Narrow Localized Surface Plasmon Resonance Research Articles

Experimental and Theoretical Studies on Ag Nanoparticles with Enhanced Plasmonic Response, Formed Within Al2O3 Thin Films Deposited by Magnetron Sputtering

AbstractReactive magnetron sputtering was employed to prepare nanocomposite thin films of Ag/Al2O3, on a glass substrate. The films are characterized by the formation of Ag nanoparticles embedded in the Al2O3 matrix, after thermal treatment at 600 °C, which are responsible for the appearance of an outstanding pronounced and narrow localized surface plasmon resonance (LSPR) band. Electron microscopy analysis also revealed the presence of larger Ag fractal aggregates at the film’s surface, responsible for a broad band absorption. Noteworthily, the LSPR band maximum remains at the same position (about 412 nm) for Ag concentrations ranging from 23 to 34 at.%, despite some discernible alterations in both LSPR band intensity and width. An optimized thin film is characterized by full transparency in non-resonant wavelengths due to suppression of Ag aggregates at the film’s surface, while maintaining the LSPR behavior. To better explain the plasmonic behavior of the Ag/Al2O3 films, discrete dipole approximation was used to determine the extinction, scattering, and absorption efficiencies of Ag spheres surrounded by an Al2O3 cap layer. This allowed to ascertain some nanostructural features of the films, pointing to the formation of Ag nanoparticles with average sizes in the order of 40 nm.

Synthesis of silver nanoplates with a narrow LSPR band for chemical sensing through a plasmon-mediated process using photochemical seeds

The plasmon-mediated process is one of the most common and well-studied methods to synthesize silver nanoplates (AgNPts). In a typical plasmon-mediated process, silver seeds are generated by chemical reduction using NaBH4 (abbreviated as CR seeds) before the plasmon-mediated process. However, a broad localized surface plasmon resonance (LSPR) band of AgNPts (usually broader than 150 nm) synthesized using the typical plasmon-mediated process would possibly limit their further applications. In this study, silver seeds are generated using a photochemical reduction method (abbreviated as PCR seeds). These PCR seeds then convert to AgNPts with irradiation by green LEDs or by a sodium lamp through the plasmon-mediated process. Furthermore, a very narrow LSPR bandwidth (approximately 67 nm) can be obtained when these AgNPts are further irradiated with red LEDs. Due to high refractive index sensitivity and sharp LSPR bandwidth, the as-prepared AgNPts have a high figure of merit (FOM) and can be used for spectroscopic chemical sensing applications. The silver seeds generated by this photochemical method can provide another choice for the plasmon-mediated process to synthesize AgNPts with high optical quality.

Synthesis of Silver Nanoplates With a Narrow LSPR Band for Chemical Sensing Through a Plasmon-Mediated Process Using Photochemical Seeds

The plasmon-mediated process is one of the most common and well-studied methods to synthesize silver nanoplates (AgNPts). In a typical plasmon-mediated process, silver seeds are generated by chemical reduction using NaBH4 (abbreviated as CR seeds) before the plasmon-mediated process. However, a broad localized surface plasmon resonance (LSPR) band of AgNPts (usually broader than 150 nm) synthesized using the typical plasmon-mediated process would possibly limit their further applications. In this study, silver seeds are generated using a photochemical reduction method (abbreviated as PCR seeds). These PCR seeds then convert to AgNPts with irradiation by green LEDs or by a sodium lamp through the plasmon-mediated process. Furthermore, a very narrow LSPR bandwidth (approximately 67 nm) can be obtained when these AgNPts are further irradiated with red LEDs. Due to high refractive index sensitivity and sharp LSPR bandwidth, the as-prepared AgNPts have a high figure of merit (FOM) and can be used for spectroscopic chemical sensing applications. The silver seeds generated by this photochemical method can provide another choice for the plasmon-mediated process to synthesize AgNPts with high optical quality.

Reproducible Plasmonic Nanopyramid Array of Various Metals for Highly Sensitive Refractometric and Surface-Enhanced Raman Biosensing.

