Tunable Localized Surface Plasmon Resonance Research Articles

Surface Modification of Gold Nanorods: Multifunctional Strategies and Application Prospects.

Gold nanorods (AuNRs), as an important type of gold nanomaterials, have attracted much attention in the nano field. Compared with gold nanoparticls, AuNRs have broader application potential due to their tunable localized surface plasmon resonance properties and anisotropic shapes. Yet, conventional synthesis methods using surfactants have limited the use of AuNRs in a variety of fields such as biomedical applications, plasma-enhanced fluorescence, optics and optoelectronic devices. To solve this problem and improve the stability and biocompatibility of AuNRs, researchers in recent years have used surface modification and functionalization to modify AuNRs, among which the introduction of organic ligands to prepare organic/gold hybrid nanorods has become an effective strategy. Organic materials have better toughness and easy processing, and by introducing organic ligands into the surface of AuNRs, the molecular-level composite of organic and inorganic materials can be realized, thus obtaining hybrid nanorods with excellent properties. This paper reviews the research progress of hybrid nanocomposites, and introduces the synthesis methods of AuNRs and the development of surface ligand modification, then summaries the applications of a wide variety of ligands. Also, the advantages and disadvantages of different ligands and their roles in further self-assembly processes are discussed.

Dynamically Tunable Localized Surface Plasmon Resonance in Self‐Assembled SrCoOx‐Au Vertically Aligned Nanocomposite Thin Films

AbstractWhile the physical principles for regulating localized surface plasmon resonance (LSPR) are well established, dynamically tuning the LSPR in a given material post synthesis remains challenging. Herein, this study demonstrates a strategy for dynamically tuning the LSPR of Au nanostructures by selectively altering the dielectric environment. Au is integrated with an electrochemically gatable oxide, i.e., SrCoOx (SCO), into vertically aligned nanocomposite thin films via a self‐assembly growth mechanism, where Au develops into nanopillars embedded in the SCO matrix. By selectively controlling the tri‐state phase transitions of SCO matrix via varying the bias voltage polarity in ionic liquid gating (ILG), the LSPR behavior of Au nanopillars can be dynamically tuned. Specifically, gating with a negative bias fully suppresses the LSPR, while a positive bias leads to a continuous blueshift of the LSPR wavelength upon increasing the ILG duration. This work not only opens new directions for the dynamic control of LSPR of noble metal nanostructures, but also offers insight to the voltage control of multifunctionalities via structural and physical intercoupling between different phases in self‐assembled nanocomposites.

Seed‐Mediated Synthesis of Gold Nanobipyramids at Low CTAB Concentration Using Binary Surfactants

AbstractThe conventional method for synthesizing gold nanobipyramids (AuNBPs) is well established. However, the cytotoxicity resulting from the conjugates between hexadecyltrimethylammonium bromide (CTAB) and gold limits their biomedical applications. This study introduces a dual surfactant approach with CTAB and sodium oleate (NaOL) in the seed‐mediated synthesis of the AuNBPs, which can significantly reduce the CTAB concentration to 10 mM. Additionally, optimal growth conditions are achieved by varying the volumes of seed solution, AgNO3, and HCl. Under low CTAB concentrations, AuNBPs with tunable sizes and localized surface plasmon resonances between 600 and 1200 nm are successfully synthesized, as characterized by UV–vis‐NIR spectroscopy, transmission electron microscopy (TEM), and finite‐difference time‐domain (FDTD) simulations. This work demonstrates a method for synthesizing AuNBPs at low CTAB concentrations using binary surfactants and provides a framework applicable to the synthesis of other metallic nanomaterials.

Pentatwinned AuAg Nanorattles with Tailored Plasmonic Properties for Near-Infrared Applications.

