, S.; Xie, H.
  • Nature Materials, Vol. 5, Issue 12
  • DOI: 10.1038/nmat1774

Investigating nanoscale mineral compositions: Iron L 3 -edge spectroscopic evaluation of iron oxide and oxy-hydroxide coordination
journal, March 2017

  • von der Heyden, Bjorn P.; Roychoudhury, Alakendra N.; Tyliszczak, Tolek
  • American Mineralogist, Vol. 102, Issue 3
  • DOI: 10.2138/am-2017-5805

Raman spectroscopy of Fe 2 O 3 to 62 GPa
journal, February 2002


Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin Films Produced by Vapor Deposition
journal, September 2010

  • Jubb, Aaron M.; Allen, Heather C.
  • ACS Applied Materials & Interfaces, Vol. 2, Issue 10
  • DOI: 10.1021/am1004943

Infrared spectroscopic properties of goethite: anharmonic broadening, long-range electrostatic effects and Al substitution
journal, December 2013

  • Blanchard, Marc; Balan, Etienne; Giura, Paola
  • Physics and Chemistry of Minerals, Vol. 41, Issue 4
  • DOI: 10.1007/s00269-013-0648-7

Theoretical study of electronic, magnetic, and structural properties of α- Fe 2 O 3 (hematite)
journal, March 1995


In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction
journal, June 1999

  • Gualtieri, Alessandro F.; Venturelli, Paolo
  • American Mineralogist, Vol. 84, Issue 5-6
  • DOI: 10.2138/am-1999-5-624

Variation of hydrogen bonded O…O distances in goethite at high pressure
journal, October 2003

  • Nagai, Takaya; Kagi, Hiroyuki; Yamanaka, Takamitsu
  • American Mineralogist, Vol. 88, Issue 10
  • DOI: 10.2138/am-2003-1005

Goethite, α-FeO(OH), from single-crystal data
journal, November 2006

  • Yang, Hexiong; Lu, Ren; Downs, Robert T.
  • Acta Crystallographica Section E Structure Reports Online, Vol. 62, Issue 12
  • DOI: 10.1107/S1600536806047258

Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes
journal, March 2011

  • Sivula, Kevin; Le Formal, Florian; Grätzel, Michael
  • ChemSusChem, Vol. 4, Issue 4
  • DOI: 10.1002/cssc.201000416

Visible Light Induced Photocatalytic Degradation of Rhodamine B on One-Dimensional Iron Oxide Particles
journal, July 2010

  • Zhou, Xuemei; Yang, Hongchao; Wang, Chenxuan
  • The Journal of Physical Chemistry C, Vol. 114, Issue 40
  • DOI: 10.1021/jp103816e

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
  • DOI: 10.1021/jz401997d

The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges
journal, October 2010


Diffuse Reflectance Spectra of Al Substituted Goethite: A Ligand Field Approach
journal, January 1999


The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy
journal, April 2013

  • Miedema, Piter S.; de Groot, Frank M. F.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 187
  • DOI: 10.1016/j.elspec.2013.03.005

Origin of Stretched Exponential Relaxation for Hopping-Transport Models
journal, October 2003


Kinetic Monte Carlo model of charge transport in hematite (α-Fe2O3)
journal, September 2007

  • Kerisit, Sebastien; Rosso, Kevin M.
  • The Journal of Chemical Physics, Vol. 127, Issue 12
  • DOI: 10.1063/1.2768522

Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations
journal, August 2017


Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes
journal, March 2011

  • Sivula, Kevin; Le Formal, Florian; Grätzel, Michael
  • ChemSusChem, Vol. 4, Issue 4
  • DOI: 10.1002/cssc.201000416

Infrared spectroscopic properties of goethite: anharmonic broadening, long-range electrostatic effects and Al substitution
journal, December 2013

  • Blanchard, Marc; Balan, Etienne; Giura, Paola
  • Physics and Chemistry of Minerals, Vol. 41, Issue 4
  • DOI: 10.1007/s00269-013-0648-7

In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction
journal, June 1999

  • Gualtieri, Alessandro F.; Venturelli, Paolo
  • American Mineralogist, Vol. 84, Issue 5-6
  • DOI: 10.2138/am-1999-5-624

Works referencing / citing this record:

Synthesis and Characterization of Ti-Fe Oxide Nanomaterials for Lead Removal
journal, November 2018

  • Abebe, Buzuayehu; Ananda Murthy, H. C.
  • Journal of Nanomaterials, Vol. 2018
  • DOI: 10.1155/2018/9651039

In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells
journal, September 2019


Transient absorption spectroscopy using high harmonic generation: a review of ultrafast X-ray dynamics in molecules and solids
journal, April 2019

  • Geneaux, Romain; Marroux, Hugo J. B.; Guggenmos, Alexander
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
  • DOI: 10.1098/rsta.2017.0463

Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy
journal, September 2019

  • Biswas, Somnath; Wallentine, Spencer; Bandaranayake, Savini
  • The Journal of Chemical Physics, Vol. 151, Issue 10
  • DOI: 10.1063/1.5115163

In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells
journal, September 2019


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