SERS Signal Enhancement Research Articles

Coupling annealed silver nanoparticles with a porous silicon Bragg mirror SERS substrate and machine learning for rapid non-invasive disease diagnosis.

Ag2O-Ag-porous silicon Bragg mirror (PSB) composite SERS substrates were successfully synthesized by using a combination of electrochemical and thermochemical methods. Test results showed that the SERS signal increased and decreased as the annealing temperature used for the substrate increased, where the most intense SERS signal was obtained using a substrate annealed at 300°C. Stability test results showed substantial enhancement of the SERS signal intensity of the Ag2O-Ag-PSB composite one month after preparation compared with that of conventional Ag-PSB. We conclude that Ag2O nanoshells play an essential role in SERS signal enhancement. Ag2O prevents natural oxidation of Ag nanoparticles (AgNPs) and has a solid localized surface plasmon resonance (LSPR). SERS signal enhancement was tested using this substrate for serum from patients with Sjögren's syndrome (SS) and Diabetic nephropathy (DN), as well as from healthy controls (HC). SERS feature extraction was performed using principal component analysis (PCA). The extracted features were analyzed by a support vector machine (SVM) algorithm. Finally, a rapid screening model for SS and HC, as well as DN and HC, was developed and used to perform controlled experiments. The results showed that the diagnostic accuracy, sensitivity and selectivity for SERS technology combined with machine learning algorithms reached 90.7%, 93.4% and 86.7% for SS/HC and 89.3%, 95.6% and 80% for DN/HC, respectively. The results of this study show that the composite substrate has excellent potential to be developed into a commercially available SERS chip for medical testing.

Silent-enhancement of multiple Raman modes via tuning optical properties of graphene nanostructures

Raman scattering signal can be enhanced through localization of incident field into sub-wavelength hot-spots through plasmonic nano-structures (Surface-enhanced Raman scattering-SERS). Recently, further enhancement of SERS signal via quantum objects are proposed by [1] without increasing the hot-spot intensity (\textit{silent-enhancement}) where this suggestion prevents the modification of vibrational modes or the breakdown of molecules. The method utilizes path interference in the non-linear response of Stokes-shifted Raman modes. In this work, we extend this phenomenon to tune the spectral position of \textit{silent-enhancement} factor where the multiple vibrational modes can be detected with a better signal-to-noise ratio, simultaneously. This can be achieved in two different schemes by employing either (i) graphene structures with quantum emitters or (ii) replacing quantum emitters with graphene spherical nano-shell in \cite{Postaci2018}. In addition, the latter system is exactly solvable in the steady-state. These suggestions not only preserve conventional non-linear Raman processes but also provide flexibility to enhance (silently) multiple vibrational Raman modes due to the tunable optical properties of graphene.

Ameliorating SERS Sensitivity for Pesticide Malathion Detection with Synergistic Boosting Effect by Hydrogen Cations and Chloride Anions.

Although SERS has been widely recognized as one of the highly sensitive analytical methods that can be deployed in the field with high sensitivity and short analysis time, reports regarding the fast determination of malathion at low concentrations are still scarce. Here, in this work, the solution pH and various halogen co-adsorbates were explored to promote the SERS signal of malathion using the citrate-reduced Ag NPs. It was found that chloride anions were the most efficient signal booster among the three halogen ions screened. Further examination of the SERS profile of the malathion in the presence of different halogen species found that the stretching mode of the P-S bond shifted to a lower frequency with Cl-, which may imply closer (and stronger) binding of malathion to the Ag NPs. This concurs with literature reports that halogen ions could facilitate the adsorption of a certain analyte onto the SERS substrate. In addition, hydrogen ions showed a synergistic effect on SERS signal enhancement when combined with chloride anions. At optimum conditions, the malathion could be detected with a limit of detection (LOD) of 3 ppb. Malathion-spiked cherry tomatoes and oranges were analyzed, and the recovery rates were found to be within 85-100%.

Colorimetry and SERS dual-mode sensing of serotonin based on functionalized gold nanoparticles

In this study, we reported a colorimetry and SERS dual-mode sensing of serotonin (5-HT) based on functionalized gold nanoparticles (AuNPs). Based on the amino and hydroxyl groups in 5-HT can react with dithiobis succinimidyl propionate (DSP) and N-acetyl-L-cysteine (NALC) respectively, we synthesized two kinds of functionalized AuNPs (DSP-AuNPs and NALC-AuNPs). A double interaction between functionalized nanoparticles and the hydroxyl and the amino group of serotonin led to interparticle-crosslinking aggregation. The aggregation of the two functionalized AuNPs can cause the plasmon coupling of AuNPs resulting in a color change visible to the naked eye and the enlargement of SERS “hot spot” area and the enhancement of SERS signal. Furthermore, two kinds of functionalized AuNPs can specifically recognize 5-HT and effectively reduce the interference of biomolecules with similar structure to 5-HT in the experiment. This dual-mode system has the advantages of low detection limit, high sensitivity and good selectivity, and the detection limit is 0.15 nmol L-1. Besides, the system was applied to the determination of 5-HT content in human serum, and the relative standard deviation (RSD) was lower than 3.75%, which indicated that the system had a good application prospect in the determination of biological samples.