Localized surface plasmon resonance (LSPR) biosensors show great potential for practical/commercial use in clinical diagnosis, home healthcare, environmental analysis, and public healthcare. However, two main issues, that is, low refractometric sensitivity and low reproducibility (large-area uniformity and batch-to-batch consistency), hinder the extensive applications of LSPR biosensors. Therefore, plasmonic nanostructures with high sensitivity and excellent reproducibility are desirable for preparing reliable LSPR sensors. Herein, we have fabricated plasmonic nanopyramid arrays (NPAs) for several batches with reproducible morphology and optical properties by elastic soft lithography and metal thermal evaporation. NPAs of various metals (i.e., Al, Au, and Ag) were also prepared by thermal evaporation with the according metals. The transmission spectra of these NPAs showed several narrow LSPR peaks in the visible-infrared wavelength region. The refractometric sensitivities of the LSPR peaks were systematically studied, and high refractometric sensitivities of 774.0, 472.8, and 421.0 nm/RIU were achieved on Al, Au, and Ag NPAs, respectively. To demonstrate the potential of the NPAs for multiplex applications, we first applied this highly sensitive Al NPA biosensor to monitoring the process of proliferation of HeLa cancer cells, in situ and in real time. Then, we demonstrated that the Au NPA was able to identify the absorbed analytes on its surface through the surface-enhanced Raman scattering spectrum. In addition, the finite difference time domain simulations were performed to reveal the electromagnetic field enhancement on NPAs. Because of the properties of high sensitivity and excellent reproducibility of the metal NPA LSPR substrates, as well as the simplicity and cost efficiency of the fabrication method, our proposed work will accelerate the practical use of LSPR sensors.

Origin of strong and narrow localized surface plasmon resonance of copper nanocubes

Inexpensive copper nanoparticles are generally thought to possess weak and broad localized surface plasmon resonance (LSPR). The present experimental and theoretical studies show that tailoring the Cu nanoparticle to a cubic shape results in a single intense, narrow, and asymmetric LSPR line shape, which is even superior to round-shaped gold nanoparticles. In this study, the dielectric function of copper is decomposed into an interband transition component and a free-electron component. This allows interband transition-induced plasmon damping to be visualized both spectrally and by surface polarization charges. The results reveal that the LSPR of Cu nanocubes originates from the corner mode as it is spectrally separated from the interband transitions. In addition, the interband transitions lead to severe damping of the local electromagnetic field but the cubic corner LSPR mode survives. Cu nanocubes display an extinction coefficient comparable to the dipole mode of a gold nanosphere with the same volume and show a larger local electromagnetic field enhancement. These results will guide development of inexpensive plasmonic copper-based nanomaterials.

Thin films of Ag–Au nanoparticles dispersed in TiO2: influence of composition and microstructure on the LSPR and SERS responses

Thin films containing monometallic (Ag,Au) and bimetallic (Ag–Au) noble nanoparticles were dispersed in TiO2, using reactive magnetron sputtering and post-deposition thermal annealing. The influence of metal concentration and thermal annealing in the (micro)structural evolution of the films was studied, and its correlation with the localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) behaviours was evaluated. The Ag/TiO2 films presented columnar to granular microstructures, developing Ag clusters at the surface for higher annealing temperatures. In some cases, the films presented dendrite-type fractal geometry, which led to an almost flat broadband optical response. The Au/TiO2 system revealed denser microstructures, with Au nanoparticles dispersed in the matrix, whose size increased with annealing temperature. This microstructure led to the appearance of LSPR bands, although some Au segregation to the surface hindered this effect for higher concentrations. The structural results of the Ag–Au/TiO2 system suggested the formation of bimetallic Ag–Au nanoparticles, which presence was supported by the appearance of a single narrow LSPR band. In addition, the Raman spectra of Rhodamine-6G demonstrated the viability of these systems for SERS applications, with some indication that the Ag/TiO2 system might be preferential, contrasting to the notorious behaviour of the bimetallic system in terms of LSPR response.

Femtosecond laser reshaping yields gold nanorods with ultranarrow surface plasmon resonances.

The irradiation of gold nanorod colloids with a femtosecond laser can be tuned to induce controlled nanorod reshaping, yielding colloids with exceptionally narrow localized surface plasmon resonance bands. The process relies on a regime characterized by a gentle multishot reduction of the aspect ratio, whereas the rod shape and volume are barely affected. Successful reshaping can only occur within a narrow window of the heat dissipation rate: Low cooling rates lead to drastic morphological changes, and fast cooling has nearly no effect. Hence, a delicate balance must be achieved between irradiation fluence and surface density of the surfactant on the nanorods. This perfection process is appealing because it provides a simple, fast, reproducible, and scalable route toward gold nanorods with an optical response of exceptional quality, near the theoretical limit.

Stabilized gold nanoparticles by laser ablation in ferric chloride solutions

In this study, laser ablation of gold was performed in different ferric chloride solutions and water as a reference. The ferric chloride solutions included hexachloro iron(III) and aquachloro iron(III) having low and high hydrolysis degree. Transmission electron microscope (TEM) images showed spherical gold nanoparticles (GNPs) in water, particles which are strongly agglomerated with intimate contact at their interfaces in hexachloro iron(III) and individual separated particles with a halo of an iron component in aquachloro iron(III). In addition, no combination of Au and Fe was found in HAADF analysis or X-ray diffraction (XRD) patterns. In optical investigations, it was observed that gold nanoparticles made in hexachloro iron(III) solutions have localized surface plasmon resonance (LSPR) peaks broader than in the case of water that are quenched after a few hours, while ablation in the aquachloro iron(III) solution provides narrow LSPR absorption with a long-term stability. According to X-ray photoelectron spectroscopy (XPS) there are metallic Au and Fe2+ states in the drop-casted samples. By comparison of cyclic voltammetry of solutions before and after laser ablation, strong agglomeration in hexachloro iron(III) was attributed to the reducing role of iron(III) creating an unstable gold surface in the chloride solution. In aquachloro iron(III), however, the observed stability was attributed to the formation of the halo of an iron compound around the particles.

