Tunable plasmonic and structural properties of SnO2: Au thin films deposited via GLAD-enhanced DC Sputtering

Metals are commonly used in plasmonic devices because of their strong plasmonic property. However, such properties are not easily tuned. For applications such as spatial light modulators and beam steering, tunable plasmonic properties are essential, and neither metals nor other plasmonic materials possess truly tunable plasmonic properties. In this work, we show that the silver alloy silver–ytterbium (Ag-Yb) possesses tunable plasmonic properties; its plasmonic response strength can be adjusted as a function of Yb concentration. Such tunability can be explained in terms of the influence of Yb on bound charge and interaction of its dielectric with the dielectric of Ag. The change in transition characteristics progressively weakens Ag’s plasmonic properties. With a spectral ellipsometric measurement, it was shown that the Ag-Yb alloy thin film retains the properties of Ag with high transmission efficiency. The weakened surface plasmon coupling strength without dramatic change in the coupling wavelengths implies that the tunability of the Ag-Yb alloy is related to its volume ratio. The principle mechanism of the plasmonic change is theoretically explained using a model. This work points to a potential new type of tunable plasmonic material.

We report a simple and fast microwave-assisted method to grow silver nanoparticle films with tunable plasmon resonance band. Microwaving time controls nucleation and growth as well as particle agglomeration, cluster formation, particle morphology, and the plasmonic properties. Films produced with times shorter than 30 s presented a single well-defined plasmon resonance band (~ 400 nm), whereas films produced with times longer than 40 s presented higher wavelength resonances modes (> 500 nm). Plasmon band position and intensity can be easily tuned by controlling microwaving time and power. SEM and AFM images suggested the growth of asymmetrical silver nanoparticles. Simulated extinction spectra considering particles as spheres, hemispheres, and spherical caps were performed. The films were employed to enhance the sensitivity of ionizing radiation detectors assessed by optically stimulated luminescence (OSL) via plasmon-enhanced luminescence. By tuning the plasmon resonance band to overlap with the OSL stimulation (530 nm), luminescence enhancements of greater than 100-fold were obtained, demonstrating the importance of tuning the plasmon resonance band to maximize the OSL intensity and detector sensitivity. This versatile method to produce silver nanoparticle films with tunable plasmonic properties is a promising platform for developing small-sized radiation detectors and advanced sensing technologies.

Construction of silica-encapsulated gold-silver core-shell nanorod: Atomic facets enrichment and plasmon enhanced catalytic activity with high stability and reusability

Engineering magnetic nanoparticles with tunable structural properties and magnetism is critical to develop desirable magnetic particle imaging (MPI) tracers for biomedical applications. Here we present a new superparamagnetic metal oxide nanoparticle with a controllable chemical composition and magnetism for imaging tumor xenografts in living mice. Superparamagnetic Zn/Fe mixed metal oxide (ZnFe-MMO) nanoparticles are fabricated via a facile one-pot co-precipitation method in water followed by thermal decomposition with tunable Zn/Fe ratios and at various calcination temperatures. This work, for the first time, presented LDH-derived metal oxides for an MPI application. The metal composition is tunable to present an optimized MPI performance. The analytical results demonstrate that ZnFe-MMO nanoparticles at the designed molar ratio of Zn/Fe = 2:1 after 650 °C calcination demonstrate a higher saturation magnetization (MS) value and optimal MPI signal than the samples presented with other conditions. The excellent biocompatibility of ZnFe-MMO is demonstrated in both breast cancer cells and fibroblast cell cultures. In vivo imaging of 4T1 tumor xenografts in mice using ZnFe-MMO as a tracer showed that the mean signal intensity is 1.27-fold higher than the commercial tracer VivoTrax at 72 h post-injection, indicating ZnFe-MMO's promise for prolonged MPI imaging applications.

ZnO thin films have attracted significant interest in the past decades owing to their unique wide band gap properties, piezoelectric properties, non-linearity and plasmonic properties. Recent efforts have been made in coupling ZnO with secondary phases to enhance its functionalities, such as Au-ZnO nanocomposite thin films with tunable optical and plasmonic properties. In this work, magnetic nanostructures of Ni are incorporated in ZnO thin films in a vertically aligned nanocomposite (VAN) form to couple magnetic and plasmonic response in a complex hybrid metamaterial system. Nickel (Ni) is of interest due to its ferromagnetic and plasmonic properties along with gold (Au) which is also plasmonic. Therefore, two approaches, namely, tuning of the deposition pressure and use of a ZnO-Au seeding layer have been attempted to achieve unique Ni nanostructures in addition to tuning of the microstructure. Together, both approaches demonstrate a range of microstructures such as core-shell, nanodisk, nanocup, and nanocube-like morphologies not previously attempted. Additionally, there is effective tuning of properties. Specifically, the seeding layer thickness causes hyperbolic behavior as well as redshift in the surface plasmon resonance (SPR) wavelength. The addition of the ZnO-Au seeding layer directly influences the optical properties. Plus, regardless of the different approaches, the films demonstrate magnetic anisotropy based on the composition and microstructure of the film which impacted the saturation magnetization and coercivity. This study demonstrates the potential of ZnO-based complex hybrid metamaterials with coupled electro-magneto-optical properties for integrated photonic devices.

