Raman Enhancement Research Articles

Raman enhancement induced by exciton hybridization in molecules and 2D materials

Surface-enhanced Raman spectroscopy (SERS) is a powerful technique for trace-level fingerprinting. Recently, layered two-dimensional (2D) materials have gained significant interest as SERS substrates for providing stable, uniform, and reproducible Raman enhancement with the potential for trace-level detection. Yet, the development of effective 2D SERS substrates is still hindered by the lack of fundamental understanding of the coupling mechanism between target molecules and substrates. Here, we report a systematic excitation-dependent Raman spectroscopy investigation on the coupling between 2D materials such as SnS2, MoS2, WSe2, and graphene and small organic molecules like rhodamine 6G (Rh 6G). Strong coupling between SnS2 and Rh 6G is found due to their degenerate excitons through Raman excitation profiles (REP), leading to the enhancement of Rh 6G vibrational modes that are observable down to 10−13 M. Our study shows that exciton coupling in the substrate-adsorbate complex plays a vital role in the Raman enhancement effect, opening a new route for designing SERS substrates for high sensitivity.

Gold-Deposited Graphene Nanosheets for Self-Cleaning Graphene Surface-Enhanced Raman Spectroscopy with Superior Charge-Transfer Contribution.

The interaction of graphene with metals initiates charge-transfer interaction-induced chemical enhancements, which critically depend on the doping effect from deposited metallic configurations. In this paper, we have explored the gold nanoparticle-decorated monolayer graphene nanosheets for the large graphene-induced Raman enhancement of adsorbed analytes, indicating the surface-enhanced Raman spectroscopy (SERS) capabilities of metal-doped graphene (G-SERS). Here, the systematically sputtered Au thickness optimization procedure revealed noticeable modifications in the graphene Raman spectra and photoluminescence (PL) background quenching, which indicated favorable charge transfer through n-type doping of chemical vapor deposition-grown graphene nanosheets. The highly consistent, individually distributed morphology of the gold nanoislands over graphene nanosheets depicted a reproducibly uniform G-SERS signal with excellent relative standard deviation values (<5%), resulting in the strongest Raman intensity enhancement factors of ∼108 (MB) (methylene blue) and 107 (DPA) (2,6-pyridinedicarboxylic acid) composed of the weakest PL background. The combined charge-transfer-induced chemical enhancement and electromagnetic enhancement from individual Au nanoislands result in a lowering of detectability down to 10-16 M (MB) and 10-11 M (DPA) concentrations with efficient time-dependent signal stability. Additionally, the GAu demonstrated its effective (∼94.4%) photocatalytic degradation capabilities by decomposing MB dye molecules from a concentration of 1 μM to 2.52 fM within 60 min. Therefore, the prominent charge-transfer contribution through controlled Au decoration over graphene nanosheets provides a potential strategy for fabricating superior SERS sensors and photocatalysts exhibiting adequate signal consistency, stability, and photodegradation efficiency through overcoming the limitations of the traditional sensing platforms.

The structure of chemical vapor deposited graphene substrates for graphene-enhanced Raman spectroscopy

Defects and nanocrystalline grain structures play a critical role in graphene-enhanced Raman spectroscopy (GERS). In this study, we selected three types of few-layer, polycrystalline graphene films produced by chemical vapor deposition (CVD), and we tested them as GERS substrates. The graphene structure was controlled by decreasing the CVD temperature, thus obtaining (i) polycrystalline with negligible defect density, (ii) polycrystalline with high defect density, (iii) nanocrystalline. We applied rhodamine 6G as a probe molecule to investigate the Raman enhancement. Our results show that nanocrystalline graphene is the most sensitive GERS substrate, indicating that the GERS effect is primarily connected to the nanocrystalline structure, rather than to the presence of defects.

Photoluminescence emission and Raman enhancement in TERS: an experimental and analytic revisiting

Abstract An analytic model is used to calculate the Raman and fluorescence enhancement of a molecule in between two closely spaced gold nanospheres. Instead of using the conventional approach that only the dipolar plasmonic mode is considered, we calculate the electric field enhancement in the nanometre sized gap, by taking account of the higher order modes in one gold sphere, which couples to the dipolar mode of the other sphere. The experimental confirmation is performed by gap-dependent tip-enhanced Raman spectroscopy (TERS) measurements. The photoluminescence and Raman enhancement are both observed with different growing trends as the gap width decreases. Red-shift of the background spectra is observed and implies the increasing coupling between the nanospheres. This analytic model is shown to be able to interpret the enhancement mechanisms underlying gap-dependent TERS experimental results.

