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SCIENCE ADVANCES, Volume: 3, Issue: 11,NOV 2017

 

Ultrafast direct electron transfer at organic semiconductor and metal interfaces

By:Xiang, B (Xiang, Bo)1 ] Li, YM (Li, Yingmin)1 ] Pham, CH (Pham, C. Huy)2 ] Paesani, F (Paesani, Francesco)1,2 ] Xiong, W (Xiong, Wei)1,2 ]

 

SCIENCE ADVANCES, Volume: 3, Issue: 11

Published: NOV 2017

Document Type:Article

Abstract

The ability to control direct electron transfer can facilitate the development of new molecular electronics, light-harvesting materials, and photocatalysis. However, control of direct electron transfer has been rarely reported, and the molecular conformation-electron dynamics relationships remain unclear. We describe direct electron transfer at buried interfaces between an organic polymer semiconductor film and a gold substrate by observing the first dynamical electric field-induced vibrational sum frequency generation (VSFG). In transient electric field-induced VSFG measurements on this system, we observe dynamical responses (<150 fs) that depend on photon energy and polarization, demonstrating that electrons are directly transferred from the Fermi level of gold to the lowest unoccupied molecular orbital of organic semiconductor. Transient spectra further reveal that, although the interfaces are prepared without deliberate alignment control, a subensemble of surface molecules can adopt conformations for direct electron transfer. Density functional theory calculations support the experimental results and ascribe the observed electron transfer to a flat-lying polymer configuration in which electronic orbitals are found to be delocalized across the interface. The present observation of direct electron transfer at complex interfaces and the insights gained into the relationship between molecular conformations and electron dynamics will have implications for implementing novel direct electron transfer in energy materials.

Author Information

Reprint Address: Xiong, W (reprint author)

Show more Univ Calif San Diego, Mat Sci & Engn Program, La Jolla, CA 92093 USA.

Reprint Address: Xiong, W (reprint author)

Show more Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA.

 

Addresses:

Show more [ 1 ] Univ Calif San Diego, Mat Sci & Engn Program, La Jolla, CA 92093 USA
Show more [ 2 ] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

 

E-mail Addresses:w2xiong@ucsd.edu

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