Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface

Katrin R. Siefermann, Chaitanya D. Pemmaraju, Stefan Neppl, Andrey Shavorskiy, Amy A. Cordones, Josh Vura-Weis, Daniel S. Slaughter, Felix P. Sturm, Fabian Weise, Hendrik Bluhm, Matthew L. Strader, Hana Cho, Ming Fu Lin, Camila Bacellar, Champak Khurmi, Jinghua Guo, Giacomo Coslovich, Joseph S. Robinson, Robert A. Kaindl, Robert W. SchoenleinAli Belkacem, Daniel M. Neumark, Stephen R. Leone, Dennis Nordlund, Hirohito Ogasawara, Oleg Krupin, Joshua J. Turner, William F. Schlotter, Michael R. Holmes, Marc Messerschmidt, Michael P. Minitti, Sheraz Gul, Jin Z. Zhang, Nils Huse, David Prendergast, Oliver Gessner

Research output: Contribution to journalArticle

55 Scopus citations

Abstract

Understanding interfacial charge-transfer processes on the atomic level is crucial to support the rational design of energy-challenge relevant systems such as solar cells, batteries, and photocatalysts. A femtosecond time-resolved core-level photoelectron spectroscopy study is performed that probes the electronic structure of the interface between ruthenium-based N3 dye molecules and ZnO nanocrystals within the first picosecond after photoexcitation and from the unique perspective of the Ru reporter atom at the center of the dye. A transient chemical shift of the Ru 3d inner-shell photolines by (2.3 ± 0.2) eV to higher binding energies is observed 500 fs after photoexcitation of the dye. The experimental results are interpreted with the aid of ab initio calculations using constrained density functional theory. Strong indications for the formation of an interfacial charge-transfer state are presented, providing direct insight into a transient electronic configuration that may limit the efficiency of photoinduced free charge-carrier generation.

Original languageEnglish (US)
Pages (from-to)2753-2759
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume5
Issue number15
DOIs
StatePublished - Aug 7 2014

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Keywords

  • X-ray free electron laser
  • constrained density functional theory
  • dye-sensitized solar cells
  • interfacial charge transfer
  • photocatalysis
  • time-resolved X-ray photoelectron spectroscopy

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Siefermann, K. R., Pemmaraju, C. D., Neppl, S., Shavorskiy, A., Cordones, A. A., Vura-Weis, J., Slaughter, D. S., Sturm, F. P., Weise, F., Bluhm, H., Strader, M. L., Cho, H., Lin, M. F., Bacellar, C., Khurmi, C., Guo, J., Coslovich, G., Robinson, J. S., Kaindl, R. A., ... Gessner, O. (2014). Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface. Journal of Physical Chemistry Letters, 5(15), 2753-2759. https://doi.org/10.1021/jz501264x