Naturally grown Ag nanoparticles on quartz substrates as SERS substrate excited by a 488 nm diode laser system for SERDS

A silver nanoparticle ensemble was prepared under ultrahigh vacuum (UHV) conditions by Volmer–Weber growth on a quartz substrate for surface-enhanced Raman scattering (SERS) investigations of pyrene molecules. To tune the surface plasmon resonance frequency in the vicinity of the excitation wavelength of 488 nm of the diode laser, the morphology of the silver nanoparticles was optimized. The substrates were mounted in a flow-through cell as part of the optical Raman set-up. A microsystem diode laser generates two slightly different emission wavelengths (λ=487.61 nm and λ=487.91 nm) with a spectral width <10 pm and an optical power of 20 mW, i.e. SERS experiments are possible but also shifted excitation Raman difference spectroscopy (SERDS) can be carried out. For trace analysis of pyrene in water we demonstrate SERS/SERDS experiments which lead to a limit of detection of 2 nmol/l for pyrene. These results suggest that with silver nanoparticle ensembles excited at their plasmon resonance at 488 nm combined SERS/SERDS measurements can be effectively performed for in-situ trace analysis of pollutant chemicals in water.     

Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.     

Application of calixarene to high active surface‐enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater

The characteristics of the sol–gel matrix embedding Ag nanoparticles functionalized with 25,27‐dimercaptoacetic acid‐26,28‐dihydroxy‐4‐tert‐butylcalix[4]arene (DMCX) suitable for the in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater is presented. The DMCX‐functionalized silver nanoparticles were produced by the thermal reduction method in xerogel film. The silver colloid blocks were formed in the sol–gel matrix, with a diameter ranging from 50 to 120 nm. DMCX forming the monolayer on the silver nanoparticle surface contributes to the surface‐enhanced Raman scattering (SERS) activity due to the aggregation of silver nanoparticles and the preconcentration of PAH molecules within the zone of electromagnetic enhancement. When selected, PAH molecules e.g. pyrene and naphthalene were adsorbed onto the SERS substrate; Raman band positions of PAH were slightly shifted. A calibration procedure reveals that this type of SERS substrate has a limit of detection of 3 × 10⁻¹⁰ mol/l for pyrene and 13 × 10⁻⁹ mol/l for naphthalene in artificial seawater. The Raman signal response on a pyrene concentration change in artificial seawater was evaluated using a 671‐nm Raman setup with a flow‐through cell. This type of SERS substrate will be suitable for the in situ trace detection of pollutant chemicals in seawater. Copyright © 2012 John Wiley & Sons, Ltd.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

Size‐dependent SERS enhancement of colloidal silver nanoplates: the case of 2‐amino‐5‐nitropyridine

Surface‐enhanced Raman scattering (SERS) spectra of 2‐amino‐5‐nitropyridine (ANP) adsorbed on colloidal silver triangular nanoplates were obtained using samples with different mean sizes and surface plasmon frequencies. The relative SERS enhancement factor for each sample was determined by the analysis of the normalized SERS excitation profiles of ANP vibrational modes for nanoplates in suspension, without aggregation. The SERS profiles are blue‐shifted in relation to the localized surface plasmon peak. The detailed characterization of both morphology and concentration of the samples in addition to a rigorous normalization of the SERS spectra allowed a quantitative correlation between the SERS profiles and the mean size of the nanoplates. This correlation indicated the existence of an optimum size of the nanoplates for maximum Raman enhancement. Copyright © 2008 John Wiley & Sons, Ltd.     

