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

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
ORCiD logo [1];  [1];  [2];  [2];  [3];  [4];  [1]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Tongji Univ., Shanghai (China)
  3. Univ. of Colorado, Boulder, CO (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231; DMR-1548924; DMR-1420736
OSTI ID:
1604801
Alternate ID(s):
OSTI ID: 1625054; OSTI ID: 1760227
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 117, Issue 13; ISSN 0027-8424
Publisher:
National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

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Figures / Tables (7)

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71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Science & technology - other topics
infrared spectroscopy
molecular vibrations
scattering-scanning near-field optical microscopy (s-SNOM)
vibrational exciton
molecular energy transport