Tunable Localized Surface Plasmon Resonance Research Articles

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.

Diffusion-controlled bridging of the Au Island and Au core in Au@Rh(OH)3 core-shell structure.

Hybrid nanostructures have garnered considerable interest because of their fascinating properties owing to the hybridization of materials and their structural varieties. In this study, we report the synthesis of [Au@Rh(OH)3]-Au island heterostructures using a seed-mediated sequential growth method. Through the thiol ligand-mediated interfacial energy, Au@Rh(OH)3 core-shell structures with varying shell thicknesses were successfully obtained. On these Au@Rh(OH)3 core-shell seeds, by modulating the diffusion of HAuCl4 in the porous Rh(OH)3 shell, site-specific growth of Au islands on the inner Au core or on the surface of the outer Rh(OH)3 shell was successfully achieved. Consequently, two types of distinct structures, the Au island-on-[Au@Rh(OH)3] dimer and Au island-Au bridge-[Au@Rh(OH)3] dumbbell structures with thin necks were obtained. Further modulations of the growth kinetics led to the formation of Au plate-Au bridge-[Au@Rh(OH)3] heterostructures with larger structural anisotropy. The flexible structural variations were demonstrated to be an effective means of modulating the plasmonic properties; the Au-Au heterostructures exhibited tunable localized surface plasmon resonance in the visible-near-infrared spectral region and can be used as surface-enhanced Raman scattering (SERS) substrates capable of emitting strong SERS signals. This diffusion-controlled growth of Au bridges in the Rh(OH)3 shells (penetrating growth) is an interesting new approach for structural control, which enriches the tool box for colloidal nanosynthesis. This advancement in structural control is expected to create new approaches for colloidal synthesis of sophisticated nanomaterials, and eventually enable their extensive applications in various fields.

Controlled synthesis of monodisperse gold nanorods with a small diameter of around 10 nm and largest plasmon wavelength of 1200 nm.

Gold nanorods have been widely used in various fields due to their tunable anisotropic localized surface plasmon resonance (SPR) property. The facile preparation of gold nanorods with a tunable SPR wavelength extending to a near-infrared window, and at the same time, a relatively small particle size for facilitating applications especially in the biomedical field is of great value yet highly challenging. In this work, a new reducing agent, 1,6-dihydroxynaphthalene, is proposed for the synthesis of gold nanorods. The results indicate that gold nanorods with good monodispersity, high shape yield, maximum SPR wavelength of 1200 nm, and especially small diameter of around 10 nm can be acquired simultaneously. In terms of spectral and size controls, by respectively varying the experimental parameters including the amount of silver ions, reducing agents, and gold seeds not only can a good linear correlation be acquired corresponding to a SPR wavelength ranging from around 600 nm to 1200 nm, but a regular change in the particle diameter from 10.5 nm to 7.5 nm could also be observed. The structural and morphological evolutions of the particle for each changed parameter were carefully studied, and insights were gained into the growth mechanism based on the detailed analysis of particle evolution at a specific stage of the growth process.

Perovskite/Hole Transport Layer Interfacial Engineering with Substoichiometric Tungsten Oxide Rich in Oxygen Vacancies to Boost the Photovoltaic Performance of Perovskite Solar Cells

The collaborative strategy of optical design and charge transport dynamics optimization can provide double guarantee to achieve high‐efficient planar perovskite solar cells (PSCs). Herein, WO3−X nanorods with tunable localized surface plasmon resonance (LSPR) effect are introduced at the interface between perovskite and hole transport layer (HTL) via antisolvent method during the preparation of perovskite films. The photocurrent of WO3−X nanorods‐based devices significantly increases due to the extension of absorption region caused by LSPR effect. The charge transfer at the perovskite/HTL interface is also accelerated due to the electromagnetic near‐field enhancement via the LSPR effect. The synchronized improvement in photocurrent and charge transfer by WO3−X nanorods leads to a power conversion efficiency of 21.14% in MAPbI3‐based PSCs. This work not only provides an effective approach to enhance the photovoltaic performance of PSCs, but also demonstrates the potential application of inorganic oxide semiconductors with LSPR in other optoelectronic devices.

