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. Schoenlein; Ali 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

doi:10.1021/jz501264x

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 journal › Article › peer-review

77 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 language	English (US)
Pages (from-to)	2753-2759
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	5
Issue number	15
DOIs	https://doi.org/10.1021/jz501264x
State	Published - Aug 7 2014
Externally published	Yes

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

General Materials Science
Physical and Theoretical Chemistry

Access to Document

10.1021/jz501264x

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

Siefermann, KR, Pemmaraju, CD, Neppl, S, Shavorskiy, A, Cordones, AA, Vura-Weis, J, Slaughter, DS, Sturm, FP, Weise, F, Bluhm, H, Strader, ML, Cho, H, Lin, MF, Bacellar, C, Khurmi, C, Guo, J, Coslovich, G, Robinson, JS, Kaindl, RA, Schoenlein, RW, Belkacem, A, Neumark, DM, Leone, SR, Nordlund, D, Ogasawara, H, Krupin, O, Turner, JJ, Schlotter, WF, Holmes, MR, Messerschmidt, M, Minitti, MP, Gul, S, Zhang, JZ, Huse, N, Prendergast, D & Gessner, O 2014, 'Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface', Journal of Physical Chemistry Letters, vol. 5, no. 15, pp. 2753-2759. https://doi.org/10.1021/jz501264x

@article{3be49779b66c456ab8411701d57021ec,

title = "Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface",

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.",

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

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

year = "2014",

month = aug,

day = "7",

doi = "10.1021/jz501264x",

language = "English (US)",

volume = "5",

pages = "2753--2759",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Atomic-scale perspective of ultrafast charge transfer at a dye-semiconductor interface

AU - Siefermann, Katrin R.

AU - Pemmaraju, Chaitanya D.

AU - Neppl, Stefan

AU - Shavorskiy, Andrey

AU - Cordones, Amy A.

AU - Vura-Weis, Josh

AU - Slaughter, Daniel S.

AU - Sturm, Felix P.

AU - Weise, Fabian

AU - Bluhm, Hendrik

AU - Strader, Matthew L.

AU - Cho, Hana

AU - Lin, Ming Fu

AU - Bacellar, Camila

AU - Khurmi, Champak

AU - Guo, Jinghua

AU - Coslovich, Giacomo

AU - Robinson, Joseph S.

AU - Kaindl, Robert A.

AU - Schoenlein, Robert W.

AU - Belkacem, Ali

AU - Neumark, Daniel M.

AU - Leone, Stephen R.

AU - Nordlund, Dennis

AU - Ogasawara, Hirohito

AU - Krupin, Oleg

AU - Turner, Joshua J.

AU - Schlotter, William F.

AU - Holmes, Michael R.

AU - Messerschmidt, Marc

AU - Minitti, Michael P.

AU - Gul, Sheraz

AU - Zhang, Jin Z.

AU - Huse, Nils

AU - Prendergast, David

AU - Gessner, Oliver

PY - 2014/8/7

Y1 - 2014/8/7

N2 - 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.

AB - 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.

KW - X-ray free electron laser

KW - constrained density functional theory

KW - dye-sensitized solar cells

KW - interfacial charge transfer

KW - photocatalysis

KW - time-resolved X-ray photoelectron spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=84905750503&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84905750503&partnerID=8YFLogxK

U2 - 10.1021/jz501264x

DO - 10.1021/jz501264x

M3 - Article

AN - SCOPUS:84905750503

SN - 1948-7185

VL - 5

SP - 2753

EP - 2759

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 15

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this