Surface-enhanced Raman scattering (SERS) is an emerging analytical method used in biological and non-biological structure characterization. Since the nanostructure plasmonic properties is a significant factor for SERS performance, nanostructure fabrication with tunable plasmonic properties are crucial in SERS studies. In this study, a novel method for fabrication of tunable plasmonic silver nanodomes (AgNDs) is presented. The convective-assembly method is preferred for the deposition of latex particles uniformly on a regular glass slide and used as a template for polydimethylsiloxane (PDMS) to prepare nanovoids on a PDMS surface. The obtained nanovoids on the PDMS are used as a mold for AgNDs fabrication. The nanovoids are filled with Ag deposition by the electrochemical method to obtain metallic AgNDs. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used for characterization of the structural properties of all fabricated AgNDs. The optical properties of AgNDs are characterized with the evaluation of SERS activity of 4-aminothiphonel and rhodamine 6G. In addition to experimental characterizations, the finite difference time domain (FDTD) method is used for the theoretical plasmonic properties calculation of the AgNDs. The experimental and theoretical results show that the SERS performance of AgNDs is strongly dependent on the heights and diameters of the AgNDs.

A very simple protocol, which involves the chemical reduction of AgNO3 and Fe(NO3)3 with ethylene glycol as reducing agent, has been developed for synthesizing Ag@Fe3O4 core/shell nanostructures in which the silver nanoparticle core was covered by a thicker layer of the Fe3O4 nanoparticle shell. The obtained Ag@Fe3O4 core/shell nanostructures simultaneously possess both strong magnetic responsiveness and tunable plasmonic properties. The plasmonic properties of the composite nanospheres are profoundly influenced by the high dielectric constant of the outer Fe3O4 shell layer and could be conveniently modulated over a broad spectral range spanning from the ultraviolet to near-infrared (NIR) regions (789 nm) by simply altering the thickness of the Fe3O4 shell. The localized surface plasmon resonances of the core/shell nanocomposites red-shifted with increasing thickness of the Fe3O4 shell. The morphology transformation of the Ag/Fe3O4 nanocomposites from core/shell structures with a continuous dense coating to flower-like nanostructures also allows the tuning of their plasmonic properties to be blue-shifted (to 510 nm). Catalytic degradation of rhodamine 6G (R6G) experiments show that the Ag/Fe3O4 composite nanostructures exhibit high catalytic activity by sodium borohydride. Due to the efficient optical response through localized surface plasmon resonances, the catalytic performance from the silver core and external magnetic manipulation from the Fe3O4 shell, such multifunctional nanoparticles will provide an opportunity for simultaneous optical detection and catalytic reduction with the additional benefit of relatively facile recovery and regeneration.

Stimuli-responsive assembly of gold nanoparticles (AuNPs) with precise control of the plasmonic properties, assembly size, and stimuli responsivity has shown potential benefits with regard to biosensing devices and drug-delivery systems. Here we present a new pH-responsive coassembly system of oligo(ethylene glycol) (OEG)-coated AuNPs with anionic polymers as an external mediator via hydrogen bonding in water. Hydrogen-bond-driven coassemblies of OEG-AuNPs with poly(acrylic acid) (PAA) were confirmed by the monitoring of plasmonic peaks and hydrodynamic diameters. In this system, the protonation of anionic polymers on change in pH triggered the formation of hydrogen bond between the OEG-AuNPs and polymers, providing sensitive pH responsivity. The plasmonic properties and assembly size are affected by both the ratio of PAA to AuNPs and the molecular weight of PAAs. In addition, the attachment of hydrophobic groups to the surface ligand or anionic polymer changed the responsive pH range. These results demonstrated that the coassembly with an external mediator via hydrogen bonding provides a stimuli-responsive assembly system with tunable plasmonic properties, assembly size, and stimuli responsivity.

