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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.

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


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.


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


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