Noble metal nanoparticles, particularly gold and silver nanoparticles, have garnered significant attention due to their ability to manipulate light at the nanoscale through their localized surface plasmon resonance (LSPR). While their LSPRs below 1100 nm were extensively exploited in a wide range of applications, their potential in the near-infrared (NIR) region, crucial for optical communication and sensing, remains relatively underexplored. One primary reason is likely the limited strategies available to obtain highly stable plasmonic nanoparticles with tailored optical properties in the NIR region. Herein, we synthesized AuAg nanorattles (NRTs) with tailored and narrow plasmonic responses ranging from 1000 to 3000 nm. Additionally, we performed comprehensive characterization, employing advanced electron microscopy and various spectroscopic techniques, coupled with finite difference time domain (FDTD) simulations, to elucidate their optical properties. Notably, we unveiled the main external and internal LSPR modes by combining electron energy-loss spectroscopy (EELS) with surface-enhanced Raman scattering (SERS). Furthermore, we demonstrated through surface-enhanced infrared absorption spectroscopy (SEIRA) that the NRTs can significantly enhance the infrared signals of a model molecule. This study not only reports the synthesis of plasmonic NRTs with tunable LSPRs over the entire NIR range but also demonstrates their potential for NIR sensing and optical communication.

A Surface-Enhanced Raman Scattering Substrate with Tunable Localized Surface Plasmon Resonance Absorption Based on AgNPs.

In this paper, a three-layer structure of silver particle (AgNP)-dielectric-metal is proposed and constructed based on the characteristics of AgNPs that can excite LSPR (Localized Surface Plasmon Resonance) in free space. In order to overcome the problem of AgNPs easily oxidizing in the air, this paper synthesizes AgNPs using the improved Tollens method and effectively suppresses the coffee-ring effect by changing the solution evaporation conditions, so that the distribution of AgNPs in the deposition area is relatively uniform. The structure proposed in this paper takes advantage of the flexibility of nanoparticle application. The AgNPs deposited on the dielectric layer can effectively localize energy and regulate the LSPR of the device well. The structure can not only achieve precise regulation of the LSPR resonance peak of AgNPs but also can be used as a SERS substrate.

Laser irradiation-induced surface-enhanced Raman scattering of Sn@SnO composite films

In this work, Sn@SnO composite films were obtained by Nd:YAG fiber pulsed laser ablation at room temperature. The effects of laser ablation on the microstructure, optical properties, and Raman scattering properties of the films were investigated. Tunable Localized Surface Plasmon resonance(LSPR)of Sn nanoparticles was realized in the wavelength range of 380–450 nm by varying the scanning rate to modulate the degree of oxidation of Sn nanoparticles. Surface enhanced Raman scattering (SERS) was also observed in the composite structure, which was demonstrated excellent stability and SERS sensitivity with the detectable concentration of methylene blue (MB) as low as 10−9 M and an enhancement factor of 1.75 × 105 as well as a good uniformity. Finally, the electric field distribution of the samples before and after the laser treatment is simulated by the finite difference in time domain (FDTD) method, and the results are consistent with those of experimental ones.

Ultra-Broadband Plasmon Resonance in Gold Nanoparticles Precipitated in ZnO-Al2O3-SiO2 Glass

Optical materials with a tunable localized surface plasmon resonance (LSPR) are of great interest for applications in photonics and optoelectronics. In the present study, we explored the potential of generating an LSPR band with an ultra-broad range of over 1000 nm in gold nanoparticles (NPs), precipitated through a thermal treatment in ZnO-Al2O3-SiO2 glass. Using optical absorption spectroscopy, we demonstrated that the LSPR band’s position and shape can be finely controlled by varying the thermal treatment route. Comprehensive methods including Raman spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy were used to study the glass structure, while computational approaches were used for the theoretical description of the absorption spectra. The obtained results allowed us to suggest a scenario responsible for an abnormal LSPR band broadening that includes a possible interparticle plasmonic coupling effect taking place during the liquid–liquid phase separation of the heat-treated glass. The formation of gold NPs with an ultra-broad LSPR band in glasses holds promise for sensitizing rare earth ion luminescence for new photonics devices.

