Micro-Raman imaging of isomeric segregation in small-molecule organic semiconductors

Chiung Wei Huang; Xiao You; Peter J. Diemer; Anthony J. Petty; John E. Anthony; Oana D. Jurchescu; Joanna M. Atkin

doi:10.1038/s42004-019-0122-7

Micro-Raman imaging of isomeric segregation in small-molecule organic semiconductors

Chiung Wei Huang
, Xiao You
, Peter J. Diemer
, Anthony J. Petty
, John E. Anthony
, Oana D. Jurchescu
, Joanna M. Atkin

Producción científica: Article › revisión exhaustiva

19 Citas (Scopus)

Resumen

Charge transport in organic semiconductors is highly sensitive to film heterogeneity and intermolecular interactions, but probing these properties on the length scales of disorder is often difficult. Here we use micro-Raman spectroscopy to assign vibrational modes of isomerically pure syn and anti 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES ADT) by comparing to density functional theory calculations. With polarization-dependent measurements, we determine the orientation of crystallites in pure isomers. In mixed-isomer samples, we observe narrow linewidths and superposition spectra, indicating coexistence of isomerically pure sub-domains on length scales smaller than the probe area. Using the ring breathing modes close to 1300 cm⁻¹ as indicators of the pure isomer crystalline sub-domains, we image their spatial distribution with 200-nm resolution. These results demonstrate the power of micro-Raman spectroscopy for investigating spatial heterogeneities and clarifying the origin of the reduced charge carrier mobility displayed in mixed-isomer diF-TES ADT.

Idioma original	English
Número de artículo	22
Publicación	Communications Chemistry
Volumen	2
N.º	1
DOI	https://doi.org/10.1038/s42004-019-0122-7
Estado	Published - dic 1 2019

Nota bibliográfica

Publisher Copyright:
© 2019, The Author(s).

Financiación

A portion of this work was performed using the Raman microspectrometer in the UNC EFRC Instrumentation Facility established by the UNC EFRC Center for Solar Fuels, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0001011. P.J.D. and O.D.J. acknowledge support from the NSF ECCS 1254757. A.J.P. and J.E.A. thank NSF DMREF-162748 for support. We also thank Prof. Kizhanipuram Vinodgopal for allowing us to use the Raman microspectrometer at North Carolina Central University.

Financiadores	Número del financiador
National Science Foundation Arctic Social Science Program
U.S. Department of Energy EPSCoR
Division of Materials Research	162748
Division of Materials Research
Directorate for Computer and Information Science and Engineering	1254757
Directorate for Computer and Information Science and Engineering
Office of Science Programs
DOE Basic Energy Sciences	DE-SC0001011
DOE Basic Energy Sciences
University of North Carolina and North Carolina State University

ASJC Scopus subject areas

General Chemistry
Materials Chemistry
Biochemistry
Environmental Chemistry

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10.1038/s42004-019-0122-7

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title = "Micro-Raman imaging of isomeric segregation in small-molecule organic semiconductors",

abstract = "Charge transport in organic semiconductors is highly sensitive to film heterogeneity and intermolecular interactions, but probing these properties on the length scales of disorder is often difficult. Here we use micro-Raman spectroscopy to assign vibrational modes of isomerically pure syn and anti 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES ADT) by comparing to density functional theory calculations. With polarization-dependent measurements, we determine the orientation of crystallites in pure isomers. In mixed-isomer samples, we observe narrow linewidths and superposition spectra, indicating coexistence of isomerically pure sub-domains on length scales smaller than the probe area. Using the ring breathing modes close to 1300 cm−1 as indicators of the pure isomer crystalline sub-domains, we image their spatial distribution with 200-nm resolution. These results demonstrate the power of micro-Raman spectroscopy for investigating spatial heterogeneities and clarifying the origin of the reduced charge carrier mobility displayed in mixed-isomer diF-TES ADT.",

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AU - Huang, Chiung Wei

AU - You, Xiao

AU - Diemer, Peter J.

AU - Petty, Anthony J.

AU - Anthony, John E.

AU - Jurchescu, Oana D.

AU - Atkin, Joanna M.

PY - 2019/12/1

Y1 - 2019/12/1

N2 - Charge transport in organic semiconductors is highly sensitive to film heterogeneity and intermolecular interactions, but probing these properties on the length scales of disorder is often difficult. Here we use micro-Raman spectroscopy to assign vibrational modes of isomerically pure syn and anti 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES ADT) by comparing to density functional theory calculations. With polarization-dependent measurements, we determine the orientation of crystallites in pure isomers. In mixed-isomer samples, we observe narrow linewidths and superposition spectra, indicating coexistence of isomerically pure sub-domains on length scales smaller than the probe area. Using the ring breathing modes close to 1300 cm−1 as indicators of the pure isomer crystalline sub-domains, we image their spatial distribution with 200-nm resolution. These results demonstrate the power of micro-Raman spectroscopy for investigating spatial heterogeneities and clarifying the origin of the reduced charge carrier mobility displayed in mixed-isomer diF-TES ADT.

AB - Charge transport in organic semiconductors is highly sensitive to film heterogeneity and intermolecular interactions, but probing these properties on the length scales of disorder is often difficult. Here we use micro-Raman spectroscopy to assign vibrational modes of isomerically pure syn and anti 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES ADT) by comparing to density functional theory calculations. With polarization-dependent measurements, we determine the orientation of crystallites in pure isomers. In mixed-isomer samples, we observe narrow linewidths and superposition spectra, indicating coexistence of isomerically pure sub-domains on length scales smaller than the probe area. Using the ring breathing modes close to 1300 cm−1 as indicators of the pure isomer crystalline sub-domains, we image their spatial distribution with 200-nm resolution. These results demonstrate the power of micro-Raman spectroscopy for investigating spatial heterogeneities and clarifying the origin of the reduced charge carrier mobility displayed in mixed-isomer diF-TES ADT.

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Micro-Raman imaging of isomeric segregation in small-molecule organic semiconductors

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