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Title: Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu 2O photoelectrodes

Abstract

Cuprous oxide (Cu 2O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu 2O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu 2O surface as well as the interface between Cu 2O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu 2O and provide guidance for future material development.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin (Germany)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); German Research Foundation (DFG)
OSTI Identifier:
1559216
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Borgwardt, Mario, Omelchenko, Stefan T., Favaro, Marco, Plate, Paul, Höhn, Christian, Abou-Ras, Daniel, Schwarzburg, Klaus, van de Krol, Roel, Atwater, Harry A., Lewis, Nathan S., Eichberger, Rainer, and Friedrich, Dennis. Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu2O photoelectrodes. United States: N. p., 2019. Web. doi:10.1038/s41467-019-10143-x.
Borgwardt, Mario, Omelchenko, Stefan T., Favaro, Marco, Plate, Paul, Höhn, Christian, Abou-Ras, Daniel, Schwarzburg, Klaus, van de Krol, Roel, Atwater, Harry A., Lewis, Nathan S., Eichberger, Rainer, & Friedrich, Dennis. Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu2O photoelectrodes. United States. doi:10.1038/s41467-019-10143-x.
Borgwardt, Mario, Omelchenko, Stefan T., Favaro, Marco, Plate, Paul, Höhn, Christian, Abou-Ras, Daniel, Schwarzburg, Klaus, van de Krol, Roel, Atwater, Harry A., Lewis, Nathan S., Eichberger, Rainer, and Friedrich, Dennis. Wed . "Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu2O photoelectrodes". United States. doi:10.1038/s41467-019-10143-x. https://www.osti.gov/servlets/purl/1559216.
@article{osti_1559216,
title = {Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu2O photoelectrodes},
author = {Borgwardt, Mario and Omelchenko, Stefan T. and Favaro, Marco and Plate, Paul and Höhn, Christian and Abou-Ras, Daniel and Schwarzburg, Klaus and van de Krol, Roel and Atwater, Harry A. and Lewis, Nathan S. and Eichberger, Rainer and Friedrich, Dennis},
abstractNote = {Cuprous oxide (Cu2O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu2O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu2O surface as well as the interface between Cu2O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu2O and provide guidance for future material development.},
doi = {10.1038/s41467-019-10143-x},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {5}
}

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