Seedless synthesis of Au nanoplates with tunable plasmonic peaks

Au nanoplates with tunable in-plane dipolar localized surface plasmon resonance peaks in a broad range from the visible to near-infrared region were obtained in high yield using a seedless wet chemical growth method after purification. Cetyltrimethylammonium chloride was used as a surfactant, while hydrogen peroxide and sodium borohydride were used as the weak and strong reducing agents, respectively. The edge length and in-plane dipolar localized surface plasmon resonance peak of the Au nanoplates could be adjusted by varying the amounts of hydrogen peroxide and sodium borohydride. The Au nanoplates were further used as the saturable absorber to generate pulsed laser output in a passively Q-switched solid-state laser at approximately 2 µm. Our study offers a new method for obtaining Au nanoplates with tunable plasmonic peaks over a broad range.

ZnO Matrices as a Platform for Tunable Localized Surface Plasmon Resonances of Silver Nanoparticles

In this study, the localized surface plasmon resonances (LSPRs) of Ag nanoparticles (NPs) embedded in ZnO dielectric matrices were studied. Initially, continuous Ag thin films were deposited on Corning glass substrates via magnetron sputtering, followed by post annealing, resulting in the formation of self-assembled nanoparticles. In some cases, a heated substrate holder was employed to induce NP formation during the deposition. The morphology of nanoparticles was studied using atomic force microscopy (AFM). Ultraviolet–visible spectroscopy (UV-Vis) probed the LSPRs. Subsequently, a 70 nm thick ZnO layer was deposited on top of the Ag thin films. For the Ag films, LSPR characteristics were found to depend on the initial film thickness. The ZnO capping layer induced an intense red shift, suggesting its potential as a mechanism for tailoring LSPRs. Lastly, theoretical calculations with the rigorous coupled-wave analysis (RCWA) method were carried out for comparison with the experimental results.

(Invited) Metal and Nonmetal Plasmonic Nanostructures for Surface-Enhanced Raman Spectroscopy Detection

Toxic small molecules such as pesticides, food additives, plasticizers and dyes have been posing increasing threat to human health. Surface-enhanced Raman scattering spectroscopy (SERS) is a powerful sensing strategy for these small molecules with advantages including fast response, high sensitivity and fingerprint identification.Based on the surface plasmon effect, gold and silver nanostructures are the typical plasmonic sensing materials for rapid detection with SERS. However, the crucial challenges for realizing on-site real detection application is to fabricate reproducible and highly sensitive SERS substrates and portable instrument. We fabricated several long-range ordered sensitive nanostructure arrays based on anodic aluminum oxide templates which could provide reproducible structural patterns. Then, we developed a portable instrument integrated with database of the standard Raman spectra of common contaminants and a software for automatic identification and comparison of the test spectrum with the standard database, which can identify the specific analytes. Combined with the sensitive and reproducible SERS substrates, we realized the on-site and rapid detection of various toxic contaminants.Recently, as an inexpensive candidate, nonmetal plasmonic materials like oxide semiconductors have attracted increasing interests, which induced by the increase of free charge carriers via introducing oxygen vacancies. We synthesized oxygen-deficient WO3-x and NayWO3-x nanosheets and realized the localized surface plasmon resonance (LSPR) band in visible range (~530 nm) as same as the gold nanoparticles, which is the bluest. Then, SERS detection of dyes has also been realized on nonmetal substrate. Moreover, the plasmonic oxygen-deficient oxides showed wide LSPR tuning window from visible to infrared range and plasmon-driven photocatalysis, which may open potentials for biological applications.

Chromogenic Mechanisms of Colorimetric Sensors Based on Gold Nanoparticles.