The Synergistic Effect on the Mimetic Optical Structure of Feline Eyes toward Household Health Monitoring of Acute and Chronic Diseases.

A breakthrough in the performance of bionic optical structures will only be achieved if we can obtain an in-depth understanding of the synergy mechanisms operating in natural optical structures and find ways to imitate them. In this work, inspired by feline eyes, an optical substrate that takes advantage of a synergistic effect that occurs between resonant and reflective structures was designed. The synergistic effect between the reflective and resonant components leads to a Raman enhancement factor (EF) of 1.16 × 107, which is much greater than that achieved using the reflective/resonant cavities on their own. Finite-difference time-domain (FDTD) simulations and experimental results together confirm that the mechanism of this synergistic effect is achieved by realizing multiple reflections and repeated absorptions of light, generating a strong local electric field. Thus, a 2-3 order of magnitude increase in sensitivity could be achieved. More importantly, with the homemade centrifugal device, above optical substrates were further used to develop a rapidly highly sensitive household health monitoring system (detection time <3 min). It can thus be used to give early warning of acute diseases with high risk (e.g., acute myocardial infarction (AMI) and cerebral peduncle). Due to the good reusability and storability (9% and 8% reduction in EF after washing 30 times and 9 months of storage, respectively) of the substrates, the substrates thus reduce detection costs (to ∼$1), making them much cheaper to use than the current gold-standard methods (e.g., ∼$16 for gout detection).

Porous carbon film/WO3-x nanosheets based SERS substrate combined with deep learning technique for molecule detection

The Surface-enhanced Raman scattering (SERS) is an attractive optical detecting method with high sensitivity and detectivity, however challenges on large-area signal uniformity and complex spectra analysis methods always retards its wide application. Herein, a highly sensitive and uniform SERS detection strategy supported by porous carbon film/WO3-x nanosheets (PorC/WO3-x) based noble-metal-free SERS substrate and deep learning algorithm are reported. Experimentally, the PorC/WO3-x substrate was prepared by high-temperature annealing the PorC/WO3 films under the argon atmosphere. The defect density of the WO3 was controlled by tuning the reducing reaction time during the annealing process. The SERS performance was evaluated by using R6G as the Raman reporter, it showed that the SERS intensity obtained on the substrate with the optimal annealing time of 3 h was about 8 times as high as that obtained on the PorC/WO3 substrate without annealing treatment. And detection limit of 10-7 M and Raman enhancement factor of 106 could be achieved. Moreover, the above optimal SERS substrate was utilized to detect flavonoids of quercetin, 3-hydroxyflavone and flavone, and a deep learning algorithms was incorporated to identify the quercetin. It revealed that quercetin can be accurately detected within the above flavonoids, and lowest detectable concentration of 10-5 M can be achieved.

Electrochemically generated CuI and CuSCN nanocrystals on Cu surfaces as Raman enhancing substrates

Raman enhancing strategies, such as Surface-Enhance Raman scattering (SERS), are a key piece for the development of spectroscopic and analytical strategies based on Raman spectroscopy, due to the intrinsic low sensitivity of the Raman scattering. Some years ago, our group reported an unexpected Raman enhancement process observed during the electrochemical oxidation of metallic electrodes, named Electrochemical Oxidation Surface-Enhanced Raman scattering (EC-SOERS). This Raman enhancement phenomenon was recently explained as an interaction of the analyte and the SERS dielectric substrate promoted by a metal cation. The elucidation of the origin of this enhancement is now leading to the development of new Raman enhancing substrates, such as copper-based substrates. In this work, we present an overview of the use of copper electrodes as EC-SOERS substrates. The presented strategies allow the electrosynthesis of SERS-active CuI nanocrystals on a metallic copper surface, which provides Raman enhancement for a wide number of molecules. The influence of the electrochemical conditions and the structure of the studied molecules are discussed. The use of CuSCN nanocrystals is also explored as substrates to promote Raman enhancement.

