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Title: Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Abstract

Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s -SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins.

Authors:
ORCiD logo; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1604801
Grant/Contract Number:  
AC02- 05CH11231
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: 117 Journal Issue: 13; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Muller, Eric A., Gray, Thomas P., Zhou, Zhou, Cheng, Xinbin, Khatib, Omar, Bechtel, Hans A., and Raschke, Markus B. Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals. United States: N. p., 2020. Web. doi:10.1073/pnas.1914172117.
Muller, Eric A., Gray, Thomas P., Zhou, Zhou, Cheng, Xinbin, Khatib, Omar, Bechtel, Hans A., & Raschke, Markus B. Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals. United States. doi:10.1073/pnas.1914172117.
Muller, Eric A., Gray, Thomas P., Zhou, Zhou, Cheng, Xinbin, Khatib, Omar, Bechtel, Hans A., and Raschke, Markus B. Fri . "Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals". United States. doi:10.1073/pnas.1914172117.
@article{osti_1604801,
title = {Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals},
author = {Muller, Eric A. and Gray, Thomas P. and Zhou, Zhou and Cheng, Xinbin and Khatib, Omar and Bechtel, Hans A. and Raschke, Markus B.},
abstractNote = {Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s -SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins.},
doi = {10.1073/pnas.1914172117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 13,
volume = 117,
place = {United States},
year = {2020},
month = {3}
}

Journal Article:
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DOI: 10.1073/pnas.1914172117

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