New Nano Architecture for SERS Applications (original) (raw)
FDTD Study on Evolution of Trimer Silver@Silica Nanospheres to Dimer for SERS Characteristics
Plasmonics, 2021
Light enhancement occurs strongly within the plasmonic clusters by interaction with surface plasmons. Surface-enhanced Raman spectroscopic (SERS) characteristics of a series of silver@silica trimer core-shell (CS) nanosphere (NS) clusters are investigated in this paper. It is significant to understand the electric field (EF) enhancement mechanism behind the SERS technique. The effect of symmetry breaking is studied for the series starting from the highly symmetric trimer cluster and transformed to linear dimer geometry which progresses through the gradual reduction in the vertex NS. The optical activity such as the evolution of LSPR peak is discussed, the formation of hot spots is demonstrated and the strength of the local EF enhancement is calculated and correlated with the plasmon dipolar modes by using plasmon hybridization theory to understand the underlying physical concepts.
Nanoscale advances, 2022
The impact of variation in the interparticle gaps in dimers and trimers of gold nanoparticles (AuNPs), modified with Raman reporter (2-MOTP), on surface-enhanced Raman scattering (SERS) intensity, relative to the SERS intensity of a single AuNP, is investigated in this paper. The dimers, trimers, and single particles are investigated on the surfaces of four substrates: gold (Au), aluminium (Al), silver (Ag) film, and silicon (Si) wafer. The interparticle distance between AuNPs was tuned by selecting mercaptocarboxylic acids of various carbon chain lengths when each acid forms a mixed SAM with 2-MOTP. The SERS signal quantification was accomplished by combining maps of SERS intensity from a Raman microscope, optical microscope images (Â100), and maps/images from AFM or SEM. In total, we analysed 1224 SERS nanoantennas (533 dimers, 648 monomers, and 43 trimers). The average interparticle gaps were measured using TEM. We observed inverse exponential trends for the Raman intensity ratio and enhancement factor ratio versus gap distance on all substrates. Gold substrate, followed by silicon, showed the highest Raman intensity ratio (9) and dimer vs. monomer enhancement factor ratio (up to 4.5), in addition to the steepest inverse exponential curve. The results may help find a balance between SERS signal reproducibility and signal intensity that would be beneficial for future agglomerated NPs in SERS measurements. The developed method of 3 to 1 map combination by an increase in image transparency can be used to study structure-activity relationships on various substrates in situ, and it can be applied beyond SERS microscopy.
Rapid, solution-based characterization of optimized SERS nanoparticle substrates
Journal of The American Chemical Society, 2009
We demonstrate the rapid optical characterization of large numbers of individual metal nanoparticles freely diffusing in colloidal solution by confocal laser spectroscopy to guide nanoparticle engineering and optimization. We use ratios of the Rayleigh and Raman scattering response and rotational diffusion timescales of individual nanoparticles to show that hollow gold nanospheres and solid silver nanoparticle dimers linked with a bifunctional ligand, both specifically designed nanostructures, exhibit significantly higher monodispersity than randomly aggregated gold and silver nanoparticles.
Monomer functionalized silica coated with Ag nanoparticles for enhanced SERS hotspots
Applied Surface Science, 2018
Mesoporous silica (SiO 2) spheres are well-known for their excellent chromatographic properties such as the relatively high specific surface, large pore volume, uniform particle size, narrow pore size distribution with favorable pore connectivity; whereas the noble metal Ag nanoparticles have unique size/shape dependant surface plasmon resonance with wide ranging applications. Thus, the desire to synchronize both their properties for specific applications has naturally prompted research in the design and synthesis of core-shell type novel nanoAg@mesoSiO 2 nanocomposites, which display potential utility in applications such as photothermal therapy, photocatalysis, molecular sensing, and photovoltaics. In the present work, SiO 2 spheres were carefully functionalized with the monomer, N-vinyl pyrrolidone (NVP), which cohesively controls the uniform mass transfer of Ag + metal ions, thereby enabling its sequential reduction to zerovalent Ag (in the presence of slightly excess NaOH) by electron transfer from nucleophilic attack of the NVP vinyl group by the water molecules even under ambient conditions. Complete metal nanoshell coverage of the silica surface was obtained after multiple Ag deposition cycles, as systematically confirmed from the BET, TEM, optical and FTIR characterization. Our present Ag-coated silica spheres were directly utilized as viable SERS substrates with high sensitivity in contrast with other long chain polymer/surfactant coated silica spheres, owing to the presence of significant number of nanogaps enhanced SERS 'hotspots', which were methodically analyzed utilizing two example analytes, such as crystal violet (CV) and calendula officinalis (CaF).
