Tunable Plasmonic Properties Research Articles

Engineering Carrier Density and Effective Mass of Plasmonic TiN Films by Tailoring Nitrogen Vacancies.

The introduction of nitrogen vacancies has been shown to be an effective way to tune the plasmonic properties of refractory titanium nitrides. However, its underlying mechanism remains debated due to the lack of high-quality single-crystalline samples and a deep understanding of electronic properties. Here, a series of epitaxial titanium nitride films with varying nitrogen vacancy concentrations (TiNx) were synthesized. Spectroscopic ellipsometry measurements revealed that the plasmon energy could be tuned from 2.64 eV in stoichiometric TiN to 3.38 eV in substoichiometric TiNx. Our comprehensive analysis of electrical and plasmonic properties showed that both the increased electronic states around the Fermi level and the decreased carrier effective mass due to the modified electronic band structures are responsible for tuning the plasmonic properties of TiNx. Our findings offer a deeper understanding of the tunable plasmonic properties in epitaxial TiNx films and are beneficial for the development of nitride plasmonic devices.

Tunable surface plasmon properties of hollow cylindrical nanocomposite structures

Tunable surface plasmon properties of hollow cylindrical nanocomposite structures

Low-loss plasmons in Weyl semimetals Mn3Sn

We report the optical reflectance measurement for Weyl semimetal Mn3Sn single crystal at room temperature. We observe a low-loss plasmon in the UV energy ranges. This low plasmonic loss is associated with a large electron scattering rate contributed by electron-electron interaction and scattering of conduction electrons by Mn atoms. The incorporation of more Mn atoms simultaneously adds more elastic scattering centers and increases the strength of electron-electron correlation which generates multiple plasmons with lower plasmonic loss in Mn3+xSn1-x. The UV tunable plasmonic properties in Mn3+xSn1-x have great potential for plasmonic and spintronic applications. We also discuss the plasmonic loss in Mn3Sn to the other conducting materials including correlated and non-correlated systems establishing the crucial role of electron correlation on the plasmonic loss. Our result suggests novel and effective strategies for obtaining lower plasmonic loss in the class of correlated materials.

Design of Biopolymer-Coated Gold Nanorods as Biorelevant Photothermal Agents.

Gold nanorods (AuNRs) are emerging metallic nanoparticles utilized to generate heat for photothermal therapy (PTT) in cancer. The tunable plasmonic properties of AuNRs make them a remarkable candidate for hyperthermia. However, the cytotoxicity of AuNRs limits its biological applicability due to the existence of cetyltrimethylammonium bromide (CTAB) on the surface as a common surfactant. In this study, AuNRs are synthesized by seed-mediated growth and then the optical properties are optimized by altering AgNO3 concentration. Afterward, CTAB is replaced with biopolymers which are BSA:Dextran and BSA:Guar Gum conjugates resulting in enhanced cellular viability, enabling to use of them as biologically relevant photothermal agents. The biocompatibility of AuNRs is improved to utilize them at high concentrations for laser studies, in which similar heat generation success of CTAB- and biopolymer-coated AuNRs are shown for potential PTT applications. CTAB and biopolymer-coated AuNRs in concentrations of 0.5 and 1mg mL-1 are irradiated under NIR light at 808nm laser at 0.5, 0.75, and 1W cm-2 for 300 s. The biopolymer-coated gold nanorods with different coatings preserve photothermal properties while reducing the cytotoxicity effects of CTAB and thus they are promising photothermal agents for potential PTT.

Self-Assembled TiN-Metal Nanocomposites Integrated on Flexible Mica Substrates towards Flexible Devices.