Visible-frequency plasmonic enhancement at the edge of graphene/h-BN heterostructures on silicon substrate

Heterostructures of graphene and hexagonal boron nitride (G/h-BN) have been widely studied for controlling and utilizing graphene electronic properties. Here we characterize specific optical and electronic properties of G/h-BN heterostructures made of a high-quality single layer chemical vapor deposition (CVD) graphene laid over h-BN flakes, with focus on plasmonic effects. We compare the G/h-BN properties on Si and SiO2 substrates by micro-Raman spectroscopy mapping, Kelvin probe force microscopy, optical and atomic force microscopy. We observe highly enhanced Raman intensity (up to 280 %) from Si as well as graphene along the G/h-BN edge. It is attributed to localized concentration of electrons in graphene and suitable perpendicular orientation of plasmonic vibrations at the edge. The plasmonic Raman enhancement occurs under a visible light excitation (532 nm) and the effect can be tuned by the h-BN flake thickness (10–150 nm). The enhancement is specific to G/h-BN/Si structures, on G/h-BN/SiO2 structures the Raman signal is suppressed while I2D/IG ratio is increased. Vice versa, change of surface potential under visible light illumination (photovoltage) is on G/h-BN/Si negligible (within 10 mV) compared to the G/h-BN/SiO2 structures. These results open new prospects for broad utilization of localized visible plasmonic effects in graphene.

A Compact Device of Optical Fiber Taper Coupled Monolayer Silver Nanoparticles for Raman Enhancement

A Compact Device of Optical Fiber Taper Coupled Monolayer Silver Nanoparticles for Raman Enhancement

Enhancing charge transfer in a W18O49/g-C3N4 heterostructure via band structure engineering for effective SERS detection and flexible substrate applications.

Chemical mechanism (CM)-related surface-enhanced Raman spectroscopy (SERS) has received tremendous interest due to its exceptional stability and excellent uniformity. Nevertheless, there remains a demand for ingenious methodologies for promoting effective charge transfer (CT) to improve SERS sensitivity further. Herein, a band structure engineered W18O49/g-C3N4 heterostructure (WCN) was first employed as a CM-based SERS substrate with remarkable enhancement and sensitivity. To investigate the Raman enhancement properties of the substrate, malachite green (MG) was employed as the Raman probe with the excitation of a 633 nm laser. The WCN substrate exhibits a Raman enhancement factor (EF) of 2.6 × 107, achieving a limit of detection (LOD) of 1.9 × 10-10 M for MG. The outstanding Raman amplification behavior can be attributed to the heterojunction-induced efficient CT process, energy band matching resonance due to minor doping with g-C3N4 serving as a band gap modifier, and improved photo-induced charge transfer (PICT) efficiency via the oxygen vacancies in the W18O49 units. Additionally, a flexible SERS substrate based on WCN was constructed using a vacuum filtration method and utilized to detect prohibited pharmaceutical residues on fish skin. The integration of this WCN and a nylon membrane not only preserves the Raman activity of the WCN for sensitive detection but also endows the Raman substrate with high flexibility and good mechanical durability, making it a potential candidate for in situ detection in particular environments.

Unveiling brain disorders using liquid biopsy and Raman spectroscopy.

Brain disorders, including neurodegenerative diseases (NDs) and traumatic brain injury (TBI), present significant challenges in early diagnosis and intervention. Conventional imaging modalities, while valuable, lack the molecular specificity necessary for precise disease characterization. Compared to the study of conventional brain tissues, liquid biopsy, which focuses on blood, tear, saliva, and cerebrospinal fluid (CSF), also unveils a myriad of underlying molecular processes, providing abundant predictive clinical information. In addition, liquid biopsy is minimally- to non-invasive, and highly repeatable, offering the potential for continuous monitoring. Raman spectroscopy (RS), with its ability to provide rich molecular information and cost-effectiveness, holds great potential for transformative advancements in early detection and understanding the biochemical changes associated with NDs and TBI. Recent developments in Raman enhancement technologies and advanced data analysis methods have enhanced the applicability of RS in probing the intricate molecular signatures within biological fluids, offering new insights into disease pathology. This review explores the growing role of RS as a promising and emerging tool for disease diagnosis in brain disorders, particularly through the analysis of liquid biopsy. It discusses the current landscape and future prospects of RS in the diagnosis of brain disorders, highlighting its potential as a non-invasive and molecularly specific diagnostic tool.

