The fabrication of highly ordered silver nanodot patterns by platinum assisted nanoimprint lithography

Silver has been widely used for optical sensing and imaging applications which benefit from localized surface plasmon resonance (LSPR) in a nanoscale configuration. Many attempts have been made to fabricate and control silver nanostructures in order to improve the high performance in sensing and other applications. However, a fatal mechanical weakness of silver and a lack of durability in oxygen-rich conditions have disrupted the manufacturing of reproducible nanostructures by the top-down lithography approach. In this study, we suggest a steady fabrication strategy to obtain highly ordered silver nanopatterns that are able to provide tunable LSPR characteristics. By using a protecting layer of platinum on a silver surface in the lithography process, we successfully obtained large-area (2.7 × 2.7 mm(2)) silver nanopatterns with high reproducibility. This large-area silver nanopattern was capable of enhancing the low concentration of a Cy3 fluorescence signal (～10(-10) M) which was labeled with DNA oligomers.     

Ellipsometric advances for local surface plasmon resonance to determine chitosan adsorption on layer-by-layer gold nanoparticles

The ellipsometric measurement of local surface plasmon resonance (LSPR) caused by the adsorption of chitosan on layer-by-layer gold nanoparticles (Au NPs) was investigated. Six nanometer (6 nm) Au NPs were prepared and layer-by-layer Au NPs were fabricated to shift the LSPR to 520, 540, and 560 nm, respectively, due to the Mie theory. The thicknesses and the fractions of the layer-by-layer Au NPs were measured accurately using a combination of the Fresnel equation and the Maxwell-Garnett equations for ellipsometry. Furthermore, the position of the LSPR was shifted by chitosan. Using trajectory to record the trace of polarized light for ellipsometry resulting from LSPR, it was found that LSPR is predominantly induced when the LSPR position is close to the wavelength of the ellipsometric measurement. The trajectory circle of LSPR is very large for an increase of chitosan adsorption on Au NPs when the LSPR position is close to the detected wavelength. The linear approximation aspect quantifying the trajectory corresponds with the change of LSPR for the adsorption of chitosan, except for cases with low incidence and Brewster angles. The aspects and technologies of ellipsometry will benefit from the findings in this study, with potential applications in the fields of determination of molecular adsorption.     

A Novel Hierarchical Nanostructure for Enhanced Optical Nonlinearity Based on Scattering Mechanism

Surface modification of nonlinear optical materials (NOMs) is widely applied to fabricate diverse photonic devices, such as frequency combs, modulators, and all‐optical switches. In this work, a double‐layer nanostructure with heterogeneous nanoparticles (NPs) is proposed to achieve enhanced third‐order optical nonlinearity of NOMs. The mechanism of modified optical nonlinearity is elucidated to be the scattering‐induced energy transfer between adjacent NPs layers. Based on the LiNbO₃ platform, as a typical example, double layers of embedded Cu and Ag NPs are synthesized by sequential ion implantation, demonstrating twofold magnitude of near‐infrared enhancement factor and modulation depth in comparison with a single layer of Cu NPs. With the elastic collision model and thermolysis theory being considered, the shift of the localized surface plasmon resonance (LSPR) peak reveals the formation mechanism of the double‐layer nanostructure. Utilizing the enhanced optical nonlinearity of LiNbO₃ as modulators, a Q‐switched mode‐locked waveguide laser at 1 µm is achieved with shorter pulse duration. It suggests potential applications to improve the performance of nonlinear photonic devices by using double‐layer metallic nanostructures.     

Site-selective synthesis of silver nanoparticles in pre-patterned trenches and their localized surface plasmon resonances

A method for depositing silver nanoparticles in a pre-patterned trench by site-selective synthesis is described. In the trench patterns with various shapes, silver nanoparticles can be selectively nucleated and grown only on polyvinylpyrrolidone (PVP) domains by attraction (or repulsion) between silver ions and the hydrophilic PVP island domains in a silica matrix of the trench (or the hydrophobic fluorosilane layer). Regarding the silver nanoparticles in the trench, localized surface plasmon resonance (LSPR) could be excited by obliquely incident light, reradiating the enhanced electromagnetic field in the far- and near-fields. Even in the case of a large angle incidence in total internal reflection (TIR), the patterned silver nanoparticle clusters underwent strong scattering with a high intensity, due to the LSPR effect.     