Nafion membrane incorporated with silver nanoparticles as optical test strip for dissolved hydrogen peroxide: Preparation, deployment and the mechanism of action

We report the preparation of an optical test strip for quantitative assay of hydrogen peroxide (H2O2) in aqueous solution. Silver nanoparticles(AgNPs) with good optical quality are synthesized by in-situ reduction of silver ions in Nafion-117 membrane previously absorbed with ascorbate ion (HA−). The nanocomposite membrane exhibits a narrow Localized Surface Plasmon Resonance (LSPR) band at 413nm. The extent of decrease in intensity of the LSPR band in presence of H2O2 solution gives quantitative estimate of H2O2 concentration. The detector has been found to show a good analytical response towards H2O2 detection at pH 7 over a wide concentration range. The detection limit has been calculated to be 2.6×10−8molL−1, which is lower than the conventional enzyme based biosensors. The present test strip has been succesfully employed for the quantitative assay of H2O2 in milk. The mechanism of change in LSPR in presence of H2O2 (1.0×10−3molL−1) has been explored for the first time using time resolved Small-Angle X-ray Scattering and radiotracer techniques. The results show that at this concentration of H2O2, its sharp oxidative sawing action is responsible for cutting off the nanoparticles into smaller fragments resulting in rapid reduction of absorption crossection.

Effective Optoelectrical Switching by Using Pseudo-Single Crystal of Monolayer Array of 2D Polymer–Plasmonic Nanoparticles System

The Langmuir–Blodgett (LB) technique is used to assemble molecular compounds and colloidal nanoparticles into a monolayer on the surface of a substrate. Although the LB technique was used successfully in the assembly of the nanoparticles and molecules into monolayer, ordering of the nanoparticles or the molecules inside the LB film was not highly controlled. Functionalization of long chain polymers, which are able to semicrystallize into a monolayer, with the surface of colloidal nanoparticles can lead to highly ordered 2D arrays upon LB assembly. Poly(ethylene glycol) (PEG) with an average molecular weight of 30 000 g/mol is able to organize both isotropic 40 nm gold nanocubes (AuNCs) and anisotropic 40 nm gold nanorods into highly ordered 2D arrays. The separation distances between the nanoparticles in such LB assemblies are comparable, and the distances decreased upon increasing LB surface pressure. A strong sharp localized surface plasmon resonance (LSPR) spectrum of 2D AuNC arrays of full width at half-maximum (fwhm) of 46 nm is obtained when they are organized into highly ordered, well-separated 2D arrays on the surface of a substrate. The high efficiency of the plasmonic AuNC 2D arrays is exploited for optoelectrical switching applications. The LSPR peak of the AuNC 2D arrays coated with a thin film of poly(3-hexylthiophene), an electrochromic polymer that changes its optical properties upon electrochemical oxidation, reversibly blue-shifts by 9 nm upon the electrochemical oxidation of the polymer and shifts back after electrochemical reduction. The narrow LSPR spectrum of the fabricated 2D arrays decreases the value of the figure of merit and thus improves their sensing efficiency.

Radiation synthesized poly(n-vinyl-2-pyrrolidone)-stabilized-gold nanoparticles as LSPR-based optical sensor for mercury ions estimation

Poly(n-vinyl-2-pyrrolidone)-stabilized-gold nanoparticles (PVP-Au-NPs) have been synthesized via a green-60Co-Gamma radiolytic route and employed as a localized surface plasmon resonance (LSPR)-based optical sensor for estimation of trace quantities of Hg2+ ion in aqueous solutions. The in situ generated PVP-Au-NPs were characterized using UV–vis spectroscopy, transmission electron microscopy, and particle size analysis techniques. Reaction conditions were optimized to obtain uniformly dispersed PVP-Au-NPs with average particle size of 7.1 ± 1.6 nm (±s), which exhibited a narrow LSPR band at ~527 nm. The decrease in LSPR band intensity of PVP-Au-NPs with increase in Hg2+ ion concentration was found to be linear in the Hg2+ ion concentration range of 0–100 nM. The LSPR-based PVP-Au-NPs optical sensor system was found to be selective for Hg2+ and independent of interference from other metal ions such as Ca2+, Cu2+, Cd2+, and Fe2+ up to a concentration of 500 nM.