Photonic-plasmonic resonator for SERS biodetection.

To improve the laser utilization efficiency and avoid photodamage in surface-enhanced Raman spectroscopy (SERS), it is imperative to introduce photon technology into the field of SERS detection. A major challenge is the inefficient interaction between the substrate and the incident wavelength, resulting in limited Raman enhancement at a relatively low level. Here, we sputtered plasmonic Au nanoparticles (NPs) onto photonic TiOx nanocavities, creating a novel hybrid photonic-plasmonic resonator that achieves a large degree of optical manipulation and long-term localization. By facilely controlling the size of Au NPs, the resonance wavelength of plasmonic Au NPs can be matched with the photonic nanocavity to maximize the light trapping intensity, which leads to a synergistic enhancement of SERS via the electromagnetic and chemical mechanisms, resulting in a SERS enhancement up to 1.75 × 109 under non-resonant excitation. In particular, the substrate can achieve strong absorption and localization for long wavelengths, thus enabling a large SERS enhancement with a small light intensity, which can effectively avoid the photodamage that may occur in Raman testing. The substrate can detect various biomolecules, including biomarkers in serum, thus realizing the differentiation of different cancers. This study provides a powerful and sensitive platform for SERS, facilitating bioanalysis and disease diagnosis in complex systems.

Dynamic repulsive interaction enables an asymmetric electron-phonon coupling for improving Raman scattering.

Two-dimensional (2D) materials are an excellent platform for surface-enhanced Raman spectroscopy (SERS). For ReS2, the Raman enhancement effect can be highly improved through the dipole-dipole interactions and synergistic resonance effects in the phase-engineering ReS2 films. However, the performance of the substrate can be improved further through regulating the electronic interaction between the ReS2 and probe molecules. Herein, a dynamic coulomb repulsion strategy is proposed to trigger an electronic state redistribution by asymmetric electrostatic interactions. With the phase-engineering ReS2/graphene heterostructure as a prototype, under laser excitation, the generated hot electrons in graphene and ReS2 can repel each other due to Coulomb interaction, which breaks the symmetrical distribution of hot electrons in ReS2, and increases the electronic concentration at the interface between ReS2 and the probe molecule. With R6G as the probe molecule, the asymmetric electron distribution and synergistic resonance effects on their interface improve the limit of detection to 10-12 M with an EF of 2.15 × 108. Meanwhile, the heterostructure also shows good uniformity, stability as well as unique anisotropy. This strategy can be generalized to other 2D heterostructures to obtain the ultrasensitive SERS substrates.

Flexible nanohybrid substrates utilizing gold nanocubes/nano mica platelets with 3D lightning-rod effect for highly efficient bacterial biosensors based on surface-enhanced Raman scattering.

In this study, gold nanocubes (AuNCs) were quickly synthesized using the seed-mediated growth method and reduced onto the surface of two-dimensional (2D) delaminated nano mica platelets (NMPs), enabling the development of AuNCs/NMPs nanohybrids with a 3D lightning-rod effect. First, the growth-solution amount can be changed to easily adjust the AuNCs average-particle size within a range of 30-70 nm. The use of the cationic surfactant cetyltrimethylammonium chloride as a protective agent allowed the surface of AuNCs and nanohybrids to be positively charged. Positively charged nanohybrid surfaces presented a good adsorption effect for detecting molecules with negative charges on the surface. Additionally, the NMP surfaces were rich in ionic charges and provided a large specific surface area for stabilizing the growth of AuNCs. Delaminated AuNCs/NMPs nanohybrids can generate a 3D hotspot effect through self-assembly to enhance the Raman signal. Surface-enhanced Raman scattering (SERS) is highly sensitive in detecting adenine biomolecules. Its limit of detection (LOD) and Raman enhancement factor reached 10-9 M and 3.6 × 108, respectively. Excellent reproducibility was obtained owing to the relatively regular arrangement of AuNC particles, and the relative standard deviation (RSD) was 10.7%. Finally, the surface of NMPs was modified by adding the hydrophilic poly(oxyethylene)-diamine (POE2000) and amphiphilic PIB-POE-PIB copolymer at different weight ratios. The adjustment of the surface hydrophilicity and hydrophobicity of AuNCs/NMPs nanohybrids led to better adsorption and selectivity for bacteria. AuNCs/POE/NMPs and AuNCs/PIB-POE-PIB/NMPs were further applied to the SERS detection of hydrophilic Staphylococcus aureus and hydrophobic Escherichia coli, respectively. The SERS-detection results suggest that the LOD of hydrophilic Staphylococcus aureus and hydrophobic Escherichia coli reached 92 CFU mL-1 and 1.6 × 102 CFU mL-1, respectively. The AuNCs/POE/NMPs and AuNCs/PIB-POE-PIB/NMPs nanohybrids had different hydrophilic-hydrophobic affinities, which greatly improved the selectivity and sensitivity for detecting bacteria with different hydrophilicity and hydrophobicity. Therefore, fast, highly selective, and highly sensitive SERS biological-detection results were obtained.