Multi-Wavelength-Recognizable Memristive Devices via Surface Plasmon Resonance Effect for Color Visual System

Photoelectric memristor has attracted many attentions thanks to their promising potential in optical communication chips and artificial vision systems. However, the implementation of an artificial visual system based on memristive devices remains a considerable challenge because most photoelectric memristors cannot recognize color. Herein, multi-wavelength recognizable memristive devices based on silver(Ag) nanoparticles (NPs) and porous silicon oxide (SiO_x) nanocomposites are presented. Rely on the effects of localized surface plasmon resonance (LSPR) and optical excitation of Ag NPs in SiO_x, the set voltage of the device can be gradually reduced. Moreover, the current overshoot problem is alleviated to suppress conducting filament overgrowth after visible light irradiation with different wavelengths, resulting in diverse low resistance states (LRS). Taking advantage of the characteristics of controlled switching voltage and LRS resistance distribution, color image recognition is finally realized in the present work. X-ray photoelectron spectroscopy (XPS) and conductive atomic force microscopy (C-AFM) show that the light irradiation plays an important role on resistive switching (RS) process: the photo-assisted Ag ionization leads to a significant reduction of set voltage and overshoot current. This work provides an effective method toward the development of multi-wavelength-recognizable memristive devices for future artificial color vision system.     

Synthesis and Characterization of Tunable Rainbow Colored Colloidal Silver Nanoparticles Using Single-Nanoparticle Plasmonic Microscopy and Spectroscopy

Noble metal nanoparticles (NPs) possess size- and shape- dependent optical properties, suggesting the possibility of tuning desired optical properties of ensemble NPs at single NP resolution and underscoring the importance of probing the sizes and shapes of single NPs in situ and in real-time. In this study, we synthesized twelve colloids of Ag NPs. Each colloid contains various sizes and shapes of single NPs, showing rainbow colors with peak-wavelength of absorption spectra from 393 to 738 nm. We correlated the sizes and shapes of single NPs determined by high-resolution transmission electron microscopy (HRTEM) with scattering localized surface plasmon resonance (LSPR) spectra of single NPs characterized by dark-field optical microcopy and spectroscopy (DFOMS). Single spherical (2-39 nm in diameter), rod (2-47 nm in length with aspect ratios of 1.3-1.6), and triangular (4-84 nm in length with thickness of 2-27 nm) NPs show LSPR spectra (λ(max)) at 476±5 or 533±12, 611±23, and 711±40 nm, respectively. Notably, we observed new cookie-shaped NPs, which exhibit LSPR spectra (λ(max)) at 725±10 nm with a shoulder peak at 604±5 nm. Linear correlations of sizes of any given shape of single NPs with their LSPR spectra (λ(max)) enable the creation of nano optical rulers (calibration curves) for identification of the sizes and shapes of single NPs in solution in real time using DFOMS, offering the feasibility of using single NPs as multicolored optical probes for study of dynamics events of interest in solutions and living organisms at nm scale in real time.     

银纳米颗粒的化学还原法制备简介及其应用

银纳米颗粒的光学性能,如局域表面等离子体共振(Localized Surface Plasmon Resonance,LSPR)特性可通过其形貌、尺寸、外部介电环境的调控而实现变化。不同形貌的银纳米颗粒具有强弱不同的局域表面等离子体共振效应,从而表现出独特的光学性质。综述了利用化学还原法制备不同形貌的银纳米颗粒,主要包括柠檬酸钠还原法、多元醇法以及种子介导生长法,分析了这3种合成方法的机理和特点,将近年来不同形貌银纳米颗粒的研究进展进行了综述。最后介绍了不同形貌银纳米颗粒在表面增强拉曼散射(Surface-Enhanced Roman scattering,SERS)基底、催化、抗菌领域上的应用研究,并总结和展望了银纳米颗粒在合成和相关应用领域的发展前景。     

