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

Abstract

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.

Authors:
; ; ; ; ; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
University of North Carolina, Chapel Hill, NC (United States); Duke Univ., Durham, NC (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1545923
Alternate Identifier(s):
OSTI ID: 1610482; OSTI ID: 1830748
Grant/Contract Number:  
SC0015739; SC0001011; CHE-1709497; CHE-1763207; DGE-1144081; SC0001517
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 33; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; photoelectrochemical cell; metal oxide electrode; bichromophoric dyad; excited-state transitions

Citation Formats

Shan, Bing, Nayak, Animesh, Williams, Olivia F., Yost, Dillon C., Polizzi, Nicholas F., Liu, Yanming, Zhou, Ninghao, Kanai, Yosuke, Moran, Andrew M., Therien, Michael J., and Meyer, Thomas J. Excitation energy-dependent photocurrent switching in a single-molecule photodiode. United States: N. p., 2019. Web. doi:10.1073/pnas.1907118116.
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Shan, Bing, Nayak, Animesh, Williams, Olivia F., Yost, Dillon C., Polizzi, Nicholas F., Liu, Yanming, Zhou, Ninghao, Kanai, Yosuke, Moran, Andrew M., Therien, Michael J., & Meyer, Thomas J. Excitation energy-dependent photocurrent switching in a single-molecule photodiode. United States. https://doi.org/10.1073/pnas.1907118116
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Shan, Bing, Nayak, Animesh, Williams, Olivia F., Yost, Dillon C., Polizzi, Nicholas F., Liu, Yanming, Zhou, Ninghao, Kanai, Yosuke, Moran, Andrew M., Therien, Michael J., and Meyer, Thomas J. Wed . "Excitation energy-dependent photocurrent switching in a single-molecule photodiode". United States. https://doi.org/10.1073/pnas.1907118116.
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@article{osti_1545923,
title = {Excitation energy-dependent photocurrent switching in a single-molecule photodiode},
author = {Shan, Bing and Nayak, Animesh and Williams, Olivia F. and Yost, Dillon C. and Polizzi, Nicholas F. and Liu, Yanming and Zhou, Ninghao and Kanai, Yosuke and Moran, Andrew M. and Therien, Michael J. and Meyer, Thomas J.},
abstractNote = {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.},
doi = {10.1073/pnas.1907118116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 33,
volume = 116,
place = {United States},
year = {2019},
month = {7}
}
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https://doi.org/10.1073/pnas.1907118116
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Cited by: 7 works
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Figures / Tables:

Fig. 1 Fig. 1: Structure and electronic absorption spectrum (extinction coefficients, ε/M−1·cm−1) of (PhZnRu)2+ (A) and (RuZn)2+ (B) as a function of wavenumber (ν/cm−1). The red and blue shadings represent the red- and blue-light excitation regions.
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