The colorimetric signal readout method is widely used in visualized analyses for its advantages, including visualization of test results, simple and fast operations, low detection cost and fast response time. Gold nanoparticles (Au NPs), which not only exhibit enzyme-like activity but also have the advantages of tunable localized surface plasmon resonance (LSPR), high stability, good biocompatibility and easily modified properties, provide excellent platforms for the construction of colorimetric sensors. They are widely used in environmental monitoring, biomedicine, the food industry and other fields. This review focuses on the chromogenic mechanisms of colorimetric sensors based on Au NPs adopting two different sensing strategies and summarizes significant advances in Au NP-based colorimetric sensing with enzyme-like activity and tunable LSPR characteristics. In addition, the sensing strategies based on the LSPR properties of Au NPs are classified into four modulation methods: aggregation, surface modification, deposition and etching, and the current status of visual detection of various analytes is discussed. Finally, the review further discusses the limitations of current Au NP-based detection strategies and the promising prospects of Au NPs as colorimetric sensors, guiding the design of novel colorimetric sensors.

Thermally generated Au–Ag nanostructures with tunable localized surface plasmon resonance as SERS activity substrates

Various Au–Ag bimetallic alloy nanostructures were obtained as sensitive surface-enhanced Raman scattering (SERS) substrates by changing the thermal annealing sequence. The atomic force microscopy (AFM) and scanning electron microscopy (SEM) results confirm that Au/Ag bimetallic clusters and Ag–Au core-shell like structures can be designed by thermal annealing. The absorption spectra showed that the localized surface plasmon resonance (LSPR) frequency of the annealed Au/Ag bimetallic alloy structure could effectively shift from the near ultraviolet to the visible region. At the same time, the Au/Ag bimetallic alloy films modified by thermal annealing have shown satisfactory performance as SERS substrates. Raman enhancement mechanism of Au–Ag bimetallic alloy films is verified by finite-difference time-domain (FDTD) simulation results.

Shaping the Plasmonic Response: Hollow Gold Elliptical Nanotubes

AbstractHighly tunable localized surface plasmon (LSP) resonances in metal nanostructures are of great importance for manipulating light waves and enhancing light–matter interactions at the nanoscale. Here, a new type of plasmonic resonators based on hollow elliptical nanotubes, which can generate highly tunable LSP resonances in the visible frequencies, are reported. High‐quality hollow gold (Au) elliptical nanotubes with fine controllable size and morphology are experimentally fabricated. Dark‐field scattering measurements reveal the presence of multiple plasmon resonances including longitudinal Fabry–Pérot resonances and transverse hybridized LSP resonances due to rotational symmetry breaking. Upon varying the ellipticity, the hybridized LSP resonances exhibit continuously spectral evolution behaviors, such as the hybridized modes shifting and crossing. The experimental results show good agreement with the rigorous electromagnetic modeling and Raman spectroscopic measurements. The hollow anisotropic geometries provide highly tunable plasmonic responses together with homogeneous field distributions and high surface‐to‐volume ratio, which hold great potential for practical applications in sensing, nonlinear optics, surface‐enhanced spectroscopies, and bio‐medicine.

Colorimetric sensing of Cu(II) ions in water on the basis of selective chemical etching of EDA-capped Ag nanoplates

Cu(II) ions are one of the essential mineral elements in the human body, but can pose a substantial health risk to people exposed to high concentrations of Cu(II) ions over a long period. Therefore, the ability to detect Cu(II) ions in drinking water is important. In this study, a novel colorimetric sensing probe for the easy and onsite detection of Cu(II) ions in drinking water was developed. The probe was constructed through selective chemical etching of triangular Ag nanoplates with tunable localized surface plasmon resonance (LSPR) properties. Ethylenediamine (EDA) was used as an organic capping agent to improve the chemical stability of triangular Ag nanoplates. Selective chemical etching of the EDA-capped Ag nanoplates in the presence of Cu(II) ions as a result of the formation of a coordination complex between the EDA and Cu(II) ions caused remarkable changes in the nanoplates’ LSPR characteristics. On the basis of this phenomenon, a novel colorimetric sensing probe capable of detecting Cu(II) ions in drinking water at concentrations above the safety limit was developed. Our findings were also extended to develop a portable and paper-based sensing probe with good long-term stability to overcome the shortcomings of liquid-phase colorimetric sensors without requiring a spectrometer. The proposed colorimetric sensing probes provide accurate results even with a real sample and offer numerous advantages over conventional sensing platforms, including clearly distinguishable color changes that can be observed by the naked eye; thus, the proposed probes can be used for the selective, reliable, and low-cost point-of-care detection of Cu(II) ions in water.