Fabrication of Cu-doped molybdenum oxide for bifunctional SERS and photothermal conversion

Heavily-doped semiconductor materials have attracted great attentions owing to their tunable localized surface plasmon resonance (LSPR) in the visible or near-infrared (NIR) range, which is expected to own excellent performance comparable to that of precious metals. However, the current strategies of doping MoO3 are usually tedious and not environmental-friendly, and the synergistic effects of oxygen vacancies and metal ion doping on the LSPR are rarely investigated. Herein, we report a facile supercritical CO2-assisted method to synthesize Cu-doped MoO3 nanoparticles (Cu–MoO3-x NPs) with tunable LSPR properties, and the morphology, doped Cu ion concentration and oxygen vacancies density can be modulated as the control of supercritical CO2 pressure from 10 to 16 MPa. Moreover, the Cu–MoO3-x NPs possess outstanding surface enhanced Raman spectroscopy (SERS) performance (with the enhancement factor of 3.48 × 107 and the limit of detection of 10−9 M) and relatively high photothermal conversion efficiency (62.4%). This work provides an efficient route for the fabrication of heavily-doped metal oxide semiconductors with superior LSPR performance in various light utilization fields.

Pattern Recognition Directed Assembly of Plasmonic Gap Nanostructures for Single-Molecule SERS.

Gold nanocubes (AuNCs) with tunable localized surface plasmon resonance properties are good candidates for plasmonic gap nanostructures (PGNs) with hot spots (areas with intense electric field localization). Nevertheless, it remains challenging to create shape-controllable nanogaps between AuNCs. Herein, we report a DNA origami directed pattern recognition strategy to assemble AuNCs into PGNs. By tuning the position and number of capture strands on the DNA origami template, different geometrical configurations of PGNs with nanometer-precise and shape-controllable gaps are created. The localized field enhancement in these gaps can generate hot spots that are in accordance with finite difference time domain simulations. Benefiting from the single Raman probe molecule precisely anchored at these nanogaps, the dramatic enhanced electromagnetic fields localized in hot spots arouse stronger single-molecule SERS (SM-SERS) signals. This method can be utilized in the design of ultrahigh-sensitivity photonic devices with tailored optical properties and SERS-based applications.

Nanoscale mapping of shifts in dark plasmon modes in sub 10 nm aluminum nanoantennas

In this work, we report the fabrication and spectroscopic characterization of subwavelength aluminum nanocavities—consisting of hexamer or tetramer clusters of sub 10 nm width Al nanorods—with tunable localized surface plasmon resonance (LSPR) energies on suspended SiN x membranes. Here the volume plasmon (VP) and LSPR modes of lithographically-fabricated Al nanocavities are revealed by low-loss electron energy-loss spectroscopy (EELS) in an aberration corrected scanning transmission electron microscope (STEM). We show that the existence of grain boundaries (GBs) in these nanocavities results in shifts in the VP energy and a reduction in the VP lifetime. We map the VP energy and lifetime across GBs and we observe a decrease in VP energy and lifetime at GBs that is consistent with a reduction in free carrier density and increased plasmon scattering at these locations. Dipolar LSPR modes resonant in the UV and blue regions of the electromagnetic spectrum as well as higher-energy optically dark quadrupolar and hexapolar LSPR modes are also observed and mapped by STEM and EELS. All LSPR modes are confirmed via electromagnetic simulations based on the boundary element method. Both tetramer and hexamer structures support the excitation of dipolar bright and dipolar dark modes. Finally, we find that asymmetries in fabricated nanorod hexamer and tetramer nanocavities result in a mode mixing leading to a shift in dipolar dark LSPR modes.