Nanoflower-like Ag/AAO SERS platform with quasi-photonic crystal nanostructure for efficient detection of goat serum

An effective SERS-based detection method has been developed to quantitatively diagnose the goat serum which overcomes the problem of diffusion limitation in traditional heterogeneous immunoassay. In this work, the ultra-sensitive silver/anodic aluminum oxide (Ag/AAO) SERS platform was explored via magnetron sputtering which can precisely control the sample morphology and intergap distances. Results indicated that the localized surface plasmon resonance (LSPR) effect was sharply strengthened as the sub-10 nm nanogaps generated and the enhancement factor (EF) for crystal violet (CV) was calculated to be 3.677 × 10⁷. This novel Ag/AAO substrate with substantial “hot spots” exhibited high SERS sensitivity which could obtain extremely low limits of detection (LOD) of 10⁻¹² M for CV. Importantly, this SERS platform was employed to detect goat serum and reached a LOD at 1 ng/μl. As a nondestructive detection technique, our SERS-based methodology required small sample quantity which expected to achieve more biomolecular detection.     

Trace analysis of polycyclic aromatic hydrocarbons using calixarene layered gold colloid film as substrates for surface‐enhanced Raman scattering

A surface‐enhanced Raman scattering (SERS) active substrate for the detection of polycyclic aromatic hydrocarbons (PAHs) was developed, which used 25, 27‐dimercaptoacetic acid‐26, 28‐dihydroxy‐4‐terbutyl calix[4]arene (DMCX) to functionalize a gold colloid film. This SERS‐active substrate prepared by self‐assembly method exhibits a high sensitivity, especially for the detection of PAHs. With the use of this SERS‐active substrate and with the application of the shifted excitation Raman difference spectroscopy (SERDS) technique, Raman signals of pyrene and anthracene in aqueous solutions at low concentration level (500 pM) can be obtained. Moreover, because PAHs are blocked from being directly adsorbed on gold colloid by DMCX and the photochemical reactions of adsorbates are avoided, the Raman bands of PAHs adsorbed on DMCX‐fuctionalized gold colloid film can be one‐to‐one correspondence with those of solid PAHs, and additionally, this SERS‐active substrate can be easily cleaned and reused. The obtained results demonstrate that the DMCX‐functionalized gold colloid films prepared by self‐assembly method have great potential to be developed to an in situ PAHs detection substrate. Copyright © 2012 John Wiley & Sons, Ltd.     

New SERS feature of β‐carotene: consequences for quantitative SERS analysis

While recording SERS spectra of pure β‐carotene at sub‐micromole concentrations for reference purpose, we discovered an unusual spectral response never reported before. In pre‐resonance conditions with the 532‐nm line, SERS of β‐carotene with AgNPs exhibits among the strong υ(CC) mode at 1512 cm⁻¹ unshifted from normal Raman spectrum, additional strong bands at 1649, 1575 and 1387 cm⁻¹ as well as other medium bands not observed in the Raman spectrum of the crystalline powder. Such behavior is explained in terms of selection rules relaxation upon cyclohexene terminal rings of the β‐carotene interaction with the NP surface. AFM images of the SERS system suggested dimers and trimers clustering of the nanoparticles with adsorbed β‐carotene. In light of the new SERS feature the consequences in correct interpretation of the SERS imaging from complex biosystems containing carotenoids are discussed. Relative intensity ratio of the β‐carotene band at 1512 cm⁻¹ and water against concentration allowed a reliable SERS calibration curve for 50 to 500 nmol l⁻¹ concentration range and provided quantitative SERS assessment of the carotenoid content in the sea urchin (Paracentrotus lividus) gonads extracts. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering studies of carbon nanotubes using Ag‐core Au‐shell nanoparticles

Surface‐enhanced Raman scattering from carbon nanotube bundles adsorbed with plasmon‐tunable Ag‐core Au‐shell nanoparticles (Ag@Au nps) was carried out for the first time. By utilizing nanoparticles whose plasmon resonance peak (541, 642 nm) closely matches the commonly used Raman excitation sources (532, 632.81 nm), we can observe a large enhancement in the Raman signatures of carbon nanotubes. We obtain greater enhancement in the Raman signal for the above case when compared to nanotubes adsorbed with conventional Ag, Au or other ‘off resonant’ Ag@Au nps. The power‐dependent SERS experiment on single‐walled nanotubes (SWNTs) with resonant Ag@Au nps reveals a linear behavior between the G‐band intensity and the photon flux density, which is in agreement with the vibrational pumping model of SERS. The observed enhancement by resonance matching is pronounced for carbon nanotubes and may lead to insights into understanding nanotube–nanoparticle interaction. Copyright © 2009 John Wiley & Sons, Ltd.     