Optimizing Gold Nanoparticle Size and Shape for the Fabrication of SERS Substrates by Means of the Langmuir-Blodgett Technique.

The Langmuir–Blodgett technique, in which a layer of nanoparticles is spread at the water/air interface and further transferred onto a solid support, is a versatile approach for the preparation of SERS substrates with a controllable arrangement of hotspots. In a previous work, we demonstrated that fine-tuning the lateral packing and subsequent seed growth of 10 nm gold nanoparticles led to a quasi-resonant enhanced in the SERS signal of a test analyte. Here, we explore further enhancements by modifying the size and shape of the spread gold nanoparticles in order to take advantage of the inherent interparticle repulsion mechanisms present at the interface. We show that the size of the used nanoparticles is also a determinant factor, which cannot be compensated by the subsequent electroless growth. We also show that, although the seeded growth leads to rough hotspots, the sensitivity can be optimized by self-assembling urchin-shaped nanoparticles, with a roughness that is fine-tuned a priori. Our results suggest an intriguing correlation between surface homogeneity and SERS signal enhancement, indicating that regular substrates will have the optimal performance.

Colloidal lithography with electrochemical nickel deposition as a unique method for improved silver decorated nanocavities in SERS applications

Two types of metallised nanocavities (single and hybrid) were fabricated by colloid lithography followed by electrochemical deposition of Ni and subsequently Ag layers. Introductory Ni deposition step iniciates more homogenous decoration of nanocavities with Ag nanoparticles. Silver nanocavity decoration has been so performed with lower nucleation rate and with Ag nanoparticles homogeinity increase. By this, two step Ni and Ag deposition trough polystyrene nanospheres (100, 300, 500, 700, 900nm), the various Ag surfaces were obtained. Ni layer formation in the first step of deposition enabled more precise controlling of Ag film deposition and thus final Ag surface morphology. Prepared substrates were tested as active surfaces in SERS application. The best SERS signal enhancement was observed at 500nm Ag nanocavities with normalised thickness Ni layer ∼0.5. Enhancement factor has been established at value 1.078×1010; time stability was determined within 13 weeks; charge distribution at nanocavity Ag surfaces as well as reflection spectra were calculated by FDTD method. Newly prepared nanocavity surface can be applied in SERS analysis, predominantly.

Controlled Growth of Gold Nanostars: Effect of Spike Length on SERS Signal Enhancement.

Two different types of gold nanostars (Au NS), namely, short-spiked nanostars (SSNS) and long-spiked nanostars (LSNS), are prepared by using a hexagonal lyotropic liquid-crystalline (LLC) phase as a template. The formation, size and length of spikes or arms of the resultant Au NS are controlled by preparation in either a hexagonal LLC phase or an isotropic phase. These NS are anchored onto indium tin oxide (ITO) electrodes through a self-assembled monolayer of 3-mercaptopropyltrimethoxysilane, which acts as a linker molecule. Structural and morphological characterisations of SSNS- and LSNS-anchored ITO electrodes are performed by means of microscopic and spectroscopic analyses. Further electrochemical techniques, namely, cyclic voltammetry and electrochemical impedance spectroscopy, are also used to confirm the immobilisation of these Au NS on ITO electrodes and to study the electrochemical characteristics. These studies clearly reveal the formation of star-shaped, branched, anisotropic nanostructures of gold during the template preparation method and these Au NS are successfully anchored onto ITO electrodes through a covalent immobilisation strategy. Furthermore, the SERS activity of these Au NS is analysed by using glutathione and crystal violet as analytes and by employing glass and ITO as substrates. It is interesting to note that SSNS show a significant enhancement in SERS signals relative to those of LSNS.

