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.
- Authors:
-
more »
- 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}
}
Works referenced in this record:
Hole-Phonon Relaxation and Photocatalytic Properties of Titanium Dioxide and Zinc Oxide: First-Principles Approach
journal, January 2014
- Zhukov, V. P.; Tyuterev, V. G.; Chulkov, E. V.
- International Journal of Photoenergy, Vol. 2014
Direct and real-time observation of hole transport dynamics in anatase TiO2 using X-ray free-electron laser
journal, May 2022
- Park, Sang Han; Katoch, Abhishek; Chae, Keun Hwa
- Nature Communications, Vol. 13, Issue 1
Revealing the competing contributions of charge carriers, excitons, and defects to the non-equilibrium optical properties of ZnO
journal, May 2019
- Foglia, Laura; Vempati, Sesha; Tanda Bonkano, Boubacar
- Structural Dynamics, Vol. 6, Issue 3
Springer Handbook of Electronic and Photonic Materials
book, January 2017
- Kasap, Safa; Capper, Peter
- Springer Handbooks
Charge Carrier Screening in Photoexcited Epitaxial Semiconductor Nanorods Revealed by Transient X-ray Absorption Linear Dichroism
journal, November 2021
- Rossi, Thomas C.; Dykstra, Conner P.; Haddock, Tyler N.
- Nano Letters, Vol. 21, Issue 22
ZnO Luminescence and scintillation studied via photoexcitation, X-ray excitation and gamma-induced positron spectroscopy
journal, August 2016
- Ji, J.; Colosimo, A. M.; Anwand, W.
- Scientific Reports, Vol. 6, Issue 1
Phonon-Driven Selective Modulation of Exciton Oscillator Strengths in Anatase TiO 2 Nanoparticles
journal, July 2018
- Baldini, Edoardo; Palmieri, Tania; Dominguez, Adriel
- Nano Letters, Vol. 18, Issue 8
Spectral and dynamical characterization of multiexcitons in colloidal CdSe semiconductor quantum dots
journal, May 2005
- Bonati, C.; Mohamed, M. B.; Tonti, D.
- Physical Review B, Vol. 71, Issue 20
A study of electron transfer in Ru(dcbpy) 2 (NCS) 2 sensitized nanocrystalline TiO 2 and SnO 2 films induced by red-wing excitation
journal, January 2008
- Myllyperkiö, Pasi; Benkő, Gábor; Korppi-Tommola, Jouko
- Phys. Chem. Chem. Phys., Vol. 10, Issue 7
Ultrafast dynamics in ZnO/ZnMgO multiple quantum wells
journal, July 2007
- Wen, X. M.; Davis, J. A.; McDonald, D.
- Nanotechnology, Vol. 18, Issue 31
Femtosecond study of the intensity dependence of electron-hole dynamics in TiO2 nanoclusters
journal, January 1995
- Philip Colombo, D.; Roussel, Kirsten A.; Saeh, Jamal
- Chemical Physics Letters, Vol. 232, Issue 3
Ultrafast fluorescence studies of dye sensitized solar cells
journal, January 2012
- Bräm, Olivier; Cannizzo, Andrea; Chergui, Majed
- Physical Chemistry Chemical Physics, Vol. 14, Issue 22
Influence of the Electron-Cation Interaction on Electron Mobility in Dye-Sensitized ZnO and Nanocrystals: A Study Using Ultrafast Terahertz Spectroscopy
journal, May 2010
- Němec, H.; Rochford, J.; Taratula, O.
- Physical Review Letters, Vol. 104, Issue 19
Ultrafast relaxation dynamics of charge carriers relaxation in ZnO nanocrystalline thin films
journal, March 2004
- Bauer, Christophe; Boschloo, Gerrit; Mukhtar, Emad
- Chemical Physics Letters, Vol. 387, Issue 1-3
Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems
journal, November 2017
- Teuscher, Joël; Brauer, Jan C.; Stepanov, Andrey
- Structural Dynamics, Vol. 4, Issue 6
Analysis of the Urbach tails in absorption spectra of undoped ZnO thin films
journal, April 2013
- Rai, R. C.
- Journal of Applied Physics, Vol. 113, Issue 15
Exciton control in a room temperature bulk semiconductor with coherent strain pulses
journal, November 2019
- Baldini, Edoardo; Dominguez, Adriel; Palmieri, Tania
- Science Advances, Vol. 5, Issue 11
Interfacial Electron Injection Probed by a Substrate-Specific Excitonic Signature
journal, August 2017
- Baldini, Edoardo; Palmieri, Tania; Rossi, Thomas
- Journal of the American Chemical Society, Vol. 139, Issue 33
Ultraviolet lasing behavior in ZnO optical microcavities
journal, December 2017
- Dong, Hongxing; Zhou, Beier; Li, Jingzhou
- Journal of Materiomics, Vol. 3, Issue 4
Recent developments of zinc oxide based photocatalyst in water treatment technology: A review
journal, January 2016
- Lee, Kian Mun; Lai, Chin Wei; Ngai, Koh Sing
- Water Research, Vol. 88
Femtosecond fluorescence upconversion setup with broadband detection in the ultraviolet
journal, December 2007
- Cannizzo, A.; Bräm, O.; Zgrablic, G.
