Molecular engineering of organic semiconductors enables noble metal-comparable SERS enhancement and sensitivity

Gokhan Demirel (), Rebecca L. M. Gieseking, Resul Ozdemir, Simon Kahmann, Maria A. Loi, George C. Schatz (), Antonio Facchetti () and Hakan Usta ()
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Gokhan Demirel: Gazi University
Rebecca L. M. Gieseking: Northwestern University
Resul Ozdemir: Gazi University
Simon Kahmann: University of Groningen
Maria A. Loi: University of Groningen
George C. Schatz: Northwestern University
Antonio Facchetti: Northwestern University
Hakan Usta: Abdullah Gül University

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: Abstract Nanostructured molecular semiconductor films are promising Surface-Enhanced Raman Spectroscopy (SERS) platforms for both fundamental and technological research. Here, we report that a nanostructured film of the small molecule DFP-4T, consisting of a fully π-conjugated diperfluorophenyl-substituted quaterthiophene structure, demonstrates a very large Raman enhancement factor (>105) and a low limit of detection (10−9 M) for the methylene blue probe molecule. This data is comparable to those reported for the best inorganic semiconductor- and even intrinsic plasmonic metal-based SERS platforms. Photoluminescence spectroscopy and computational analysis suggest that both charge-transfer energy and effective molecular interactions, leading to a small but non-zero oscillator strength in the charge-transfer state between the organic semiconductor film and the analyte molecule, are required to achieve large SERS enhancement factors and high molecular sensitivities in these systems. Our results provide not only a considerable experimental advancement in organic SERS figure-of-merits but also a guidance for the molecular design of more sensitive SERS systems.

Date: 2019
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DOI: 10.1038/s41467-019-13505-7

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