A surface enhanced Raman scattering quantitative analytical platform for detection of trace Cu coupled the catalytic reaction and gold nanoparticle aggregation with label-free Victoria blue B molecular probe

With development of economy and society, there is an urgent need to develop convenient and sensitive methods for detection of Cu2+ pollution in water. In this article, a simple and sensitive SERS sensor was proposed to quantitative analysis of trace Cu2+ in water. The SERS sensor platform was prepared a common gold nanoparticle (AuNP)-SiO2 sol substrate platform by adsorbing HSA, coupling with the catalytic reaction of Cu2+-ascorbic acid (H2A)-dissolved oxygen, and using label-free Victoria blue B (VBB) as SERS molecular probes. The SERS sensor platform response to the AuNP aggregations by hydroxyl radicals (•OH) oxidizing from the Cu2+ catalytic reaction, which caused the SERS signal enhancement. Therefore, by monitoring the increase of SERS signal, Cu2+ in water can be determined accurately. The results show that the SERS sensor platforms owns a linear response with a range from 0.025 to 25μmol/L Cu2+, and with a detection limit of 0.008μmol/L. In addition, the SERS method demonstrated good specificity for Cu2+, which can determined accurately trace Cu2+ in water samples, and good recovery and accuracy are obtained for the water samples. With its high selectivity and good accuracy, the sensitive SERS quantitative analysis method is expected to be a promising candidate for determining copper ions in environmental monitoring and food safety.

Correlative SEM SERS for quantitative analysis of dimer nanoparticles.

A Raman microscope integrated with a scanning electron microscope was used to investigate plasmonic structures by correlative SEM-SERS analysis. The integrated Raman-SEM microscope combines high-resolution electron microscopy information with SERS signal enhancement from selected nanostructures with adsorbed Raman reporter molecules. Correlative analysis is performed for dimers of two gold nanospheres. Dimers were selected on the basis of SEM images from multi aggregate samples. The effect of the orientation of the dimer with respect to the polarization state of the laser light and the effect of the particle gap size on the Raman signal intensity is observed. Additionally, calculations are performed to simulate the electric near field enhancement. These simulations are based on the morphologies observed by electron microscopy. In this way the experiments are compared with the enhancement factor calculated with near field simulations and are subsequently used to quantify the SERS enhancement factor. Large differences between experimentally observed and calculated enhancement factors are regularly detected, a phenomenon caused by nanoscale differences between the real and 'simplified' simulated structures. Quantitative SERS experiments reveal the structure induced enhancement factor, ranging from ∼200 to ∼20 000, averaged over the full nanostructure surface. The results demonstrate correlative Raman-SEM microscopy for the quantitative analysis of plasmonic particles and structures, thus enabling a new analytical method in the field of SERS and plasmonics.

SERS Substrates by the Assembly of Silver Nanocubes: High-Throughput and Enhancement Reliability Considerations

Small clusters of nanoparticles are ideal substrates for SERS measurements, but the SERS signal enhancement by a particular cluster is strongly dependent on its structural characteristics and the measurement conditions. Two methods for high-throughput assembly of silver nanocubes into small clusters at predetermined locations on a substrate are presented. These fabrication techniques make it possible to study both the structure and the plasmonic properties of hundreds of nanoparticle clusters. The variations in SERS enhancement factors from cluster to cluster were analyzed and correlated with cluster size and configuration, and laser frequency and polarization. Using Raman instruments with 633 nm and 785 nm lasers and linear clusters of nanocubes, an increase in the reproducibility of the enhancement and an increase in the average enhancement values were achieved by increasing the number of nanocubes in the cluster, up to 4 nanocubes per cluster. By examining the effect of cluster configuration, it is shown that linear clusters with nanocubes attached in a face-to-face configuration are not as effective SERS substrates as linear clusters in which nanocubes are attached along an edge.

Physics in plasmonic and Mie scattered near-field for efficient surface-enhanced Raman scattering template

We describe the physics of the SERS based on the optical near-field intensity enhancement on the metallic (plasmonic) and the nonmetallic (Mie scattering) nanostructured substrates with two-dimensional (2D) periodic nanohole arrays. The calculation by the Finite-Difference Time-Domain (FDTD) method revealed that the optical intensity enhancement increases with the increase of the thickness of a gold film coating on the nonmetallic (dielectric) nanostructured Si, GaAs, and SiC substrates. The resonance spectrum shifts with the changes in the geometrical structure of the void diameter and inter-void distance. It was clarified that the optical intensity enhancement obtained with the gold-coated substrate is equivalent to that with a gold substrate at 70-nm thick gold coating on the dielectric substrates in this structure. The resonance spectral bandwidth for Mie scattering and plasmonic near-fields is different. Therefore, if the Stokes line of the Raman scattering is located within the resonance bandwidth, the SERS signal is enhanced proportionally to the fourth power of the electric near-field. However, if the Stokes shift is located out of the resonance bandwidth, the SERS signal enhancement is only proportional to the square of the scattered near-field.