Dual-Functional Capping Agent-Mediated Transformation of Silver Nanotriangles to Silver Nanoclusters for Dual-Mode Biosensing.

The localized surface plasmon resonance (LSPR) property, depending on the structure (morphology and assembly) of nanoparticles, is very sensitive to the environmental fluctuation. Retaining the colorimetric effect derived from the LSPR property while introducing new optical properties (such as fluorescence) that provide supplementary information is an effective means to improve the controllability in structures and reproducibility in optical properties. DNA as a green and low-cost etching agent has been demonstrated to effectively control the morphology and optical properties (the blue shift of the LSPR peak) of the plasmonic nanoparticles. Herein, taking silver nanotriangles (AgNTs) as a proof of concept, we report a novel strategy to induce precisely tunable LSPR and fluorescence-composited dual-mode signals by using mono-DNA first as an etching agent for etching the morphology of AgNTs and later as a template for synthesizing fluorescent silver nanoclusters (AgNCs). In addition, common templates for synthesizing AgNCs, such as l-glutathione and bovine serum albumin, were demonstrated to have the capability to serve as etching agents. More importantly, these biomolecules as dual-functional capping agents (etching agents and templates) follow the size-dependent rule: as the size of the thiolated biomolecule increases, the blue shift of the LSPR peak increases; at the same time, the fluorescence intensity increases. The enzyme that can change the molecular weight (size) of the biomolecular substrates (DNA, peptides, and proteins) through an enzymatic cleavage reaction was explored to regulate the LSPR and fluorescent properties of the resulting nanoparticles (by etching of AgNTs and synthesis of AgNCs), achieving excellent performance in detection of cancer-related proteases. This study can be expanded to other biopolymers to impact both fundamental nanoscience and applications and provide powerful new tools for bioanalytical biosensors and nanomedicine.

Facile Preparation of Monodisperse Silver Nanorods with Tunable Plasmon Resonances in the Near-Infrared Region: Implications for SERS-Based Sensing

The facile synthesis of silver nanorods with uniform size and tunable localized surface plasmon resonances is of great significance for plasmon resonance-related applications, such as surface-enhanced Raman spectroscopy (SERS)-based sensing, biomedical diagnostics, and photothermal therapy. However, improving reproducibility is difficult for nonexpert researchers since general synthesis methods involve multiple steps. Addressing this issue, this work develops a facile, effective synthetic strategy for monodisperse silver nanorods with tunable plasmon resonance in the near-infrared region assisted by in situ monitoring via an optical microfiber in the seed formation stage and surfactant-assisted purification of the final product. The optical microfiber monitoring ensures the formation of monodisperse bipyramid templates, guaranteeing the synthesis of the final product. The surfactant-assisted purification of the final product ensures the monodispersity of the final Ag nanorods. This study provides a flexible and alternative approach for nonexpert researchers and may present an opportunity for solving the reproducibility problem faced by nanomaterial synthesis.

Hot Spot Engineering in Hierarchical Plasmonic Nanostructures

The controllable nanogap structures offer an effective way to obtain strong and tunable localized surface plasmon resonance (LSPR). A novel hierarchical plasmonic nanostructure (HPN) is created by incorporating a rotating coordinate system into colloidal lithography. In this nanostructure, the hot spot density is increased drastically by the long-range ordered morphology with discrete metal islands filled in the structural units. Based on the Volmer-Weber growth theory, the precise HPN growth model is established, which guides the hot spot engineering for improved LSPR tunability and strong field enhancement. The hot spot engineering strategy is examined by the application of HPNs as the surface-enhanced Raman spectroscopy (SERS) substrate. It is universally suitable for various SERS characterization excited at different wavelengths. Based on the HPN and hot spot engineering strategy, single-molecule level detection and long-range mapping can be realized simultaneously. In that sense, it offers a great platform and guides the future design for various LSPR applications like surface-enhanced spectra, biosensing, and photocatalysis.