The integration of nanocomposite thin films with combined multifunctionalities on flexible substrates is desired for flexible device design and applications. For example, combined plasmonic and magnetic properties could lead to unique optical switchable magnetic devices and sensors. In this work, a multiphase TiN-Au-Ni nanocomposite system with core-shell-like Au-Ni nanopillars embedded in a TiN matrix has been demonstrated on flexible mica substrates. The three-phase nanocomposite film has been compared with its single metal nanocomposite counterparts, i.e., TiN-Au and TiN-Ni. Magnetic measurement results suggest that both TiN-Au-Ni/mica and TiN-Ni/mica present room-temperature ferromagnetic property. Tunable plasmonic property has been achieved by varying the metallic component of the nanocomposite films. The cyclic bending test was performed to verify the property reliability of the flexible nanocomposite thin films upon bending. This work opens a new path for integrating complex nitride-based nanocomposite designs on mica towards multifunctional flexible nanodevice applications.

Welded Gold Nanoparticle Assemblies Defined Plasmonic Coupling.

Nanoparticle assemblies with interparticle ohmic contacts are crucial for nanodevice fabrication. Despite tremendous progress in DNA-programmable nanoparticle assemblies, seamlessly welding discrete components into welded continuous three-dimensional (3D) configurations remains challenging. Here, we introduce a single-stranded DNA-encoded strategy to customize welded metal nanostructures with tunable morphologies and plasmonic properties. We demonstrate the precise welding of gold nanoparticle assemblies into continuous metal nanostructures with interparticle ohmic contacts through chemical welding in solution. We find that the welded gold nanoparticle assemblies show a consistent morphology with welded efficiency over 90%, such as the rod-like, triangular, and tetrahedral metal nanostructures. Next, we show the versatility of this strategy by welding gold nanoparticle assemblies of varied sizes and shapes. Furthermore, the experiment and simulation show that the welded gold nanoparticle assemblies exhibit defined plasmonic coupling. This single-stranded DNA encoded welding system may provide a new route for accurately building functional plasmonic nanomaterials and devices.

Tunable Plasmonic Properties of Spatially Overlapping Asymmetric Nanoparticle Dimers

Tunable Plasmonic Properties of Spatially Overlapping Asymmetric Nanoparticle Dimers

INFLUENCE OF THE REDUCING AGENTS ON MORPHOLOGY AND PROPERTIES OF SIVER STRUCTURES ON PAPER

Abstract. A paper-based SERS substrate with tunable plasmonic properties and excellent flexibility has been applied in various fields. These SERS substrates were prepared using a direct chemical reduction synthesis method for the present work. The isotropic and anisotropic morphology of silver structures on cellulose paper fiber were controlled by the types of reducing agents: (1) sodium borohydride (NaBH4), (2) ascorbic acid (L-AA), (3) glucose, (4) formaldehyde (HCHO). The plasmon characterization of silver structures on paper was systematically investigated. The fabricated paper-based SERS substrates were used to detect melamine in an aqueous solution and determine the influence of type reducing agents on the enhancement factor (EF) and signal uniformity of SERS substrates.

Controlled formation of gold nanoparticles with tunable plasmonic properties in tellurite glass

Silicate glasses with metallic nanoparticles (NPs) have been of intense interest in art, science and technology as the plasmonic properties of these NPs equip glass with light modulation capability. The so-called striking technique has enabled precise control of the in situ formation of metallic NPs in silicate glasses for applications from coloured glasses to photonic devices. Since tellurite glasses exhibit the unique combination of comparably easy fabrication, low phonon energy, wide transmission window and high solubility of luminescent rare earth ions, there has been a significant amount of work over the past two decades to adapt the striking technique to form gold or silver NPs in tellurite glasses. Despite this effort, the striking technique has remained insufficient for tellurite glasses to form metal NPs suitable for photonic applications. Here, we first uncover the challenges of the traditional striking technique to create gold NPs in tellurite glass. Then, we demonstrate precise control of the size and concentration of gold NPs in tellurite glass by developing new approaches to both steps of the striking technique: a controlled gold crucible corrosion technique to incorporate gold ions in tellurite glass and a glass powder reheating technique to subsequently transform the gold ions to gold NPs. Using the Mie theory, the size, size distribution and concentration of the gold NPs formed in tellurite glass are determined from the plasmonic properties of the NPs. This fundamental research provides guidance for designing and manipulating the plasmonic properties in tellurite glass for photonics research and applications.