- Optics Letters, Vol. 32, Issue 24
Ultrafast Exciton Formation at the Surface
journal, July 2014
- Deinert, J. -C.; Wegkamp, D.; Meyer, M.
- Physical Review Letters, Vol. 113, Issue 5
Femtosecond study of the size‐dependent charge carrier dynamics in ZnO nanocluster solutions
journal, October 1995
- Cavaleri, Joseph J.; Skinner, David E.; Colombo, D. Philip
- The Journal of Chemical Physics, Vol. 103, Issue 13
Mechanisms behind green photoluminescence in ZnO phosphor powders
journal, May 1996
- Vanheusden, K.; Warren, W. L.; Seager, C. H.
- Journal of Applied Physics, Vol. 79, Issue 10
Electron transport in probed by THz time-domain spectroscopy
journal, February 2004
- Hendry, E.; Wang, F.; Shan, J.
- Physical Review B, Vol. 69, Issue 8
Ultrafast carrier dynamics in ZnO nanorods
journal, July 2005
- Sun, Chi-Kuang; Sun, Shih-Ze; Lin, Kung-Hsuan
- Applied Physics Letters, Vol. 87, Issue 2
Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy
journal, February 2018
- Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.
- Nature Communications, Vol. 9, Issue 1
Native point defects in ZnO
journal, October 2007
- Janotti, Anderson; Van de Walle, Chris G.
- Physical Review B, Vol. 76, Issue 16
Two types of excited electron dynamics in zinc oxide
journal, September 2010
- Zhukov, V. P.; Echenique, P. M.; Chulkov, E. V.
- Physical Review B, Vol. 82, Issue 9
Direct observation of the electronic states of photoexcited hematite with ultrafast 2p3d X-ray absorption spectroscopy and resonant inelastic X-ray scattering
journal, January 2020
- Ismail, Ahmed S. M.; Uemura, Yohei; Park, Sang Han
- Physical Chemistry Chemical Physics, Vol. 22, Issue 5
Picosecond and femtosecond X-ray absorption spectroscopy of molecular systems
journal, February 2010
- Chergui, Majed
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 66, Issue 2
Oxygen vacancies in ZnO
journal, September 2005
- Janotti, Anderson; Van de Walle, Chris G.
- Applied Physics Letters, Vol. 87, Issue 12
Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes
journal, March 2009
- Gawelda, W.; Pham, V. -T.; van der Veen, R. M.
- The Journal of Chemical Physics, Vol. 130, Issue 12
Mapping of the Photoinduced Electron Traps in TiO 2 by Picosecond X-ray Absorption Spectroscopy
journal, May 2014
- Rittmann-Frank, M. Hannelore; Milne, Chris J.; Rittmann, Jochen
- Angewandte Chemie International Edition, Vol. 53, Issue 23
Femtosecond visible-to-IR spectroscopy of TiO 2 nanocrystalline films: dynamics of UV-generated charge carrier relaxation at different excitation wavelengths
conference, September 2007
- Furube, Akihiro; Tamaki, Yoshiaki; Murai, Miki
- SPIE Proceedings
Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy
journal, July 2017
- Santomauro, Fabio G.; Grilj, Jakob; Mewes, Lars
- Structural Dynamics, Vol. 4, Issue 4
Bound exciton and donor–acceptor pair recombinations in ZnO
journal, February 2004
- Meyer, B. K.; Alves, H.; Hofmann, D. M.
- physica status solidi (b), Vol. 241, Issue 2
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results
journal, May 1995
- Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T.
- Chemical Reviews, Vol. 95, Issue 3
Valence-band ordering in ZnO
journal, July 1999
- Reynolds, D. C.; Look, D. C.; Jogai, B.
- Physical Review B, Vol. 60, Issue 4
Fundamentals of zinc oxide as a semiconductor
journal, October 2009
- Janotti, Anderson; Van de Walle, Chris G.
- Reports on Progress in Physics, Vol. 72, Issue 12
Correlation between photoluminescence and oxygen vacancies in ZnO phosphors
journal, January 1996
- Vanheusden, K.; Seager, C. H.; Warren, W. L.
- Applied Physics Letters, Vol. 68, Issue 3
Characterizing the Structure and Defect Concentration of ZnO Nanoparticles in a Colloidal Solution
journal, August 2014
- Rossi, T.; Penfold, T. J.; Rittmann-Frank, M. H.