5 nm Silver Nanoparticles Amplify Clinical Features of Atopic Dermatitis in Mice by Activating Mast Cells

The triggering effect of silver nanoparticles (NPs) on the induction of allergic reactions is evaluated, by studying the activation of mast cells and the clinical features of atopic dermatitis in a mouse model. Granule release is induced in RBL‐2H3 mast cells by 5 nm, but not 100 nm silver NPs. Increases in the levels of reactive oxygen species (hydrogen peroxide and mitochondrial superoxide) and intracellular Ca⁺⁺ in mast cells are induced by 5 nm silver NPs. In a mouse model of atopic dermatitis induced by a mite allergen, the skin lesions are more severe and appear earlier in mice treated simultaneously with 5 nm silver NPs and allergen compared with mice treated with allergen alone or 100 nm silver NPs and allergen. The histological findings reveal that number of tryptase‐positive mast cells and total IgE levels in the serum increase in mice treated with 5 nm silver NPs and allergen. The results in this study indicate that cotreatment with 5 nm silver NPs stimulates mast cell degranulation and induces earlier and more severe clinical alterations in allergy‐prone individuals.     

Patterning of polymer nanocomposite resists containing metal nanoparticles by electron beam lithography

Poly(vinyl pyrrolidone) (PVP)-stabilized silver nanoparticles (NPs) were used as a new nanocomposite resist for electron beam lithography. A nanocomposite resist prepared by reducing silver nitrate in an alcoholic PVP solution was patterned by using a scanning electron microscope equipped with a nanometer pattern generation system. Well-defined negative tone patterns with a good sensitivity of 200 microC/cm2 and a contrast of 2.83 were obtained using the prepared nanocomposite resist. In addition, the changes in the morphology and structure of the resist patterns with a thermal treatment temperature were investigated by a FE-SEM with an EDX. The results revealed that the patterns of Ag NPs were formed through sintering the formed resist patterns at above 300 degrees C.     

Hydrogen storage in Pd nanodisks characterized with a novel nanoplasmonic sensing scheme

A novel nanoplasmonic sensing scheme is introduced based on remote real-time detection of induced electronic and shape/structural changes in a metal nanoparticle during the metal-hydride formation process. The localized surface plasmon resonance (LSPR) of the nanoparticle is utilized as signal transducer for optical readout. As a model system, hydrogen storage through metal-hydride formation is studied in Pd nanodisks. The experimentally obtained plasmonic response to hydrogen uptake yields pressure-LSPR-response isotherms. These isotherms are found to obey Sievert's law in the low-pressure range and exhibit a characteristic "plateau" at 18 Torr upon hydrogen charging and 7.5 Torr upon hydrogen discharging. An additional experiment also clearly shows the typical temperature dependence of the plateau pressure. Conversion of the LSPR signal to absolute hydrogen concentration, based on a proposed linear dependence of the LSPR response to hydrogen uptake, results in p-C isotherms in excellent agreement with those in the literature. This puts forward that the LSPR response is an extremely sensitive, remote, and real-time probe for "bulk" changes in a metal nanoparticle and can readily be used to study processes such as metal-hydride formation for hydrogen storage applications, alloying on the nanoscale, thermal reshaping, and so forth.     

