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Title: Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorptionmore » spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [1] ;  [4] ;  [3] ;  [1] ;  [1] ;  [2] ;  [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences, and Biosciences Division; Energy Frontier Research Center, Argonne-Northwestern Solar Energy Research (ANSER)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 14 SOLAR ENERGY
OSTI Identifier:
1356817

Hayes, Dugan, Hadt, Ryan G., Emery, Jonathan D., Cordones, Amy A., Martinson, Alex B. F., Shelby, Megan L., Fransted, Kelly A., Dahlberg, Peter D., Hong, Jiyun, Zhang, Xiaoyi, Kong, Qingyu, Schoenlein, Robert W., and Chen, Lin X.. Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance. United States: N. p., Web. doi:10.1039/c6ee02266a.
Hayes, Dugan, Hadt, Ryan G., Emery, Jonathan D., Cordones, Amy A., Martinson, Alex B. F., Shelby, Megan L., Fransted, Kelly A., Dahlberg, Peter D., Hong, Jiyun, Zhang, Xiaoyi, Kong, Qingyu, Schoenlein, Robert W., & Chen, Lin X.. Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance. United States. doi:10.1039/c6ee02266a.
Hayes, Dugan, Hadt, Ryan G., Emery, Jonathan D., Cordones, Amy A., Martinson, Alex B. F., Shelby, Megan L., Fransted, Kelly A., Dahlberg, Peter D., Hong, Jiyun, Zhang, Xiaoyi, Kong, Qingyu, Schoenlein, Robert W., and Chen, Lin X.. 2016. "Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance". United States. doi:10.1039/c6ee02266a. https://www.osti.gov/servlets/purl/1356817.
@article{osti_1356817,
title = {Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance},
author = {Hayes, Dugan and Hadt, Ryan G. and Emery, Jonathan D. and Cordones, Amy A. and Martinson, Alex B. F. and Shelby, Megan L. and Fransted, Kelly A. and Dahlberg, Peter D. and Hong, Jiyun and Zhang, Xiaoyi and Kong, Qingyu and Schoenlein, Robert W. and Chen, Lin X.},
abstractNote = {Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.},
doi = {10.1039/c6ee02266a},
journal = {Energy & Environmental Science},
number = 12,
volume = 9,
place = {United States},
year = {2016},
month = {11}
}

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