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J Phys Chem Lett. 2015 Jan 2;6(1):6-12. doi: 10.1021/jz502253r. Epub 2014 Dec 15.

Ultrafast Electron Transfer at Organic Semiconductor Interfaces: Importance of Molecular Orientation.

Author information

1
†Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
2
‡Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
3
§Department of Organic Materials and Fiber Engineering, Soongsil University, Seoul, 156-743 Korea.

Abstract

Much is known about the rate of photoexcited charge generation in at organic donor/acceptor (D/A) heterojunctions overaged over all relative arrangements. However, there has been very little experimental work investigating how the photoexcited electron transfer (ET) rate depends on the precise relative molecular orientation between D and A in thin solid films. This is the question that we address in this work. We find that the ET rate depends strongly on the relative molecular arrangement: The interface where the model donor compound copper phthalocyanine is oriented face-on with respect to the fullerene C60 acceptor yields a rate that is approximately 4 times faster than that of the edge-on oriented interface. Our results suggest that the D/A electronic coupling is significantly enhanced in the face-on case, which agrees well with theoretical predictions, underscoring the importance of controlling the relative interfacial molecular orientation.

KEYWORDS:

charge-transfer state; core-hole clock; electron dynamics; organic photovoltaic; resonant Auger; resonant photoemission

PMID:
26263084
DOI:
10.1021/jz502253r

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