Localized surface plasmon resonance of single silver nanoparticles studied by dark-field optical microscopy and spectroscopy

Localized surface plasmon resonance (LSPR) of Ag nanoparticles (NPs) with different shapes and disk-shaped Ag NP pairs with varying interparticle distance is studied using dark-field optical microscopy and spectroscopy (DFOMS). Disk-, square-, and triangular-shaped Ag NPs were fabricated on indium tin oxide-coated glass substrates by electron beam lithography. The LSPR spectra collected from single Ag NPs within 5×5 arrays using DFOMS exhibited pronounced redshifts as the NP shape changed from disk to square and to triangular. The shape-dependent experimental LSPR spectra are in good agreement with simulations using the discrete dipole approximation model, although there are small deviations in the peak wavelengths for square- and triangular-shaped NPs. The LSPR spectra of disk-shaped Ag NP pairs with varying interparticle distances were acquired from five different locations across the pair axis. It was clearly observed that the LSPR wavelength redshifts as the interparticle distance decreases, indicating a strong interaction when two Ag NPs are close to each other.     

Comprehensive study on surfactant role on silver nanoparticles (NPs) prepared via modified Tollens process

Surfactants represent not only commonly used wetting agents but also substances that can be used as growth modifiers in the process of solid nanoparticle (NP) preparation. In this study we report influential character of different types of surfactants – i.e. ionic (SDS, CTAC) and non-ionic (Tween 80) – on fundamental characteristics of silver NPs, which were prepared by a modified Tollens process. The influential character of surfactants was evaluated throughout a reasonable improvement of the polydispersity (in the case of the tested non-ionic surfactants from 8.5% even down to 2.5%) and in the case of ionic surfactant, SDS and CTAC, also significant change of zeta potential (from −20 to −50 mV for the highest tested concentration of SDS). A slight influence of the tested surfactants was observed on the sizes of the prepared silver NPs. Therefore the obtained results from the performed surfactant-assisted syntheses revealed a possibility how to tailor silver NPs by means of their polydispersity and zeta potential according to the application demands.     

Aqueous phase synthesized CdSe magic-sized clusters: solution composition dependence of adsorption layer structure

We report dispersion solution composition dependence of the adsorption layer structure and the physical and optical properties of aqueous phase-synthesized semiconductor nanoparticles (NPs). We synthesized cysteine (Cys)-capped CdSe NPs with well-defined core structures, dispersed them in a series of aqueous solutions with different compositions, and then investigated their adsorption layer structure and physical and optical properties. Each CdSe NP consisted of a (CdSe)33 or (CdSe)34 magic-sized cluster (d - 1.45 nm) core, a ligand-Cys shell, and an adsorption layer. The dispersion solution composition strongly affected the adsorption layer structure of the CdSe NPs. The solution with a composition close to that of the as-prepared solution stabilized the physical and optical properties of the NPs. The solution with a composition different from that of the as-prepared solution, however, resulted in large changes in their adsorption layer structure and thus their physical and optical properties. The solution composed of neutral or weakly charged Cys and Cd-Cys complexes led to the adsorption layer with low charge density and that destabilized the NPs. The solution containing only neutral or weakly charged forms of Cys, without Cd-Cys complexes, was favorable to the formation of a thick adsorption layer with low charge density and that destabilized the NPs. The amount of adsorbed Cys in the adsorption layer depended on the dispersion solution composition. However, the amount of adsorbed Cd-Cys complexes in the adsorption layer was almost constant regardless of the dispersion solution composition.     

Fundamental examination of nanoparticle heating kinetics upon near infrared (NIR) irradiation

Near infrared (NIR) light, which spans wavelengths from ~700-1100 nm holds particular promise in bionanotechnology-enabled applications because both NIR light and nanoparticles (NPs) have the potential for remote activation leading to exquisite localization and targeting scenarios. In this study, aqueous solutions of carbon and metal-based NPs (carbon black, single-walled carbon nanotubes, silver nanoparticles and copper nanoparticles) were exposed to continuous NIR laser (λ = 1064 nm) irradiation at powers of 2.2W and 4.5W. The differential heating of bulk aqueous suspension of NPs with varying physicochemical properties revealed maximum temperatures of 67 °C with visible evidence of condensation and bubble formation. The basis of the NP heating is due to the strong intrinsic optical absorbance in the NIR spectral window and the transduction of this NIR photon energy into thermal energy. In this regard, UV-vis measurements can accurately predict NP heating kinetics prior to NIR irradiation. Further, a uniform thermodynamic heating model demonstrates close agreement with the experimental data for the low NIR-absorbing NPs. However, the uniform thermodynamic heating model used in this study does not accurately portray the energy release upon localized NP heating because of bubble formation for the highly absorbing NPs. Therefore, this study reveals the differential heating kinetics of NPs excited with NIR with implications in the development of novel NIR-NP-based systems.     