A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface‐enhanced Raman spectroscopy (SERS). However, large‐scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed‐mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as‐prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785‐nm excitation, respectively. Significantly, 150‐nm Ag NPs exhibit an enhancement factor exceeding 10⁸ for pyridine (Py) molecules in electrochemical SERS (EC‐SERS) measurements. Furthermore, finite‐difference time‐domain (FDTD) calculation is employed to explain the size‐dependent SERS activity. Finally, the potential of the as‐prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd.     

Detection of biologically active diterpenoic acids by Raman Spectroscopy

Three poorly detectable, biologically active diterpenoic acids, kaurenoic, abietic, and gibberellic acid, were studied by using different modes of Raman spectroscopy. Because of their structural similarities, in the absence of strongly polarizable groups, conventional Raman spectroscopy is not suitable for their unambiguous identification, especially not in solution. We attempted to increase the sensitivity by applying UV‐resonance Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS) techniques. The UV‐Raman spectra of the three compounds in ethanol/water 50:50 showed only very few enhanced Raman lines. SERS spectra with 514‐nm excitation with Ag colloids were also relatively weak. The best SERS spectra were obtained with 785‐nm excitation on a novel nanostructured substrate, ‘black silicon’ coated with a 400‐nm gold layer. The spectra showed clear differences, and these ‘fingerprints’ would be suitable for the unambiguous identification of these diterpenoic acids. Copyright © 2009 John Wiley & Sons, Ltd.     

Silver nanorods used to promote SERS as a quantitative analytical tool

We have fabricated silver nanorod arrays by electrodepositing the nanorods evenly in the shallow pores of porous anodic aluminum oxide (AAO) templates. The diameter and length were 28 and 44 nm, respectively. The maxima of the transverse and longitudinal modes of the surface plasmon were near 417 and 511 nm, respectively. A good surface‐enhanced Raman scattering (SERS) spectrum was observed by excitation with the 514.5‐nm laser line. The SERS intensity increased almost linearly upon malachite green isothiocyanate adsorption on the tips of the silver nanorods as the concentration of the mother solutions increased. Our results show that silver nanorods fabricated on AAO templates could be used as an SERS substrate for quantitative analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

785 nm激光诱导银纳米三角片聚集表面增强拉曼散射效应

为实现表面增强拉曼散射（SERS）光谱的强信号快速检测分析,报道了通过785 nm激光诱导银纳米三角片（AgNPRs）聚集的方法。采用配体辅助化学还原法制备了AgNPRs,其边长约为80 nm,表面等离子体吸收峰出现在约774 nm处,对785 nm光产生有效吸收。在785 nm光辐照下,AgNPRs逐渐聚集,对巯基苯甲酸的SERS信号逐渐增强,其源于AgNPRs吸收的光转化为热而引起的AgNPRs聚集。其增强因子高达10⁹。为快速获得强SERS信号,激发光功率需大于250 mW。     

Plasmon‐driven catalysis in aqueous solutions probed by SERS spectroscopy

Since 2010, the plasmon‐driven catalysis using surface‐enhanced Raman spectroscopy (SERS) in atmospheric environment has been experimentally reported. Recent experimental results since 2014 revealed that catalysis under aqueous condition is much better than that in atmospheric environment. In this paper, we review plasmon‐driven catalysis using SERS under aqueous condition. First, the experimental apparatus developed by ourselves is introduced in detail. Second, we demonstrate the advantages of plasmon‐driven catalysis using SERS under aqueous condition compared to that in atmospheric environment. Third, we review recent experimental results using this measurement method in different experimental settings under aqueous condition. The manipulation of reaction environment effectively provided the possibility to reveal the mechanism of surface plasmon catalysis for different reactions. This method has great potential to apply on ultrasensitive spectral analysis for SERS, catalysis, sensor and biology system under aqueous condition. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanostructured Au/Si substrate for organic molecule SERS detection