Food-borne bacteria analysis using a diatomite bioinspired SERS platform.

Rapid and sensitive detection of food-borne bacteria has remained challenging over the past few decades. We propose a surface-enhanced Raman scattering sensing strategy based on a novel bioinspired surface-enhanced Raman scattering substrate, which can directly detect dye molecular residues and food-borne pathogen microorganisms in the environment. The surface-enhanced Raman scattering platform consists of a natural diatomite microporous array decorated with a metal-phenolic network that enables the in situ reduction of gold nanoparticles. The as-prepared nanocomposites display excellent surface-enhanced Raman scattering activity with the lowest limit of detection and the maximum Raman enhancement factor of dye molecules up to 10-11 M and 1.18 × 107, respectively. For food-borne bacterial detection, a diatomite microporous array decorated with a metal polyphenol network and gold nanoparticle-based surface-enhanced Raman scattering analysis is capable of distinguishing the biochemical fingerprint information of Staphylococcus aureus and Escherichia coli, indicating the great potential for strain identification.

Waveguide‐based Raman enhancement strategies

AbstractWaveguide‐enhanced Raman scattering (WERS) is a powerful branch of enhanced Raman technologies that has gained significant progress in recent years because of its advantages, such as reproducibility and robustness. As a complementary tool to surface‐enhanced Raman spectroscopy (SERS), WERS provides a powerful solution for reproducible quantification of analytes. According to different Raman enhancement mechanisms, five major WERS implementation strategies, namely, (1) single‐mode dielectric waveguide, (2) liquid core waveguide, (3) metal cladding waveguide, (4) resonance mirror waveguide, and (5) double metal cladding waveguide, are classified and described in detail in this review. The flexibility of WERS structures makes them easy to be integrated with 2D devices to obtain a complete on‐chip detection scheme, allowing the WERS chip to combine excitation, detection, and data analysis in integrated chips, providing a powerful prospect for real‐time and on‐site analysis of target samples. This article highlights the principles, implementations, and application scenarios of WERS techniques and evaluates their advantages and limitations, respectively. Finally, the strengths and weaknesses of WERS techniques are summarized, and promising future applications are proposed. This review provides a panoramic view for researchers interested in waveguide‐enhanced Raman technology.

Urease-Powered Micromotors with Spatially Selective Distribution of Enzymes for Capturing and Sensing Exosomes.

Enzyme-catalyzed micro/nanomotors (MNMs) exhibit tremendous potential for biological isolation and sensing, because of their biocompatibility, versatility, and ready access to biofuel. However, flow field generated by enzyme-catalyzed reactions might significantly hinder performance of surface-linked functional moieties, e.g., the binding interaction between MNMs and target cargos. Herein, we develop enzymatic micromotors with spatially selective distribution of urease to enable the independent operation of various modules and facilitate the capture and sensing of exosomes. When urease is modified into the motors' cavity, the flow field from enzyme catalysis has little effect on the exterior surface of the motors. The active motion and encapsulating urease internally result in enhancement of ∼35% and 18% in binding efficiency of target cargos, e.g., exosomes as an example here, compared to their static counterparts and moving micromotors with urease modified externally, respectively. Once exosomes are trapped, they can be transferred to a clean environment by the motors for Raman signal detection and/or identification using the surface Raman enhancement scattering (SERS) effect of coated gold nanoshell. The biocatalytic micromotors, achieving spatial separation between driving module and function module, offer considerable promise for future design of multifunctional MNMs in biomedicine and diagnostics.

