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Title: Excitation energy-dependent photocurrent switching in a single-molecule photodiode

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America

The direction of electron flow in molecular optoelectronic devices is dictated by charge transfer between a molecular excited state and an underlying conductor or semiconductor. For those devices, controlling the direction and reversibility of electron flow is a major challenge. We describe here a single-molecule photodiode. It is based on an internally conjugated, bichromophoric dyad with chemically linked (porphyrinato)zinc(II) and bis(terpyridyl)ruthenium(II) groups. On nanocrystalline, degenerately doped indium tin oxide electrodes, the dyad exhibits distinct frequency-dependent, charge-transfer characters. Variations in the light source between red-light (~1.9 eV) and blue-light (~2.7 eV) excitation for the integrated photodiode result in switching of photocurrents between cathodic and anodic. Finally, the origin of the excitation frequency-dependent photocurrents lies in the electronic structure of the chromophore excited states, as shown by the results of theoretical calculations, laser flash photolysis, and steady-state spectrophotometric measurements.

Research Organization:
Duke Univ., Durham, NC (United States); University of North Carolina, Chapel Hill, NC (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE; National Science Foundation (NSF)
Grant/Contract Number:
SC0001517; SC0015739; SC0001011; CHE-1709497; CHE-1763207; DGE-1144081
OSTI ID:
1545923
Alternate ID(s):
OSTI ID: 1610482; OSTI ID: 1830748
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, Issue 33; ISSN 0027-8424
Publisher:
National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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Figures / Tables (5)