Plasmonic Nano‐Rotamers with Programmable Polarization‐Resolved Coloration

Abstract3D‐shaped artificial Mg nano‐rotamers with a programmable dihedral angle between two plasmonic arms, designed to exhibit both programmable linear and circular polarization properties, are presented. The nanoscale physical shadow growth technique offers precise control over the angular alignment in these nanostructures with 1° angular precision, thus controlling their symmetry from achiral C2v and C2h to chiral C2. As a result, they give rise to a wide range of polarization‐resolved coloration, spanning from invisible to visible colors with 46% transmission contrast for linear polarization while exhibiting 0.08 g‐factor in visible for circular polarization. These nano‐rotamers hold great potential for various applications in adaptive photonic filters, memory, and anticounterfeiting devices, benefiting from their tunable plasmonic properties.

Hybrid Integration of Au Nanoplates and Ag Nanoparticles with Controlled Nanogaps via Cu2O‐mediated Galvanic Replacement Reaction: Plasmonic Catalysis and Photothermal Conversion

AbstractRational assembling of different noble metal nanocrystals with controlled nanogaps in one entity allows the efficient coupling of electromagnetic fields of each component and versatile manipulation over the overall physiochemical properties. In the present study, we report a stepwise synthetic strategy to hybridlike assemble Au nanoplate and Ag nanoparticles without direct physical contact. Particularly, the success of current work relies on the conformal coating of Cu2O over the Au nanoplate as an intermediate layer, followed by the in situ formation of Ag nanoparticles via the galvanic replacement reaction between Cu2O and Ag+. With the anchoring of Ag nanoparticles over the Cu2O‐wrapped Au nanoplate, the resulting hybrid nanostructures exhibit noticeable multiple plasmonic absorptions across the UV‐vis‐NIR region. The potential use as the plasmonic catalyst for current Au@Cu2O‐Ag hybrid products is validated using reduction of 4‐nitrophenol as the model reaction, where the catalytic performance is greatly improved by the UV‐vis light irradiation. They also exhibit satisfactory photothermal conversion performance under the irradiation of Xe lamp. The current work provides a niche strategy to create noble‐metal hybrid nanostructures with controlled interparticle distance and tunable plasmonic properties, could be extended to other noble metal or alloys.

Silver-based plasmonic nanoparticles and their application as biosensor

The silver nanoparticles (AgNPs) exhibit unique and tunable plasmonic properties. The size and shape of these particles can manipulate their localized surface plasmon resonance (LSPR) property and their response to the local environment. The LSPR property of nanoparticles is exploited by their optical, chemical, and biological sensing. This is an interdisciplinary area that involves chemistry, biology, and materials science. In this paper, a polymer system is used with the optimization technique of blending two polymers. The two polymer composites polystyrene/poly (4-vinylpyridine) (PS/P4VP) (50:50) and (75:25) were used as found suitable by their previous morphological studies. The results of 50, 95, and 50, 150 nm thicknesses of silver nanoparticles deposited on PS/P4VP (50:50) and (75:25) were explored to observe their optical sensitivity. The nature of the polymer composite embedded with silver nanoparticles affects the size of the nanoparticle and its distribution in the matrix. The polymer composites used are found to have a uniform distribution of nanoparticles of various sizes. The optical properties of Ag nanoparticles embedded in suitable polymer composites for the development of the latest plasmonic applications, owing to their unique properties, were explored. The sensing capability of a particular polymer composite is found to depend on the size of the nanoparticle embedded in it. The optimum result has been found for silver nanoparticles of 150 nm thickness deposited on PS/P4VP (75:25).

Cysteine-assisted overgrowth of gold nanorods to prepare highly branched gold nanoantennas with tunable morphological and plasmonic properties

In this work, gold nanoantennas with high branching properties were prepared by cysteine-assisted overgrowth of gold nanorods (AuNRs).

