Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye-Semiconductor Interface.
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.
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Katrin R
KR
Siefermann
‡The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Chaitanya D
CD
Pemmaraju
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Stefan
S
Neppl
§Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Andrey
A
Shavorskiy
∥Department of Chemistry, University of California, Berkeley, California 94720, United States.
Amy A
AA
Cordones
∥Department of Chemistry, University of California, Berkeley, California 94720, United States.
Josh
J
Vura-Weis
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Daniel S
DS
Slaughter
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Felix P
FP
Sturm
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Fabian
F
Weise
§Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Hendrik
H
Bluhm
§Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Matthew L
ML
Strader
§Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Hana
H
Cho
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|∥Department of Chemistry, University of California, Berkeley, California 94720, United States.
Ming-Fu
MF
Lin
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|∥Department of Chemistry, University of California, Berkeley, California 94720, United States.
Camila
C
Bacellar
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Champak
C
Khurmi
#Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Jinghua
J
Guo
⊥Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Giacomo
G
Coslovich
⊥Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Joseph S
JS
Robinson
⊥Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Robert A
RA
Kaindl
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|⊥Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Robert W
RW
Schoenlein
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Ali
A
Belkacem
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|∥Department of Chemistry, University of California, Berkeley, California 94720, United States.
Daniel M
DM
Neumark
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|∥Department of Chemistry, University of California, Berkeley, California 94720, United States.|○Department of Physics, University of California, Berkeley, California 94720, United States.
Stephen R
SR
Leone
◆SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Dennis
D
Nordlund
◆SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Hirohito
H
Ogasawara
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.|¶European XFEL GmbH, 22761 Hamburg, Germany.
Oleg
O
Krupin
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Joshua J
JJ
Turner
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
William F
WF
Schlotter
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Michael R
MR
Holmes
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Marc
M
Messerschmidt
▽Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Michael P
MP
Minitti
#Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|+Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States.
Sheraz
S
Gul
+Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States.
Jin Z
JZ
Zhang
■Physics Department, University of Hamburg and Max-Planck Institute for Structure and Dynamics of Matter, 22761 Hamburg, Germany.
Nils
N
Huse
‡The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
David
D
Prendergast
†Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Oliver
O
Gessner
X-ray free electron laser; constrained density functional theory; dye-sensitized solar cells; interfacial charge transfer; photocatalysis; time-resolved X-ray photoelectron spectroscopy