Gold nanoparticles have been thoroughly used in designing thermal ablative therapies and in photoacoustic imaging in cancer treatment owing to their unique and tunable plasmonic properties. While the plasmonic properties highly depend on the size and structure, controllable aggregation of gold nanoparticles can trigger a plasmonic coupling of adjacent electronic clouds, henceforth leading to an increase of light absorption within the near-infrared (NIR) window. Polymer-engraftment of gold nanoparticles has been investigated to achieve the plasmonic coupling phenomenon, but complex chemical steps are often needed to accomplish a biomedically relevant product. An appealing and controllable manner of achieving polymer-based plasmon coupling is a template-assisted Au+3 reduction that ensures in situ gold reduction and coalescence. Among the polymers exploited as reducing agents are polyethyleneimines (PEI). In this study, we addressed the PEI-assisted synthesis of gold nanoparticles and their further aggregation to obtain fractal NIR-absorbent plasmonic nanoaggregates for photothermal therapy and photoacoustic imaging of colorectal cancer. PEI-assisted Au+3 reduction was followed up by UV-visible light absorption, small-angle X-ray scattering (SAXS), and photo-thermal conversion. The reaction kinetics, stability, and the photothermal plasmonic properties of the as-synthesized nanocomposites tightly depended on the PEI : Au ratio. We defined a PEI-Au ratio range (2.5-5) for the one-pot synthesis of gold nanoparticles that self-arrange into fractal nanoaggregates with demonstrated photo-thermal therapeutic and imaging efficiency both in vitro and in vivo in a colorectal carcinoma (CRC) animal model.

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.

An embedment of metal nanoparticles of well-defined sizes in thin polymer films is of significant interest for a number of practical applications, in particular, for preparing materials with tunable plasmonic properties. In this article, we present a fabrication route for metal–polymer composites based on cluster beam technique allowing the formation of monocrystalline size-selected silver nanoparticles with a ±5–7% precision of diameter and controllable embedment into poly (methyl methacrylate). It is shown that the soft-landed silver clusters preserve almost spherical shape with a slight tendency to flattening upon impact. By controlling the polymer hardness (from viscous to soft state) prior the cluster deposition and annealing conditions after the deposition the degree of immersion of the nanoparticles into polymer can be tuned, thus, making it possible to create composites with either particles partly or fully embedded into the film. Good size selection and rather homogeneous dispersion of nanoparticles in the thin polymer film lead to excellent plasmonic properties characterized by the narrow band and high quality factor of localized surface plasmon resonance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1152–1159

A simple strategy based on the synergistic modulation of inter-particle and substrate-particle interaction is applied for the large-scale fabrication of two-dimensional (2D) Au and Ag nanoparticle arrays. The surface charge of the substrate is used to redistribute the double layer electric charges on the particles and to modulate the inter-particle distance within the 2D nanoparticle arrays on the substrate. The resultant arrays, with a wide range of inter-particle distances, display tunable plasmonic properties. It can be foreseen that such 2D nanoparticle arrays possess potential applications as multiplexed colorimetric sensors, integrated devices and antennas. Herein, it is demonstrated that these arrays can be employed as wavelength-selective substrates for multiplexed acquisition of surface-enhanced Raman scattering (SERS) spectra. This simple one step process provides an attractive and low cost strategy to produce high quality and large area 2D ordered arrays with tunable properties.

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.

Bimetallic nanoparticles are widely used in chemical catalysis and energy conversion. Their practical performance can be better exploited through morphological control by adjusting the synthetic strategy. Herein, an aqueous phase route is used to achieve the controlled preparation of bimetallic Au/Pt and hollow Au/Pt/Au nanotriangles with tunable plasmonic properties and superior photocatalytic activity. By continuously adjusting the concentration of surfactant solution, the gradual growth orientation of Pt nanoparticles on Au nanotriangles is observed, which occurs first on the tips, then on the edges, and then on the facets. Three types of Au/Pt nanotriangles (including Pt on the tips (Au/Pt (tips)), Pt on the edges (Au/Pt (edges)), and Pt covering Au (Au@Pt)) with tunable plasmon resonance are obtained. Then, Au/Pt/Au nanotriangles with a hollow structure are synthesized based on Au/Pt (edges). By evaluating the reduction rate of p-nitrophenol under visible light irradiation, hollow Au/Pt/Au nanotriangles exhibit the best photocatalytic activity compared with Au and Au/Pt (edges). The hollow structure, high visible light absorption and a strong tip- and center-focused local electric field of Au/Pt/Au are thought to be responsible for their superior photocatalytic activity.

In this short review we are discussing the creation of two dimensional nanostructures based on self-assembly of latex particles. Furthermore we are showing that optical properties of these structures can be controlled with their morphology and materials used for their preparation. Two representative structures, namely two dimensional arrays of triangles and holes are discussed in detail, starting with the preparatory step, followed by the structural and optical characterization, as well as the theoretical explanation of the plasmonic properties.