Miscibility Behavior and Formation Mechanism of Stabilized Felodipine-Polyvinylpyrrolidone Amorphous Solid Dispersions

In the present study, solid dispersion systems of felodipine (FEL) with polyvinylpyrrolidone (PVP) were developed, in order to enhance solid state stability and release kinetics. The prepared systems were characterized by using Differential Scanning Calorimetry, X-Ray Diffraction, and Scanning Electron Microscopy techniques, while the interactions which take place were identified by using Fourier Transformation-Infrared Spectroscopy. Due to the formation of hydrogen bonds between the carbonyl group of PVP and the amino groups of FEL, transition of FEL from crystalline to amorphous state was achieved. The dispersion of FEL was found to be in nano-scale particle sizes and dependent on the FEL/PVP ratio. This modification leads to partial miscibility of the two components, as it was verified by DSC and optimal glass dispersion of FEL into the polymer matrix since no crystalline structure was detected with XRD. The above deformation has a significant effect on the dissolution enhancement and the release kinetics of FEL, as it causes the pattern to change from linear to logarithmic. An impressive optimization of the dissolution profile is observed corresponding to a rapid release of FEL in the system containing 10% w/w of FEL, releasing 100% in approximately 20 min. The particle size of dispersed FEL into PVP matrix could be classified as the main parameter affecting dissolution optimization. The mechanism of such enhancement consists of the lower energy required for the dissolution due to the amorphous transition and the fine dispersion, which leads to an optimal contact surface of the drug substance with the dissolution media. The prepared systems are stable during storage at 40 ± 1°C and relative humidity of 75 ± 5%. Addition of sodium docusate as surfactant does not affect the release kinetics, but only the initial burst due to its effect on the surface tension and wettability of the systems.     

Silver sulfide nanoparticle assembly obtained by reacting an assembled silver nanoparticle template with hydrogen sulfide gas

A fast, simple procedure is described for obtaining an assembly of silver sulfide nanoparticles (Ag(2)S NPs) on a glass substrate through reaction of a template of an assembled layer of silver nanoparticles (Ag NPs) with hydrogen sulfide (H(2)S) gas. The Ag NP template was prepared by assembling a monolayer of spherical Ag NPs (mean diameter of 7.4?nm) on a polyethylenimine-treated glass substrate. Exposure to pure H(2)S for 10?min converted the Ag NPs of the template to Ag(2)S NPs. The resulting Ag(2)S NP assembly, which retains the template nanostructure and particle distribution, was characterized by optical absorption spectroscopy, atomic force microscopy, transmission electron microscopy (TEM), scanning high resolution TEM, energy dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy. The Ag(2)S NPs have a crystal structure of monoclinic acanthite, and while they retained the spherical shape of the original Ag NPs, their mean particle size increased to 8.4?nm due to changes to the crystal structure when the Ag NPs are converted into Ag(2)S NPs. The measured optical absorption edge of the Ag(2)S NP assembly indicated an indirect interband transition with a band gap energy of 1.71?eV. The Ag(2)S NP assembly absorbed light with wavelengths below 725?nm, and the absorbance increased monotonically toward the UV region.     

