Nanohybrids of graphene and two-dimensional (2D) layered transition metal dichalcogenides (TMD) nanostructures can provide a promising substrate for extraordinary surface-enhanced Raman spectroscopy (SERS) due to the combined electromagnetic enhancement on TMD nanostructures via localized surface plasmonic resonance (LSPR) and chemical enhancement on graphene. In these nanohybrid SERS substrates, the LSPR on TMD nanostructures is affected by the TMD morphology. Herein, we report the first successful growth of MoS2 nanodonuts (N-donuts) on graphene using a vapor transport process on graphene. Using Rhodamine 6G (R6G) as a probe, SERS spectra were compared on MoS2 N-donuts/graphene nanohybrids substrates. A remarkably high R6G SERS sensitivity up to 2 × 10−12 M has been obtained, which can be attributed to the more robust LSPR effect than in other TMD nanostructures such as nanodiscs as suggested by the finite-difference time-domain simulation. This result demonstrates that non-metallic TMD/graphene nanohybrids substrates can have SERS sensitivity up to one order of magnitude higher than that reported on the plasmonic metal nanostructures/2D materials SERS substrates, providing a promising scheme for high-sensitivity, low-cost applications for biosensing.
more »
« less
Extraordinary Sensitivity of Surface‐Enhanced Raman Spectroscopy of Molecules on MoS 2 (WS 2 ) Nanodomes/Graphene van der Waals Heterostructure Substrates
Two‐dimensional transition metal dichalcogenides (TMDs)/graphene van der Waals (vdW) heterostructures integrate the superior light–solid interaction in TMDs and charge mobility in graphene, and therefore are promising for surface‐enhanced Raman spectroscopy (SERS). Herein, a novel TMD (MoS2and WS2) nanodome/graphene vdW heterostructure SERS substrate, on which an extraordinary SERS sensitivity is achieved, is reported. Using fluorescent Rhodamine 6G (R6G) as probe molecules, the SERS sensitivity is in the range of 10−11to 10−12
- Award ID(s):
- 1508494
- PAR ID:
- 10460137
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 7
- Issue:
- 8
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract 2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe2/graphene/n‐SnS2/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe2and SnS2of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5−7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W−1with fast photoresponse and specific detectivity up to ≈1013Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.
-
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.more » « less
-
more » « less
Abstract Surface‐enhanced Raman spectroscopy (SERS) has become a sensitive detection technique for biochemical analysis. Despite significant research efforts, most SERS substrates consisting of single‐resonant plasmonic nanostructures on the planar surface suffer from limitations of narrowband SERS operation and unoptimized nano‐bio interface with living cells. Here, it is reported that nanolaminate plasmonic nanocavities on 3D vertical nanopillar arrays can support a broadband SERS operation with large enhancement factors (>106) under laser excitations at 532, 633, and 785 nm. The multi‐band Raman mapping measurements show that nanolaminate plasmonic nanocavities on vertical nanopillar arrays exhibit broadband uniform SERS performance with diffraction‐limited resolution at a single nanopillar footprint. By selective exposure of embedded plasmonic hotspots in individual metal–insulator–metal (MIM) nanogaps, nanoscale broadband SERS operation at the single MIM nanocavity level with visible and near‐infrared (vis–NIR) excitations is demonstrated. Numerical studies reveal that nanolaminate plasmonic nanocavities on vertical nanopillars can support multiple hybridized plasmonic modes to concentrate optical fields across a broadband wavelength range from 500 to 900 nm at the nanoscale.
-
more » « less
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.