Nanoparticles of noble metals, such as gold and silver, exhibit unique and tunable optical properties on account of their surface plasmon resonance. In particular, gold nanoparticles on silicon substrates are attractive for future nanoscale sensors and optical devices due to their resistance to oxidation and due to their electrical and optical properties. In this study, we developed a nanostructured gold/macroporous silicon (Au/PS) substrate capped with 11-mercaptoundecanoic acid (11-MUA) with ultra-sensitive detection properties achieved in characterization, an approach based on surface-enhanced Raman scattering (SERS). Surface-enhanced Raman scattering allows us to detect substances at a low concentration level and to observe structural details of a thiol molecule bonded to small film thicknesses. Raman measurements were carried out at 514 nm and 785 nm. In order to emphasize the effect of the Si microstructuration on the efficiency of this new substrate (Au/PS) proposed for SERS experiments, the same molecule (11-MUA) was adsorbed on it as well as on gold/atomically flat silicon (Au/Si) and on commercial Klarite (Mesophotonics) substrates. Systematic studies realized by Raman spectroscopy, electron microscopy, and X-ray spectroscopy show the influence of silicon substrate texturing and metallic deposition conditions, including time and temperature on the optical phenomena.     

Portable smart films for ultrasensitive detection and chemical analysis using SERS and SERRS

Metallic nanostructures, much smaller than the wavelength of visible light, which support localized surface plasmon resonances, are central to the giant signal enhancement achieved in surface‐enhanced Raman scattering (SERS) and surface‐enhanced resonance Raman scattering (SERRS). Plasmonic driven SERS and SERRS is a powerful analytical tool for ultrasensitive detection down to single molecule detection. For all practical SERS applications a key issue is the development of reproducible and portable SERS‐active substrates, where the most widely used metals for nanostructure fabrication are silver and gold. Here, we report the fabrication of a ‘smart film’, containing gold nanoparticles (AuNPs), produced by in situ reduction of gold chloride III (Au⁺³) in natural rubber (NR) membranes for SERS and SERRS applications. The composite films (NR/AuNP membranes) show characteristic plasmon absorption of Au nanostructures, which notably do not influence the mechanical properties of the NR membranes. The term ‘smart film’ has to do with the fact that the SERS substrate (smart film) is flexible and standalone, which allows one to take it anywhere and to dip it into solutions containing the analyte to be characterized by SERS or SERRS technique. Besides, the synthesis of the AuNPs at the surface of NR films is much simpler than making an Au colloid and cast it onto a substrate surface or preparing an Au evaporated film. Copyright © 2012 John Wiley & Sons, Ltd.     

A portable shifted excitation Raman difference spectroscopy system: device and field demonstration

In this paper, we present a portable shifted excitation Raman difference spectroscopy (SERDS) system applied in outdoor experiments. A dual‐wavelength diode laser emitting at 785 nm is used as excitation light source. The diode laser provides two individually controllable excitation lines at 785 nm with a spectral distance of about 10 cm⁻¹ for SERDS. This monolithic light source is implemented into a compact handheld Raman probe. Both components were developed and fabricated in‐house. SERDS measurements are performed in an apple orchard, and apples and green apple leafs are used as test samples. For each excitation wavelength, a single Raman spectrum is measured with 50 mW at the sample. Strong background interference from ambient daylight and laser‐induced fluorescence obscure the Raman signals. SERDS efficiently separates the wanted Raman signals from the disturbing background signals. For the Raman spectroscopic investigations of green leafs, one accumulation with an exposure time of 0.2 s was used for each excitation wavelength to avoid detector saturation. An 11‐fold improvement of the signal‐to‐background noise is achieved using SERDS. The results demonstrate the suitability of the portable SERDS system for rapid outdoor Raman investigations. Copyright © 2016 John Wiley & Sons, Ltd.     

