Surface-enhanced Raman Scattering Systems Research Articles

Recent Development and Applications of Stretchable SERS Substrates.

Surface-enhanced Raman scattering (SERS) is a cutting-edge technique for highly sensitive analysis of chemicals and molecules. Traditional SERS-active nanostructures are constructed on rigid substrates where the nanogaps providing hot-spots of Raman signals are fixed, and sample loading is unsatisfactory due to the unconformable attachment of substrates on irregular sample surfaces. A flexible SERS substrate enables conformable sample loading and, thus, highly sensitive Raman detection but still with limited detection capabilities. Stretchable SERS substrates with flexible sample loading structures and controllable hot-spot size provide a new strategy for improving the sample loading efficiency and SERS detection sensitivity. This review summarizes and discusses recent development and applications of the newly conceptual stretchable SERS substrates. A roadmap of the development of SERS substrates is reviewed, and fabrication techniques of stretchable SERS substrates are summarized, followed by an exhibition of the applications of these stretchable SERS substrates. Finally, challenges and perspectives of the stretchable SERS substrates are presented. This review provides an overview of the development of SERS substrates and sheds light on the design, fabrication, and application of stretchable SERS systems.

Interpreting chemical enhancements of surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) provides orders of magnitude of enhancements to weak Raman scattering. The improved sensitivity and chemical information conveyed in the spectral signatures make SERS a valuable analysis technique. Most of SERS enhancements come from the electromagnetic enhancement mechanism, and changes in spectral signatures are usually attributed to the chemical enhancement mechanism. As the electromagnetic mechanism has been well studied, we will give an overview of models related to the chemical mechanism, which explain the Raman response in terms of electronic transitions or induced electron densities. In the first class of models based on electronic transitions, chemical enhancements are attributed to changes in transitions of the molecule and new charge transfer transitions. The second class of models relate chemical enhancements to charge flows near the molecule–metal interface by partitioning the induced electron density of the SERS system in real space. Selected examples will be given to illustrate the two classes of models, and connections between the models are demonstrated for prototypical SERS systems.

Factor analysis of the time series of SERS spectra reveals water arrangement and surface plasmon changes in Ag nanoparticle systems

The enhancement of Raman signals of molecules localized in the vicinity of plasmonic nanoparticles, known as surface-enhanced Raman scattering (SERS) effect, is strongly influenced by the selected excitation wavelength. The optimal excitation wavelength in SERS measurements is given by the position of the surface plasmon extinction (SPE) band of the studied system. Even a small change of the SPE band intensity, position and/or shape during the measurement may influence the SERS signal significantly. In this work, we prepared several systems of Ag nanoparticles, which were used for the demonstration how the information about SPE changes can be obtained by multivariate statistical analysis (factor analysis; FA) from SERS spectral sets, and employed in more precise and more comprehensive interpretation of the results. In non-aggregated Ag colloidal systems measured at the excitation wavelength of 445 nm, SPE band changes could be monitored by the analysis of water stretching vibration together with the vibrations in the fingerprint region. The FA of the water stretching band region was shown to provide unique information on both arrangement and disarrangement of water molecules in the vicinity of Ag NPs during the time evolution of these SERS active systems. In addition, the FA of the fingerprint region helped to monitor a rapid metalation of meso-tetrakis(N-methyl-4-pyridyl)porphine in etched SERS systems with Ag+ ions released from the NPs surface. In aggregated Ag colloidal systems measured at the excitation wavelength of 785 nm, the FA of SERS spectral sets enabled us to reveal the contribution of the 2nd electromagnetic enhancement to the overall SERS signal. The reliability of our conclusions was verified by comparing the results obtained from FA of SERS spectral sets with the data obtained from the parallel SPE measurements of the studied systems.

SERS-active substrates based on Ag-coated TiO2 nanotubes and nanograss

In this work, TiO 2 nanotubes (NT) and nanograss (NG) at the edges of nanotubes obtained by electrochemical anodizing followed by the deposition of plasmonic silver (Ag, 30μg/cm 2 ) nanoparticles were investigated as substrates for surface enhanced Raman scattering (SERS) on methylene blue molecules. The resulting nanotubes have an inner diameter of about 40–80 nm and a wall thickness of ∼10 nm. Synthesis parameters were worked out for the formation of nanograss on the edges of TiO 2 nanotubes. The deposition of an active silver layer with respect to surface plasmon resonance on the TiO 2 nanostructures makes it possible to use this composite as efficient SERS substrates. It was found that the proposed SERS systems allow to detect the Raman spectrum of methylene blue (MB) at concentrations down to 10 −12 M. The values of the analytical enhancement factor for TiO 2 NT and NG at the edges of nanotubes were estimated with respect to different reference materials.

