Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles
Abstract
The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ~1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ~100 cm-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.
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- European XFEL, Hamburg (Germany); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
- Ecole Polytechnique Federale Lausanne (EPFL) (Switzerland). Lausanne Centre for Ultrafast Science (LACUS)
- Newcastle University, Newcastle upon Tyne (United Kingdom)
- Paul Scherrer Inst. (PSI), Villigen (Switzerland); Adam Mickiewicz Univ., Poznan (Poland)
- European XFEL, Hamburg (Germany); Adam Mickiewicz Univ., Poznan (Poland); Univ. of Cantoblanco, Madrid (Spain). IMDEA Nanoscience Institute
- European XFEL, Hamburg (Germany); Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
- Technical Univ. of Denmark, Lyngby (Denmark)
- Paul Scherrer Inst. (PSI), Villigen (Switzerland)
- European XFEL, Hamburg (Germany); Japan Synchrotron Radiation Research Institute (JASRI), Hyogo (Japan)
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- European XFEL, Hamburg (Germany)
- Uppsala Univ. (Sweden)
- Tohoku Univ., Sendai (Japan)
- RIKEN SPring-8 Center, Sayo (Japan)
- Adam Mickiewicz Univ., Poznan (Poland)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); European Research Council (ERC); Swiss National Science Foundation (SNSF); Engineering and Physical Sciences Research Council (EPSRC)
- OSTI Identifier:
- 2205591
- Grant/Contract Number:
- AC02-06CH11357; EP/W008009/1; EP/X035514/1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Structural Dynamics
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 6; Journal ID: ISSN 2329-7778
- Publisher:
- American Crystallographic Association/AIP
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; disentangling; evolution of electrons; photoexcited ZnO nanoparticles; molecular dynamics; excitons; ultrafast X-rays; ultrafast fluorescence spectroscopy; nanoparticle; photoexcitations; X-ray absorption spectroscopy
Citation Formats
Milne, Christopher J., Nagornova, Natalia, Pope, Thomas, Chen, Hui-Yuan, Rossi, Thomas, Szlachetko, Jakub, Gawelda, Wojciech, Britz, Alexander, van Driel, Tim B., Sala, Leonardo, Ebner, Simon, Katayama, Tetsuo, Southworth, Stephen H., Doumy, Gilles, March, Anne Marie, Lehmann, C. Stefan, Mucke, Melanie, Iablonskyi, Denys, Kumagai, Yoshiaki, Knopp, Gregor, Motomura, Koji, Togashi, Tadashi, Owada, Shigeki, Yabashi, Makina, Nielsen, Martin M., Pajek, Marek, Ueda, Kiyoshi, Abela, Rafael, Penfold, Thomas J., and Chergui, Majed. Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles. United States: N. p., 2023.
Web. doi:10.1063/4.0000204.
Milne, Christopher J., Nagornova, Natalia, Pope, Thomas, Chen, Hui-Yuan, Rossi, Thomas, Szlachetko, Jakub, Gawelda, Wojciech, Britz, Alexander, van Driel, Tim B., Sala, Leonardo, Ebner, Simon, Katayama, Tetsuo, Southworth, Stephen H., Doumy, Gilles, March, Anne Marie, Lehmann, C. Stefan, Mucke, Melanie, Iablonskyi, Denys, Kumagai, Yoshiaki, Knopp, Gregor, Motomura, Koji, Togashi, Tadashi, Owada, Shigeki, Yabashi, Makina, Nielsen, Martin M., Pajek, Marek, Ueda, Kiyoshi, Abela, Rafael, Penfold, Thomas J., & Chergui, Majed. Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles. United States. https://doi.org/10.1063/4.0000204
Milne, Christopher J., Nagornova, Natalia, Pope, Thomas, Chen, Hui-Yuan, Rossi, Thomas, Szlachetko, Jakub, Gawelda, Wojciech, Britz, Alexander, van Driel, Tim B., Sala, Leonardo, Ebner, Simon, Katayama, Tetsuo, Southworth, Stephen H., Doumy, Gilles, March, Anne Marie, Lehmann, C. Stefan, Mucke, Melanie, Iablonskyi, Denys, Kumagai, Yoshiaki, Knopp, Gregor, Motomura, Koji, Togashi, Tadashi, Owada, Shigeki, Yabashi, Makina, Nielsen, Martin M., Pajek, Marek, Ueda, Kiyoshi, Abela, Rafael, Penfold, Thomas J., and Chergui, Majed. Fri .
"Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles". United States. https://doi.org/10.1063/4.0000204. https://www.osti.gov/servlets/purl/2205591.
@article{osti_2205591,
title = {Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles},
author = {Milne, Christopher J. and Nagornova, Natalia and Pope, Thomas and Chen, Hui-Yuan and Rossi, Thomas and Szlachetko, Jakub and Gawelda, Wojciech and Britz, Alexander and van Driel, Tim B. and Sala, Leonardo and Ebner, Simon and Katayama, Tetsuo and Southworth, Stephen H. and Doumy, Gilles and March, Anne Marie and Lehmann, C. Stefan and Mucke, Melanie and Iablonskyi, Denys and Kumagai, Yoshiaki and Knopp, Gregor and Motomura, Koji and Togashi, Tadashi and Owada, Shigeki and Yabashi, Makina and Nielsen, Martin M. and Pajek, Marek and Ueda, Kiyoshi and Abela, Rafael and Penfold, Thomas J. and Chergui, Majed},
abstractNote = {The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ~1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ~100 cm-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.},
doi = {10.1063/4.0000204},
journal = {Structural Dynamics},
number = 6,
volume = 10,
place = {United States},
year = {Fri Nov 03 00:00:00 EDT 2023},
month = {Fri Nov 03 00:00:00 EDT 2023}
}
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