Near-infrared light activatable niosomes loaded with indocyanine green and plasmonic gold nanorods for theranostic applications.

Light-mediated theranostic platforms involve the use of agents (small molecules/nanomaterials), which can absorb light to produce either heat or reactive chemical species (RCS) and emit fluorescence. Such platforms are advantageous in the field of personalized medicine, as they provide enhanced diagnostic capabilities, improved therapeutic efficiencies, and can also simultaneously monitor the treatment outcomes using imaging modalities. Specifically, agents absorbing near-infrared (NIR) light can provide minimal scattering, low autofluorescence, superior spatio-temporal resolution, and deeper tissue penetration depths. Gold nanorods (GNR) and indocyanine green (ICG) are two agents known to absorb light in the NIR region. GNR can provide tunable plasmonic properties, while ICG is an FDA-approved NIR fluorophore. However, the use of ICG and GNR suffers from various limitations, such as photobleaching, non-specificity, toxicity, and aggregation in solution. To overcome these limitations, herein, we report on NIR light-activatable niosomes loaded with GNR and ICG for cancer theranostic applications. Both agents were encapsulated into non-ionic surfactant-based biocompatible niosomes to form ICG-GNR@Nio with superior loading efficiencies and enhanced properties. ICG-GNR@Nio offers excellent storage stability, photostability, elevated temperature rise and generation of reactive oxygen species (ROS) upon 1064 nm laser irradiation. Subsequently, the enhanced phototherapeutic capabilities mediated by ICG-GNR@Nio were validated in the in vitro cellular experiments. Overall, ICG-GNR@Nio-based theranostic platforms can provide a significant benchmark in the improved diagnosis and therapeutic capabilities for biomedical clinicians to tackle various diseases.

Low-cost and simple fabrication of hierarchical Al nanopit arrays for deep ultraviolet refractive index sensing

Herein, we proposed a simple non-lithographic way to fabricate hierarchical Al nanopit arrays performed as deep ultraviolet (DUV, 200–300 nm) refractive index sensing. Only by adjusting the Al deposition thickness on the Al nanopit array, the hierarchical Al nanopit arrays with tunable plasmonic properties in the DUV region were obtained. The prepared hierarchical Al nanopit arrays are of very good time stability and its RI sensitivity and concentration detection limit of adenine ethanol solution reach 311 nm/RIU and respectively, as the Al deposition thickness is 60 nm. Furthermore, the electric field distribution simulation results show that high RI sensing characteristic are mainly attributed to the local surface plasmon resonance. This investigation provides a facile way to develop low cost, high efficient and easily fabricated Al-based RI sensor in the DUV region.

Preparation of triangular silver nanoplates by improved light-driven seed growth method

Triangular silver nanoplates have been synthesized by the improved light-driven seed growth method with only trisodium citrate as both photoreducing reagent and capping reagent under the irradiation of sodium lamp. • Triangular silver nanoplates (TSNPs) can exhibit tunable plasmonic properties across the entire visible spectrum and in the near-infrared region. • TSNPs have been synthesized by the improved light-driven seed growth method with only trisodium citrate as both photoreducing reagent and capping reagent. • The simple rapid preparation process will make it apply in large scale. Triangular silver nanoplates (TSNPs) have attracted much attention for their tunable plasmonic properties. In this letter, TSNPs have been synthesized by the improved light-driven seed growth method with only trisodium citrate (TSC) as both photoreducing reagent and capping reagent. By means of this high efficient method, TSNPs could be produced in high yield. As a kind of promising material, TSNPs will be used for chemical and biological sensing, and they can also be applied in optical limiters against high intensity laser pulse.