- The Journal of Physical Chemistry C, Vol. 118, Issue 33
Strongly bound excitons in anatase TiO2 single crystals and nanoparticles
journal, April 2017
- Baldini, E.; Chiodo, L.; Dominguez, A.
- Nature Communications, Vol. 8, Issue 1
Clocking the Ultrafast Electron Cooling in Anatase Titanium Dioxide Nanoparticles
journal, January 2018
- Baldini, Edoardo; Palmieri, Tania; Pomarico, Enrico
- ACS Photonics, Vol. 5, Issue 4
Transient birefringence and dichroism in ZnO studied with fs-time-resolved spectroscopic ellipsometry
journal, March 2021
- Herrfurth, O.; Richter, S.; Rebarz, M.
- Physical Review Research, Vol. 3, Issue 1
Optical Absorption in Degenerately Doped Semiconductors: Mott Transition or Mahan Excitons?
journal, November 2011
- Schleife, André; Rödl, Claudia; Fuchs, Frank
- Physical Review Letters, Vol. 107, Issue 23
Valence-band ordering and magneto-optic exciton fine structure in ZnO
journal, January 2002
- Lambrecht, Walter R. L.; Rodina, Anna V.; Limpijumnong, Sukit
- Physical Review B, Vol. 65, Issue 7
TiO2 photocatalysis: Design and applications
journal, September 2012
- Nakata, Kazuya; Fujishima, Akira
- Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 13, Issue 3
Electronic and optical properties of anatase
journal, March 2000
- Asahi, R.; Taga, Y.; Mannstadt, W.
- Physical Review B, Vol. 61, Issue 11
Molecular Photovoltaics
journal, May 2000
- Hagfeldt, Anders; Grätzel, Michael
- Accounts of Chemical Research, Vol. 33, Issue 5
Time-resolved Element-selective Probing of Charge Carriers in Solar Materials
journal, November 2017
- Budarz, James; Santomauro, Fabio G.; Rittmann-Frank, M. Hannelore
- CHIMIA International Journal for Chemistry, Vol. 71, Issue 11
Real-Time Observation of Photoinduced Adiabatic Electron Transfer in Strongly Coupled Dye/Semiconductor Colloidal Systems with a 6 fs Time Constant
journal, June 2002
- Huber, Robert; Moser, Jacques-E.; Grätzel, Michael
- The Journal of Physical Chemistry B, Vol. 106, Issue 25
Photoinduced Ultrafast Dye-to-Semiconductor Electron Injection from Nonthermalized and Thermalized Donor States
journal, January 2002
- Benkö, Gábor; Kallioinen, Jani; Korppi-Tommola, Jouko E. I.
- Journal of the American Chemical Society, Vol. 124, Issue 3
A comprehensive review of ZnO materials and devices
journal, August 2005
- Özgür, Ü.; Alivov, Ya. I.; Liu, C.
- Journal of Applied Physics, Vol. 98, Issue 4
Charge transport in nanostructured materials for solar energy conversion studied by time-resolved terahertz spectroscopy
journal, September 2010
- Němec, Hynek; Kužel, Petr; Sundström, Villy
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 215, Issue 2-3
Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL
journal, June 2017
- Obara, Yuki; Ito, Hironori; Ito, Terumasa
- Structural Dynamics, Vol. 4, Issue 4
Ultrafast dynamics of hot charge carriers in an oxide semiconductor probed by femtosecond spectroscopic ellipsometry
journal, August 2020
- Richter, Steffen; Herrfurth, Oliver; Espinoza, Shirly
- New Journal of Physics, Vol. 22, Issue 8
Tracking the Local Structure Change during the Photoabsorption Processes of Photocatalysts by the Ultrafast Pump-Probe XAFS Method
journal, November 2020
- Uemura, Yohei; Yokoyama, Toshihiko; Katayama, Tetsuo
- Applied Sciences, Vol. 10, Issue 21
Ultrafast Carrier Dynamics in Single ZnO Nanowire and Nanoribbon Lasers
journal, February 2004
- Johnson, Justin C.; Knutsen, Kelly P.; Yan, Haoquan
- Nano Letters, Vol. 4, Issue 2
Dynamics of photoexcited carriers in ZnO epitaxial thin films
journal, July 1999
- Yamamoto, Aishi; Kido, Takeo; Goto, Takenari
- Applied Physics Letters, Vol. 75, Issue 4
Far-infrared response of free charge carriers localized in semiconductor nanoparticles
journal, March 2009
- Němec, Hynek; Kužel, Petr; Sundström, Villy
- Physical Review B, Vol. 79, Issue 11
Temperature dependence of Raman scattering in
journal, April 2007
- Cuscó, Ramon; Alarcón-Lladó, Esther; Ibáñez, Jordi
- Physical Review B, Vol. 75, Issue 16