Seed-Mediated Synthesis of Thin Gold Nanoplates with Tunable Edge Lengths and Optical Properties

Thin Au nanoplates show intriguing localized surface plasmon resonance (LSPR) properties with potential applications in various fields. The conventional synthesis of Au nanoplates usually involves the formation of spherical nanoparticles or produces nanoplates with large thicknesses. Herein, we demonstrate a synthesis of uniform thin Au nanoplates by using Au-Ag alloy nanoframes obtained by the galvanic replacement of Ag nanoplates with HAuCl4 as the seeds and a sulfite (SO32-) as a ligand. The SO32- ligand not only complexes with the Au salt for the controlled reduction kinetics but also strongly adsorbs on Au {111} facets for effectively constraining the crystal growth on both basal sides of the Au nanoplates for controlled shape and reduced thicknesses. This seed-mediated synthesis affords Au nanoplates with a thickness of only 7.5 nm, although the thickness increases with the edge length. The edge length can be customizable in a range of 48-167 nm, leading to tunable LSPR bands in the range of 600-1000 nm. These thin Au nanoplates are applicable not only to surface-enhanced Raman spectroscopy with enhanced sensitivity and reliability but also to a broader range of LSPR-based applications.

High‐Performance Hydrogel SERS Chips with Tunable Localized Surface Plasmon Resonance for Coordinated Electromagnetic Enhancement with Chemical Enhancement

AbstractHydrogel surface‐enhanced Raman scattering (SERS) chips with tunable localized surface plasmon resonance (LSPR) wavelength are prepared to coordinate the chemical enhancement (CM) and electromagnetic enhancement (EM) effects for molecules. When detecting different molecules, a laser with matched energy is selected according to energy intervals between the molecular energy levels and the Fermi level of Ag nanoparticles to obtain the strongest CM effect. Meanwhile, a hydrogel SERS chip with the LSPR wavelength matching with the laser is selected to gain the strongest EM effect. As a result, the constructed hydrogel SERS chips show outstanding activity to many molecules. Amoxicillin, pymetrozine, and chlorpyrifos are used as the model molecules to demonstrate the great importance of CM effect and the working principle of the obtained hydrogel SERS chips. Besides the ultrahigh activity, the obtained hydrogel SERS chips also show high uniformity, long‐term stability, and strong anti‐interference to the sample matrix, and thereby are highly practical. This work not only provides an efficient strategy for building high‐performance SERS substrates, but also sheds the light on the mechanism of wave selection of SERS.

Plasmonic visible-near infrared photothermal activation of olefin metathesis enabling photoresponsive materials.

Light-induced catalysis and thermoplasmonics are promising fields creating many opportunities for innovative research. Recent advances in light-induced olefin metathesis have led to new applications in polymer and material science, but further improvements to reaction scope and efficiency are desired. Herein, we present the activation of latent ruthenium-based olefin metathesis catalysts via the photothermal response of plasmonic gold nanobipyramids. Simple synthetic control over gold nanobipyramid size results in tunable localized surface plasmon resonance bands enabling catalyst initiation with low-energy visible and infrared light. This approach was applied to the ROMP of dicyclopentadiene, affording plasmonic polymer composites with exceptional photoresponsive and mechanical properties. Moreover, this method of catalyst activation was proven to be remarkably more efficient than activation through conventional heating in all the metathesis processes tested. This study paves the way for providing a wide range of photoinduced olefin metathesis processes in particular and photoinduced latent organic reactions in general by direct photothermal activation of thermally latent catalysts.