Plasmonic high-entropy carbides

Discovering multifunctional materials with tunable plasmonic properties, capable of surviving harsh environments is critical for advanced optical and telecommunication applications. We chose high-entropy transition-metal carbides because of their exceptional thermal, chemical stability, and mechanical properties. By integrating computational thermodynamic disorder modeling and time-dependent density functional theory characterization, we discovered a crossover energy in the infrared and visible range, corresponding to a metal-to-dielectric transition, exploitable for plasmonics. It was also found that the optical response of high-entropy carbides can be largely tuned from the near-IR to visible when changing the transition metal components and their concentration. By monitoring the electronic structures, we suggest rules for optimizing optical properties and designing tailored high-entropy ceramics. Experiments performed on the archetype carbide HfTa4C5 yielded plasmonic properties from room temperature to 1500K. Here we propose plasmonic transition-metal high-entropy carbides as a class of multifunctional materials. Their combination of plasmonic activity, high-hardness, and extraordinary thermal stability will result in yet unexplored applications.

A novel method based on Ag–Au nanorings with tunable plasmonic properties for the sensitive detection of amantadine

To prevent the toxic effect of amantadine (AMD) on humans, a sensitive and direct detection method is required. The conventional enzyme-linked immunosorbent assay (ELISA) usually shows a monochromatic gradient color variation with the concentration of the target; hence, it is not a sensitive method for naked-eye detection. In this work, Ag–Au nanorings with highly tunable plasmon properties were synthesized as colorimetric nanosensors. The growth of Ag on the hollow nanorings led to rich color variations. Ag–Au nanorings were integrated into ELISA for the sensitive detection of AMD with the naked eye. The proposed method showed high sensitivity for the qualitative and quantitative detection of AMD, the visible cut-off value (0.2 ng mL−1) and limit of detection (0.071 ng mL−1) were 10-fold and 4.7-fold lower, respectively, than those of conventional ELISA. This method showed a linear range of 0.08–2 ng mL−1 and 4–12 ng mL−1. The detection results of this method on 100 samples (food samples and municipal water) agreed well with those of liquid chromatography-tandem mass spectrometry. The proposed plasmonic ELISA has high sensitivity, easy operation, and naked-eye readout.

Multifunctional plasmonic gold nanostars for cancer diagnostic and therapeutic applications.

Gold nanostar (AuNSt) has gained great attention in bioimaging and cancer therapy due to their tunable surface plasmon resonance across the visible-near infrared range. Photothermal treatment and imaging capabilities including fluorescence lifetime imaging at two-photon excitation (TP-FLIM) and dark-field microscopic imaging are considered in this work. Two types of AuNSts having plasmon absorption peaks centred at 600 and 750 nm wavelength were synthesized and studied. Both NSts exhibited low cytotoxicity on A549 human lung carcinoma cells. A strong emission at two-photon excitation was observed for both NSts, well-distinguishable from lifetimes of bio-object autofluorescence. High efficiency in raising the temperature in the NSts environment with the irradiation of near infrared, AuNSts triggered photothermal effect. The decreased cell viability of A549 observed via MTT test and the cell membrane damaging was demonstrated with trypan blue staining. These results suggest AuNSts can be agents with tunable plasmonic properties for imaging and photothermal therapy.

Doping Independent Work Function and Stable Band Gap of Spinel Ferrites with Tunable Plasmonic and Magnetic Properties.

Tuning optical or magnetic properties of nanoparticles, by addition of impurities, for specific applications is usually achieved at the cost of band gap and work function reduction. Additionally, conventional strategies to develop nanoparticles with a large band gap also encounter problems of phase separation and poor crystallinity at high alloying degree. Addressing the aforementioned trade-offs, here we report Ni-Zn nanoferrites with energy band gap (Eg) of ≈3.20 eV and a work function of ≈5.88 eV. While changes in the magnetoplasmonic properties of the Ni-Zn ferrite were successfully achieved with the incorporation of bismuth ions at different concentrations, there was no alteration of the band gap and work function in the developed Ni-Zn ferrite. This suggests that with the addition of minute impurities to ferrites, independent of their changes in the band gap and work function, one can tune their magnetic and optical properties, which is desired in a wide range of applications such as nanobiosensing, nanoparticle based catalysis, and renewable energy generation using nanotechnology.