Angewandte Chemie (International ed. in English), 2015
Quantitative analysis is a great challenge in surface-enhanced Raman scattering (SERS). Core-molecule-shell nanoparticles with two components in the molecular layer, a framework molecule to form the shell, and a probe molecule as a Raman internal standard, were rationally designed for quantitative SERS analysis. The signal of the embedded Raman probe provides effective feedback to correct the fluctuation of samples and measuring conditions. Meanwhile, target molecules with different affinities can be adsorbed onto the shell. The quantitative analysis of target molecules over a large concentration range has been demonstrated with a linear response of the relative SERS intensity versus the surface coverage, which has not been achieved by conventional SERS methods.
Enhancement in SERS intensity with hierarchical nanostructures by bimetallic deposition approach
Journal of Raman Spectroscopy, 2012
We investigate the plasmonic enhancement arising from bimetallic (Au/Ag) hierarchical structure and address the fundamental issues relating to the design of multilayered nanostructures for surface-enhanced Raman scattering (SERS) spectroscopy. SERSactive nanosphere arrays with Ag underlayer and Au overlayer were systematically constructed, with the thickness of each layer altered from 40 to 320 nm. The SERS responses of the resultant bimetallic structures were measured with 2-naphthalenethiol dye as the test sample. The results confirm the dependency of SERS enhancement on the thickness ratio (Au : Ag). Compared with Au-arrays, our optimized bimetallic structures, which exhibit nanoprotrusions on the nanospheres, were found to be 2.5 times more SERS enhancing, approaching the enhancement factor of an Ag-array. The elevated SERS is attributed to the formation of effective hot-spots associated with increased roughness of the outer Au film, resulting from subsequent sputtering of Au granules on a roughened Ag surface. The morphology and reflectance studies suggest that the SERS hot-spots are distributed at the junctions of interconnected nanospheres and over the nanosphere surface, depending on the thickness ratio between the Au and Ag layers. We show that, by varying the thickness ratio, it is possible to optimize the SERS enhancement factor without significantly altering the operating plasmon resonance wavelength, which is dictated solely by the size of the underlying nanospheres template. In addition, our bimetallic substrates show long-term stability compared with previously reported Ag-arrays, whose SERS efficiency drops by 60% within a week because of oxidation. These findings demonstrate the potential of using such a bimetallic configuration to morphologically optimize any SERS substrate for sensing applications that demand huge SERS enhancement and adequate chemical stability.
Gold aggregates on silica templates and decorated silica arrays for SERS applications
The European Physical Journal D, 2011
In this work, we report the fabrication and characterization of size controllable gold nanoparticles (NPs) aggregates for their application in surface enhanced Raman scattering (SERS). Aggregates were prepared using two methodologies: (i) by using silica particles arrays as a template to agglomerate gold NPs between the inter-particle interstices, and (ii) by functionalizing silica particles to be used as support to graft gold nanoparticles and thus to form decorated silica particle arrays. These substrates were used in the detection of Rhodamine 6G producing an enhancement factor (EF) from 10 4 to 10 6 that is associated to the increment of hot spot (HS) sites, and the fact that plasmon resonance from aggregates and absorption wavelength of test molecules are closely in resonance with excitation wavelength. The EF was also reduced when the plasmon resonance was red-shifted as a result of the increment of aggregate size. In spite of this, the EF is high enough to make these SERS substrates excellent candidates for sensing applications.
Metal Nanoparticles Deposited on Porous Silicon Templates as Novel Substrates for SERS
Croatica Chemica Acta, 2015
In this paper, results on preparation of stable and uniform SERS solid substrates using macroporous silicon (pSi) with deposited silver and gold are presented. Macroporous silicon is produced by anodisation of p-type silicon in hydrofluoric acid. The as prepared pSi is then used as a template for Ag and Au depositions. The noble metals were deposited in three different ways: by immersion in silver nitrate solution, by drop-casting silver colloidal solution and by pulsed laser ablation (PLA). Substrates obtained by different deposition processes were evaluated for SERS efficiency using methylene blue (MB) and rhodamine 6G (R6G) at 514.5, 633 and 785 nm. Using 514.5 nm excitation and R6G the limits of detection (LOD) for macroporous Si samples with noble metal nanostructures obtained by immersion of pSi sample in silver nitrate solution and by applying silver colloidal solution to pSi template were 10-9 M and 10-8 M respectively. Using 633 nm laser and MB the most noticeable SERS activity gave pSi samples ablated with 30000 and 45000 laser pulses where the LODs of 10-10 M were obtained. The detection limit of 10-10 M was also reached for 4 mA cm-2-15 min pSi sample, silver ablated with 30000 pulses. Macroporous silicon proved to be a good base for the preparation of SERS substrates.