Toward Quantitative Surface-Enhanced Raman Scattering with Plasmonic Nanoparticles: Multiscale View on Heterogeneities in Particle Morphology, Surface Modification, Interface, and Analytical Protocols.

Surface-enhanced Raman scattering (SERS) provides significantly enhanced Raman scattering signals from molecules adsorbed on plasmonic nanostructures, as well as the molecules' vibrational fingerprints. Plasmonic nanoparticle systems are particularly powerful for SERS substrates as they provide a wide range of structural features and plasmonic couplings to boost the enhancement, often up to >108-1010. Nevertheless, nanoparticle-based SERS is not widely utilized as a means for reliable quantitative measurement of molecules largely due to limited controllability, uniformity, and scalability of plasmonic nanoparticles, poor molecular modification chemistry, and a lack of widely used analytical protocols for SERS. Furthermore, multiscale issues with plasmonic nanoparticle systems that range from atomic and molecular scales to assembled nanostructure scale are difficult to simultaneously control, analyze, and address. In this perspective, we introduce and discuss the design principles and key issues in preparing SERS nanoparticle substrates and the recent studies on the uniform and controllable synthesis and newly emerging machine learning-based analysis of plasmonic nanoparticle systems for quantitative SERS. Specifically, the multiscale point of view with plasmonic nanoparticle systems toward quantitative SERS is provided throughout this perspective. Furthermore, issues with correctly estimating and comparing SERS enhancement factors are discussed, and newly emerging statistical and artificial intelligence approaches for analyzing complex SERS systems are introduced and scrutinized to address challenges that cannot be fully resolved through synthetic improvements.

Chemical Mechanism-Dominated and Reporter-Tunable Surface-Enhanced Raman Scattering via Directional Supramolecular Assembly.

Molecular resonance can be strengthened by charge transfer, profiting chemical mechanism (CM)-related surface-enhanced Raman scattering (SERS). Herein a supramolecular assembly enabled SERS system is established by functionalizing para-sulfonatocalix[4]arene (pSC4) onto Au3Cu nanocrystals (NCs). Due to the cooperation of Au and Cu, pSC4 is directionally assembled on the surface of Au3Cu NCs via van der Waals force, enabling photoinduced and hydrogen bond-induced charge transfer, which remarkably enhances the Raman scattering of methylene blue (MB) captured by pSC4. In particular, for the C-N and C-C stretching of MB, the contributions of resonance Raman scattering increase up to 80%. In addition, the SERS system is able to display affinities of different host-guest interactions, and further employed to evaluate effects of drugs for Alzheimer's disease. In this work, charge transfer is realized by performing supramolecular assembly on the surface of plasmonic nanomaterials, providing an avenue to design CM-related and reporter-tunable SERS systems.

All-fiber surface-enhanced Raman scattering detection system combining an integrated microfluidic chip and micro-lensed fiber.

It is a challenge to perform simple and rapid detection of substances due to their complex structure. Biochemical molecules play a vital role in human health and environmental testing. Surface-enhanced Raman scattering (SERS) detection has the characteristics of strong specificity and real-time performance. At present, most SERS systems are expensive and not portable. Here, we demonstrate a SERS detection system with all-fiber connection, combined with a microfluidic chip and micro-lenses. Compared with the conventional SERS system that uses the spatial optical path, the devices in our system are connected by optical fibers, making the system more stable and operable. Besides, the microfluidic chips are introduced to further improve the system integration and stability. Owing to the micro-lensed fiber probe, the detected Raman signal intensity is increased by 2-3 times. We anticipate that the presented work will lead toward a rapid and portable SERS system and corresponding detection system. It also lays the foundation for real-time recognition in various complex environments in the design of a future optical fiber system.

