Surface-enhanced Raman spectroscopy (SERS) is an important analytical tool with ultrahigh sensitivity that depends on electromagnetic mechanism (EM) and chemical mechanism (CM). The CM relies on efficient charge transfer between the probe molecules and SERS substrates, which means engineering the molecule attachment and the energy level alignment at the molecule/substrate interface is critical to optimal CM enhancement. Herein, we report enhanced CM of Rhodamine 6G (R6G) on graphene SERS substrates using combined C-band ultraviolet (UVC) irradiation and Pt nanoparticle (Pt-NPs) decoration using atomic layer deposition (ALD). An enhancement of 270% was obtained in the former, which is ascribed to the graphene surface activation and p-doping on graphene for improved R6G molecule attachment and charge transfer by its surface change from hydrophobic to hydrophilic and the down-shift of the Fermi energy (p-doping) after UVC exposure. The Pt-NPs decoration adds an additional enhancement of 250% by further p-doping graphene, which shifts the graphene’s Fermi energy to promote charge (hole) transfer at the R6G/graphene interface. Remarkably, the combination of the UVC irradiation and Pt-NPs decoration has led to enhanced R6G SERS sensitivity of 5 × 10−9 M, which represents a two-orders of magnitude enhancement over that on the pristine graphene and illustrates the importance of graphene engineering for optimal probe molecule attachment and the energy level alignment at the molecule/graphene interface toward achieving high-performance SERS biosensing.
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Molecular engineering of organic semiconductors enables noble metal-comparable SERS enhancement and sensitivity
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 moleculeDFP-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.
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- Award ID(s):
- 1760537
- PAR ID:
- 10153801
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 10
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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