Blue-Shifted Narrow Localized Surface Plasmon Resonance from Dipole Coupling in Gold Nanoparticle Random Arrays

In this work, we develop a simple method to produce highly uniform localized surface plasmon resonance (LSPR) substrates based on self-assembly of colloidal gold nanoparticles onto pretreated glass substrates. The LSPR wavelength of the gold nanoparticle arrays is blue-shifted from that of the gold nanoparticles in solution and the single gold nanoparticles on glass substrate. The LSPR width is narrower than that of the single gold nanoparticles. The blue-shifted LSPR is due to the long-range dipole coupling in the gold nanoparticle random arrays indicated from simulations using the T-matrix method. In addition to the popularly used LSPR wavelength dependence on the dielectric environment, we have found that the LSPR width of the gold nanoparticle random arrays is also sensitive to the change in the dielectric environment. The LSPR substrates are reproducible, uniform, and robust with potential applications in LSPR sensing and imaging.

Plasmonic Properties of Copper Nanoparticles Fabricated by Nanosphere Lithography

The localized surface plasmon resonance (LSPR) of oxide-free Cu nanoparticles fabricated by nanosphere lithography is examined by UV−vis extinction spectroscopy and electrodynamics theory. The LSPR of the Cu nanoparticles is significantly affected by the presence of copper oxides and the removal of the oxide species yields a dramatic difference in the observed LSPR. From a comparison of the LSPR of Cu, Ag, and Au nanoparticles of similar geometry, we conclude that Cu displays an intense and narrow LSPR peak that is comparable to Ag and Au.

Surface‐enhanced Raman sensors: early history and the development of sensors for quantitative biowarfare agent and glucose detection

AbstractSurface‐enhanced Raman spectroscopy (SERS) is a powerful technique for the sensitive and selective detection of low‐concentration analytes. This paper includes a discussion of the early history of SERS, the concepts that must be appreciated to optimize the intensity of SERS and the development of SERS‐based sensors. In order to achieve the lowest limits of detection, both the relationship between surface nanostructure and laser excitation wavelength, as well as the analyte/surface binding chemistry, must be carefully optimized. This work exploits the highly tunable nature of nanoparticle optical properties to establish the first set of optimization conditions. The SERS enhancement factor, EFSERS, is optimized when the energy of the localized surface plasmon resonance (LSPR) lies between the energy of the excitation wavelength and the energy of the vibrational band of interest. With the narrow LSPRs used in this work, it is straightforward to achieve EFSERS ∼ 108. These optimization conditions were exploited to develop SERS‐based sensors for two important target molecules: a Bacillus anthracis biomarker and glucose in a serum protein mixture. Using these optimized film‐over‐nanosphere surfaces, an inexpensive, portable Raman spectrometer was used successfully to detect the infectious dose of Bacillus subtilis spores with only a 5‐s data collection. The biomarker used to detect the Bacillus subtilis spores binds irreversibly to SERS substrates, whereas other important biomolecules, such as glucose, do not have any measurable binding affinity to a bare silver surface. To overcome this difficulty, a biocompatible partition layer was self‐assembled on the SERS substrate before exposure to the analyte solution. Using the partition layer approach to concentrate glucose near the SERS‐active substrate, physiological glucose concentrations can be detected even in the presence of interfering serum proteins. Copyright © 2005 John Wiley & Sons, Ltd.

Nanosphere Lithography: Tunable Localized Surface Plasmon Resonance Spectra of Silver Nanoparticles

The wavelength corresponding to the extinction maximum, λmax, of the localized surface plasmon resonance (LSPR) of silver nanoparticle arrays fabricated by nanosphere lithography (NSL) can be systematically tuned from ∼400 nm to 6000 nm. Such spectral manipulation was achieved by using (1) precise lithographic control of nanoparticle size, height, and shape, and (2) dielectric encapsulation of the nanoparticles in SiOx. These results demonstrate an unprecedented level of wavelength agility in nanoparticle optical response throughout the visible, near-infrared, and mid-infrared regions of the electromagnetic spectrum. It will also be shown that this level of wavelength tunability is accompanied with the preservation of narrow LSPR bandwidths (fwhm), Γ. Additionally, two other surprising LSPR optical properties were discovered: (1) the extinction maximum shifts by 2−6 nm per 1 nm variation in nanoparticle width or height, and (2) the LSPR oscillator strength is equivalent to that of atomic silver in gas or liquid phases. Furthermore, it will be shown that encapsulation of the nanoparticles in thin films of SiOx causes the LSPR λmax to red shift by 4 nm per nm of SiOx film thickness. The size, shape, and dielectric-dependent nanoparticle optical properties reported here are likely to have significant impact in several applications including but not limited to the following: surface-enhanced spectroscopy, single-molecule spectroscopy, near-field optical microscopy, nanoscopic object manipulation, chemical/biological sensing, information processing, data storage, and energy transport in integrated optical devices.