Coffee ring effect assisted improved S. aureus screening on a physically restrained gold nanoflower enriched SERS substrate

Proactive water pathogen identification process holds significance in view of increasing bioterrorism prospects, quantification of virulence properties and water supply regulation for human welfare. Strikingly, pathogen concentration is rather low in water bodies to be identified using conventional methods and usually involves three typical steps: 1) concentration 2) purification and 3) characterization and assay. Surface enhanced Raman scattering (SERS) analysis on other hand could easily surpass these steps to give a rather robust identification owing to its exceptionally high specificity and sensing abilities. In this article we use SERS as a diagnostic tool to identify low concentrations of noxious pathogens from water, using a two level confinement that results in a superlative SERS analytical assay, capable of analyte identification down to single molecule level. Unlike the regular dip coat process, we restrict the nanostructure deposition only to a very small area of the larger substrate, by restricting its application volume. In this way, we limit our data processing time, increase our probability of target interaction and also reduce nanostructure/analyte sample quantities for analysis. To enhance the signal intensities further, we use natural three phase pinning or the coffee ring effect to pre-concentrate the analytes on our spatially confined nanostructure pocket, allowing maximal deposition at the edges and subsequently higher signal intensities. The methodology was employed to measure the presence of S. aureus and R6 G in spiked drinking water. LOD achieved for R6 G and S. aureus is 10−12 M and 103 CFU/ml respectively. The increasing signal intensities share a linear relationship with analyte concentration. The acquired signals were reproducible and non-degenerate, overcoming the drawback of irregular data patterns associated with conventional metal nanostructure based SERS systems. Estimated RSD value for physical confinement and coffee ring effect measured was 11.6% and 8.37% respectively. This simple, low cost, robust and reproducible method can be useful for increasing the sensitivity of SERS based detection devices with capability to be developed into a micro total analysis system (μTAS).

Surface-enhanced Raman scattering of subwavelength metallic structures

Surface-enhanced Raman scattering (SERS) makes the Raman signals, as fingerprints of different vibration modes of chemical bonds, significant in practical applications. Two main mechanisms, chemical and physical, are attributed to the SERS of molecules adsorbed on metals. The physical mechanism plays a major role in SERS, which is the focus of our paper. Recent SERS systems are mostly based on dimer structures, i.e. nanoparticle pairs, of noble metals. Large amplification of electrical field occurs in the gap of a dimer structure compared with a single nanoparticle. The above gap positions are called as " hot spots” of SERS. In addition, the reproducibility and reliability of SERS substrates are also important for practical applications. Here we use periodical subwavelength metallic structures to meet such needs, and develop other kinds of electrical field enhancement mechanisms. We present the electrical field enhancement of the band-edge mode of surface plasmon polariton, gap plasmon polariton mode, as well as their coupling mode. We choose one-dimensional subwavelength metallic structures to clarify the physical mechanism. Our purpose is to develop subwavelength metallic structures with even and intensive " hot spots”, serving as ultrasensitive solid-state SERS substrates with excellent reproducibility and reliability.

A novel natural SERS system for crystal violet detection based on graphene oxide wrapped Ag micro-islands substrate fabricated from Lotus leaf as a template

A stable biomimetic surface enhanced Raman scattering (SERS) system was fabricated by covering graphene oxide (GO) on the Ag micro-islands substrate using micro/nanostructured Lotus leaf (L.l.) as a template via the simple magnetron sputtering system and dip-coated method. The Raman signals of crystal violet (CV) on the GO-Ag-L.l.-30 substrate (the sputtering time was 30 min) showed far better SERS performances than Ag-L.l.-30 hybrids in terms of signal enhancement, sensitivity and stability. The results suggested that the SERS activity of the bio-inspired GO-Ag-L.l.-30 substrate using CV as probe molecules showed an enhancement factor (EF) of ∼1.52 × 106. Sensitivity tests indicated that the limit of detection (LOD) for CV was as low as 5 × 10−10 M, which was two orders of magnitude lower than Ag-L.l.-30 substrate. Time-stability for 30 days was also reported which revealed that the Raman intensity of CV on GO-Ag-L.l.-30 substrate only reduced by 18.2% after aging for 30 days. Moreover, the maximum relative standard deviations (RSD) of Raman intensities was less than 7.09%, demonstrating outstanding reproducibility and uniformity of GO-Ag-L.l.-30 substrate. Therefore, the cost-efficient and high-performance SERS system shows great application prospects in biochemical sensing and attracts broad attention to many other natural materials which can be prepared as multifarious novel SERS systems.