Reflection and Absorption Techniques for Optical Characterization of Chemically Assembled Nanomaterials

This review discusses recent developments in the areas of fabrication, certain types of optical characterization, and applications of a selected class of chemically assembled nanomaterials, namely i) gold and silver nanoparticles deposited onto optically transparent glass substrates; ii) thiol‐functionalized self‐assembled monolayers (SAMs); iii) chemically stabilized gold and silver nanoparticles (monolayer protected clusters, MPCs); and iv) MPCs linked to metallic substrates and adsorbates. Six linear optical techniques for the characterization of these materials are discussed: transmission localized surface plasmon resonance spectroscopy, T‐LSPR; propagating surface plasmon resonance spectroscopy, P‐SPR; polarization‐selective Fourier transform infrared reflection absorption spectroscopy, PS‐FTIRRAS; polarization‐modulation Fourier transform infrared reflection absorption spectroscopy, PM‐FTIRRAS; surface‐enhanced infrared reflection absorption spectroscopy, SEIRRAS; and infrared ellipsometry. The review focuses particularly on providing a unified treatment of these six optical techniques by using a relatively simple stratified multilayer model.     

Electrospun titanium dioxide nanofibers containing hydroxyapatite and silver nanoparticles as future implant materials

In this study, a good combination consisting of electrospun titanium dioxide (TiO₂) nanofibers incorporated with high purity hydroxyapatite (HAp) nanoparticles (NPs) and antimicrobial silver NPs is introduced for hard tissue engineering applications. The synthesized nanofibers were characterized by various state of art techniques like; SEM, XRD, TEM, TEM EDS and XPS analyses. SEM results confirmed well oriented nanofibers and good dispersion of HAp and silver NPs, respectively. XRD results demonstrated well crystalline feature of three components used for electrospinning. Silver NPs were having a diameter in range of 5–8 nm indicated by TEM analysis. Moreover, TEM EDS analysis demonstrated the presence of each component with good dispersion over TiO₂ nanofiber. The surface analyses of nanofibers were investigated by XPS which indicated the presence of silver NPs on the surfaces of nanofibers. The obtained nanofibers were checked for antimicrobial activity by using two model organisms E. coli and S. aureus. Subsequently, antimicrobial tests have indicated that the prepared nanofibers do posses high bactericidal effect. Accordingly, these results strongly recommend the use of obtained nanofiber mats as future implant materials.     

Plasmonics and enhanced magneto-optics in core-shell co-ag nanoparticles

We present theoretical and experimental studies that explain the observed strong enhancement of the magneto-optical (MO) Faraday rotation in all-metal core-shell Co-Ag nanoparticles (NPs) attributed to localized surface plasmon resonance (LSPR). We also explain why the optical absorption and MO spectra peaks appear blue-shifted with increased Co core size while keeping the NP size constant. Further, we demonstrate direct correlation between the strong LSPR induced electromagnetic fields and the enhanced MO activity of the NPs.     

A silver nanoparticle thin film modified glass substrate as a colourimetric sensor for hydrogen peroxide

In this work, a silver nanoparticle (AgNP) coated glass slide was developed as a device for sensing hydrogen peroxide. AgNPs were synthesised using borohydride reduction with a citrate stabiliser, resulting in a negatively charged stabilised particle surface. The particles were attached to the glass surface using the layer-by-layer (LbL) technique. Poly (diallyldimethylammonium chloride) and poly (styrene sulphonate) were used as cationic and anionic polyelectrolyte layers, respectively. The glass slide was modified with polyelectrolytes leaving a cationic layer on the top surface. The AgNPs were subsequently deposited on the slide via electrostatic interaction. As a result, a dark yellow film of AgNPs was obtained with maximum absorption at 410 nm. Film fabrication based on LbL assembly provided acceptable reproducibility (relative standard deviation = 6.5%). The fabricated film had long-term stability (>6 weeks). A very small quantity of AgNPs was used in this method. Fabrication was performed under ambient conditions. Therefore this fabrication was considered as a green method. The AgNP modified slide was developed to sense hydrogen peroxide. Detection is based upon oxidation of AgNPs by hydrogen peroxide. This results in a change in colour of the film from dark yellow to colourless. Linear calibration was obtained over the range of 1.0--100.0 mM of hydrogen peroxide. The device was successfully used for measuring hydrogen peroxide in urine.