Physical mechanisms behind the SERS enhancement of pyramidal pit substrates

In this paper we theoretically consider the physical mechanisms behind the surface‐enhanced Raman scattering (SERS) enhancement produced by commercially available Klarite substrates, which consist of rectangular arrays of micrometre‐sized pyramidal pits in silicon with a thin gold coating. Full three‐dimensional numerical simulations of the pits are conducted for both a real gold metal coating and a perfect electrical conductor (PEC) to determine whether the SERS enhancement is due to diffraction or plasmon effects. The pit apex angle and metal coating thickness are also varied to determine whether it is possible to further enhance the SERS signal by optimising the structural parameters of these substrates. By decreasing the film thickness and adjusting the apex angle, it is possible to achieve an enhancement almost double that of a standard Klarite substrate. Copyright © 2010 John Wiley & Sons, Ltd.     

Nanofabricated periodic arrays of silver elliptical discs as SERS substrates

Signal enhancement observed in surface‐enhanced Raman spectroscopy (SERS) is attributable to the presence of noble‐metal nanostructures on substrate surfaces. The rational development of SERS‐active substrates depends critically on the homogeneity and intensity of surface plasmon resonances, properties that are strongly dependent on both the morphology and dielectric properties of the metals and composite materials making up the SERS substrates. Enhancement can be controlled by the shape, size, and spacing of metallic nanoparticles. Previous studies in our group have shown that arrays of elliptical nanodiscs have promising geometries for this purpose. Using electron beam lithography (EBL), we fabricate close‐packed arrays of these discs with lateral dimensions ranging from 300:50 to 300:300 nm (long axis : short axis). The arrays are composed of a negative photoresist that, once the lithography process is complete, are coated with a noble metal through physical vapor deposition (PVD). In this work, optimum thickness and deposition rate of noble metal are determined for these substrates. The lithographically produced nanopatterns are studied by Raman spectroscopy to examine the effect of altering the elliptical aspect ratio on SERS activity, while scanning electron microscopy (SEM) is used to examine pattern surfaces post lithographic development and post noble‐metal deposition. Atomic force microscopy (AFM) is used to inspect the roughness of substrate surfaces. Reproducibility between different arrays of the same pattern ranges from 12 to 28%. Homogeneity of our uniform‐morphology EBL/PVD‐fabricated substrates is examined and compared to our random‐morphology polymer nanocomposite substrates. Using rhodamine 6G as an analyte, an increase in SERS signal is noted as the aspect ratio of ellipses goes from 6:1 to 6:6. Our experimental data, in terms of trends in SERS activity, correlate with trends in field enhancements calculated using a simple electrostatic model and with the magnitude of the broad red‐shifted spectral continuum observed for the substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

SERS active Ag nanoparticles in mesoporous silicon: detection of organic molecules and peptide–antibody assays

Ag nanoparticles synthesized on porous silicon samples were studied and applied as substrates for surface‐enhanced Raman scattering (SERS). The metallic nanostructures prepared by immersion plating were characterized by UV–Vis reflectance spectroscopy and scanning electron microscopy. SERS activity of the substrates was tested using Cyanine dye 1,3,3,1′,3′,3′‐esamethyl‐5,5′‐dimethoxyindodicarbocyanine iodide (Cy5‐OCH₃) as a probe molecule. The Raman spectra obtained for different excitation wavelengths indicate amplifications ascribed to plasmonic resonances with an enhancement factor up to 10⁷. CGIYRLRS peptides were chemisorbed on the Ag nanoparticles with the plasmonic resonance tuned at the excitation energy. Such oligopeptides were used as baits for a specific polyclonal antibody. The overall Raman enhancement allowed to evidence a good selectivity to the target analyte as required by most of the SERS applications on biological assays. Copyright © 2011 John Wiley & Sons, Ltd.