Plasmon-Mediated Surface Engineering of Silver Nanowires for Surface-Enhanced Raman Scattering.

We reveal nanoscale morphological changes on the surface of a silver nanowire (AgNW) in the conventional surface-enhanced Raman scattering (SERS) measurement condition. The surface morphology changes are due to the surface plasmon-mediated photochemical etching of silver in the presence of certain Raman probes, resulting in a dramatic increase of Raman scattering intensity. This observation indicates that the measured SERS enhancement does not always originate from the as-designed/fabricated structures themselves, but sometimes with contribution from the morphological changes by plasmon-mediated photochemical reactions. Our work provides a guideline for more reliable SERS measurements and demonstrates a novel method for simple and site-specific engineering of SERS substrate and AgNW probes for designing and fabricating new SERS systems, stable and efficient TERS mapping, and single-cell SERS endoscopy.

Bifunctional plasmonic-magnetic particles for an enhanced microfluidic SERS immunoassay.

Surface-Enhanced Raman Scattering (SERS) is emerging as a promising strategy for the quantification of immunoglobulin G (IgG) due to its inherent high sensitivity and specificity; however, it remains challenging to integrate SERS detection with a microfluidic system in a simple, efficient and low-cost manner. Here, we report on a novel bifunctional plasmonic-magnetic particle-based immunoassay, in which plasmonic nanoparticles act as soluble SERS immunosubstrates, whereas magnetic particles are for promoting micromixing in a microfluidic chip. With this novel SERS immunosubstrate in conjunction with the unique microfluidic system, we could substantially reduce the assay time from 4 hours to 80 minutes as well as enhance the detection specificity by about 70% in comparison to a non-microfluidic immunoassay. Compared to previous microfluidic SERS systems, our strategy offers a simple microfluidic chip design with only one well for mixing, washing and detection.

Surface-Enhanced Raman Scattering Based on Controllable-Layer Graphene Shells Directly Synthesized on Cu Nanoparticles for Molecular Detection.

Graphene shells with a controllable number of layers were directly synthesized on Cu nanoparticles (CuNPs) by chemical vapor deposition (CVD) to fabricate a graphene-encapsulated CuNPs (G/CuNPs) hybrid system for surface-enhanced Raman scattering (SERS). The enhanced Raman spectra of adenosine and rhodamine 6G (R6G) showed that the G/CuNPs hybrid system can strongly suppress background fluorescence and increase signal-to-noise ratio. In four different types of SERS systems, the G/CuNPs hybrid system exhibits more efficient SERS than a transferred graphene/CuNPs hybrid system and pure CuNPs and graphene substrates. The minimum detectable concentrations of adenosine and R6G by the G/CuNPs hybrid system can be as low as 10(-8) and 10(-10) M, respectively. The excellent linear relationship between Raman intensity and analyte concentration can be used for molecular detection. The graphene shell can also effectively prevent surface oxidation of Cu nanoparticles after exposure to ambient air and thus endow the hybrid system with a long lifetime. This work provides a basis for the fabrication of novel SERS substrates.

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: Origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 105, and the detection limit of rhodamine 6G at DAR surfaces was 10−8M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications.

Direct Fabrication Route to Plastic-Supported Gold Nanoparticles for Flexible NIR-SERS

Stable gold nanoparticles with surface plasmon resonance tunable from visible (Vis) to near-infrared (NIR) are deposited via a direct sputtering methodology on large area polyethylene terephthalate (PET) to be used as effective, flexible NIR surface-enhanced Raman scattering (SERS) substrates. An O2 plasma treatment of PET is used to tailor growth dynamics, geometry, and plasmonic properties of nanoparticles. The O2 plasma treatment of PET results also in effective improvement of nanoparticle anchoring on the plastic substrate, providing more stable, flexible SERS systems. The functionality of fabricated SERS substrates has been tested using benzylthiol, and SERS enhancement factors in the range 104 have been achieved, which are comparable with those reported in literature for gold nanostructures fabricated on silicon substrate. These results attest the great potentiality of this methodology for the production of cost-effective flexible and reusable large-scale SERS substrates.