Tungsten Nitride with a Two-Dimensional Multilayer Structure for Boosting the Surface-Enhanced Raman Effect.

The development of high-performance surface-enhanced Raman scattering (SERS) substrates is an urgent and important task. Here, tungsten nitride (WN) with a two-dimensional (2D) multilayer structure has been successfully prepared through a nitriding WO2.90 precursor. In addition to the highly active "hot spots" formed on the surface of the WN sheets, a large number of gaps between the nanosheets also exhibit a strong local surface plasmon resonance effect, which greatly improves the SERS activity. Evaluated as the SERS substrate, the WN with a 2D multilayer structure exhibits good SERS characteristics and good homogeneity and stability, even after strong acid, strong alkali, or long-term light treatment. Significantly, typical environmental contaminants such as dichlorophenol and butylated hydroxyanisole also exhibit strong Raman enhancement signals. This research provides a new method for designing inexpensive, high-activity, and universal SERS substrates.

Combinatorial Approach to Find Nanoparticle Assemblies with Maximum Surface-Enhanced Raman Scattering.

Plasmonic nanoparticles exhibit unique properties that distinguish them from other nanomaterials, including vibrant visible colors, the generation of local electric fields, the production of hot charge carriers, and localized heat emission. These properties are particularly enhanced in the narrow nanogaps formed between nanostructures. Therefore, creating nanogaps in a controlled fashion is the key to achieving a fundamental understanding of plasmonic phenomena originating from the nanogaps and developing advanced nanomaterials with enhanced performance for diverse applications. One of the most effective approaches to creating nanogaps is to assemble individual nanoparticles into a clustered structure. In this study, we present a fast, facile, and highly efficient method for preparing core@satellite (CS) nanoassembly structures using gold nanoparticles of various shapes and sizes, including nanospheres, nanocubes (AuNCs), nanorods, and nanotriangular prisms. The sequential assembly of these building blocks on glass substrates allows us to obtain CS nanostructures with a 100% yield within 4 h. Using 9 different building blocks, we successfully produce 16 distinct CS nanoassemblies and systematically investigate the combinations to search for the highest Raman enhancement. We find that the surface-enhanced Raman scattering (SERS) intensity of AuNC@AuNC CS nanoassemblies is 2 orders of magnitude larger than that of other CS nanoassemblies. Theoretical analyses reveal that the intensity and distribution of the electric field induced in the nanogaps by plasmon excitation, as well as the number of molecules in the interfacial region, collectively contribute to the unprecedentedly large SERS enhancement observed for AuNC@AuNC. This study not only presents a novel assembly method that can be extended to produce many other nanoassemblies but also identifies a highly promising SERS material for sensing and diagnostics through a systematic search process.

Multiple‐Resonance‐Enhanced Raman Spectroscopy in 2D‐Material‐Capped Tapered‐Fiber Microcavity

AbstractPlasmon‐free surface‐enhanced Raman spectroscopy (SERS) assisted by charge‐transfer (CT) resonance in semiconductors has drawn considerable attention in the past decades due to the extraordinary advantages in chemical stability and homogeneity. Unfortunately, the weak confinement of excitation light in semiconductor nanostructures and 2D materials, due to either their limited refractive indexes or atomic thickness, results in the Raman enhancement by nonmetallic SERS substrates significantly lower than the noble ones. Here a novel plasmon‐free SERS probe is reported by a tapered optical fiber (TOF) coated with monolayer‐MoS2 (ML‐MoS2), where the TOF‐supported whispering‐gallery modes (WGMs) simultaneously regulate multiple‐resonance processes, i.e., excitonic resonance, molecular resonance, charge‐transfer resonance and fluorescence resonance energy transfer processes, in the ML‐MoS2 and analytes. The contribution of the four processes promoted by WGM to enhancement factor of Raman intensity (EFRI) is quantitatively determined by four dye molecules with different energy levels. The Raman enhancement mechanism of WGM‐promoted multiple‐resonances is therefore revealed, for the first time. The maximum EFRI is up to 1.8 × 109 for the limit of detection (LoD) down to 10−14 M. The ML‐MoS2/TOF SERS probes also demonstrated their outstanding feasibility and stability facilitating to trace detection in microdroplets for practical applications in future.