Uniformly-Assembled Metal Nanoparticles on Anodic Aluminum Oxide (AAO) Applied in Surface-Enhanced Raman Spectroscopy

ABSTRACTColloidal Au/Ag nanoparticles can be controllably assembled on anodic aluminum oxide (AAO) surfaces; monolayer coating on the membrane on AAO with smaller pores, or a nano-net arrangement along the edges of AAO with larger pores. The supported Au and Ag nanoparticles on the AAO membranes are closely packed and exhibited localized surface plasmon resonance (LSPR). Thus AAO membrane coated with Au or Ag nanoparticles is a highly surface-enhanced Raman scattering (SERS) active substrate. High quality SERS spectra were obtained using fullerene molecules C60 & C70 as the probe molecules and the filtered Au nanoparticles as the substrate. Furthermore, new SERS systems were obtained from Au nanoparticles assembled into the pores of AAO-supported fullerene nano-tubes, and the C60/C70 nano-tube arrays loaded with Au nanoparticles. The new SERS systems made use of the contributions from AAO, the LSPR of the Au nanoparticles, and a uniform assembly of the probe molecules in the nanostructures. These approaches have also been applied to small organic molecule systems using Ag nanoparticles.

Evanescent-wave excitation of surface-enhanced Raman scattering substrates by an optical-fiber taper

We present a way of guiding light to planar surface-enhanced Raman scattering (SERS) substrates by using evanescent-wave coupling. Using nanostructured chalcogenide glass-based SERS substrates, we experimentally show the incident-angle dependence of plasmon resonances of the SERS substrates, demonstrating strong resonances at large incident angles. This allows the evanescent-wave excitation of SERS substrates through tapered optical fibers. Experiments show that fiber-taper-excited SERS substrates exhibit a significant enhancement of the Raman spectra of Rhodamine-6G analyte molecules. This configuration forms the basis of fiber-optic-based, reproducible, highly compact, and sensitive SERS systems.

A new substrate for surface enhanced Raman scattering of dye Sudan molecules

A new SERS substrate was prepared using electro-polishing aluminum foils. Based on these high active SERS systems, surface enhanced Raman scattering (SERS) of Azo Dye Sudan were performed and carefully studied based on this highly active SERS substrate. High quality SERS spectra were obtained, which indicates that this kind of coarse aluminum foils is an active SERS substrate. Numbers of additional modes were presented, as well as some split peaks, which may be a consequence of symmetry lowering.

Surface-enhanced Raman scattering of water in ethanol: Electrolytic concentration dependence

With water in ethanol, we can observe surface-enhanced Raman scattering (SERS) of water molecules at electrolytic concentrations as low as 0.02 M; in the pure-water SERS systems without ethanol, however, electrolytic concentrations higher than 1 M are required to observe SERS of water molecules. Ethanol seems to be very effective in breaking the hydrogen-bonding network of water, and the freed water molecules are better adsorbed at the electrode surface in the form of hydration shells around the electrolytic ions.

Ground-state charge transfer as a mechanism for surface-enhanced Raman scattering

A model is presented for the contribution of ground-state charge transfer between a metal and adsorbate to surface-enhanced Raman scattering (SERS). It is shown that this contribution can be understood using the vibronic theory for calculating Raman intensities. The enhancement is due to vibronic coupling of the molecular ground state to the metal states, the coupling mechanism being a modulation of the ground-state charge-transfer energy by the molecular vibrations. An analysis of the coupling operator gives the selection rules for this process, which turn out to be dependent on the overall symmetry of the adsorbate-metal system, even if the charge transfer is small enough for the symmetry of the adsorbate to remain the same as that of the free molecule. It is shown that the model can yield predictions on the properties of SERS, e.g., specificity to adsorption geometry, appearance of forbidden bands, dependence on the applied potential, and dependence on the excitation wavelength. The predictions are in good agreement with experimental results. It is also deduced from this model that in many cases atomic-scale roughness is a prerequisite for the observation of SERS. A result on the magnitude of the enhancement can only be given in a crude approximation. Although in most cases an additional electromagnetic enhancement seems to be necessary to give an observable signal, this charge-transfer mechanism should be important in many SERS systems.