Surface Plasmon Resonance and Field Enhancement of Au/Ag Alloyed Hollow Nanoshells

We investigate the nanostructure, surface plasmon resonance （SPR） absorption and nonlinear enhancement of Au/Ag alloyed hollow nanoshells prepared by the replacement reaction of Ag nanoparticles in a HAuCI4 aqueous solution. As the volume of HAuCl4 increases from OmL to 0.S mL, the SPR band of the Au/Ag alloyed nanoshells is tuned from 430nm to 780nm, and the third-order nonlinear optical susceptibility is enhanced nearly by an order of magnitude, which indicates a large enhancement of local field in the Au/Ag alloyed hollow nanoshells with hole defects.     

Facile synthesis of CuO hollow nanospheres assembled by nanoparticles and their electrochemical performance

CuO hollow nanospheres with an average diameter of 400 nm and shell thickness of 40 nm have been successfully synthesized via a simple thermal oxidation strategy with Cu₂O solid nanospheres as the precursor. The products have been characterized by X-ray diffraction, transmission electron microscopy and field emission scanning electron microscopy. The formation of CuO hollow nanospheres mainly results from the Kirkendall effect on the basis of temperature-dependent experiments. Furthermore, the electrochemical performance of CuO hollow nanospheres as anode materials for lithium ion batteries has been evaluated by cyclic voltammetry and galvanostatic discharge-charge experiments. The as-prepared CuO hollow nanospheres assembled by nanoparticles exhibit higher initial discharge capacity and better cycle performance than the reported CuO nanoparticles. The hierarchical hollow nanospheres have been demonstrated to take the advantages of nanoparticles and hollow architectures, which could not only shorten the lithium ion transport distance and increase the kinetics of conversion reactions, but also provide suitable electrode/electrolyte contact area and accommodate the volume change associated with lithium ion insertion and extraction.     

Spectroscopy of vibrational modes in metal nanoshells

In this work we study the spectrum of vibrational modes in metal nanoparticles with a dielectric core. Vibrational modes are excited by the rapid heating of the particle lattice that takes place after laser excitation, and can be monitored by means of pump-probe spectroscopy as coherent oscillations of transient optical spectra. In nanoshells, the presence of two metal surfaces results in a substantially different energy spectrum of acoustic vibrations than for solid particles. We calculated the energy spectrum as well as the damping of nanoshell vibrational modes. The oscillator strength of the fundamental breathing mode is larger than that in solid nanoparticles. At the same time, in very thin nanoshells, the fundamental mode is overdamped due to instantaneous energy transfer to the surrounding medium. PACS 78.67.-n; 78.67.Bf; 63.22.+m     

Advantages of using gold hollow nanoshells in cancer photothermal therapy

Lots of studies have been conducted on the optical properties of gold nanoparticles in the first region of near infrared(650 nm–950 nm), however new findings show that the second region of near-infrared(1000 nm–1350 nm) penetrates to the deeper tissues of the human body. Therefore, using the above-mentioned region in photo-thermal therapy(PTT) of cancer will be more appropriate. In this paper, absorption efficiency is calculated for gold spherical and rod-shaped nanoshells by the finite element method(FEM). The results show that the surface plasmon frequency of these nanostructures is highly dependent on the dimension and thickness of shell and it can be adjusted to the second region of near-infrared. Thus, due to their optical tunability and their high absorption efficiency the hollow nanoshells are the most appropriate options for eradicating cancer tissues.     

A facile route to prepare hierarchical magnetic cobalt–silica hollow nanospheres with tunable shell thickness

Magnetic nanoshells composed of close-packed cobalt–silica nanoparticles have been successfully fabricated on silica spheres. The synthesis is facile and no high pressure, high temperature, or other severe reaction conditions were required. TEM images showed that two batches of the hollow-structured products have a good spherical morphology with an average diameter of 380 and 550 nm, respectively. The surface area and magnetic properties of cobalt–silica nanoshells are measured. By varying the times of the precipitation procedure, the shell thickness is successfully controlled within the 5–30 nm range and each time of procedure might increase the thickness about 5 nm. It is expected that the in situ reaction method can be extended to the synthesis of other hollow metal spheres. The prepared microcapsule with controllable shell thickness and interspaces has the potential to be used for controlled release applications.     

Chloride ion refined galvanic replacement: Boosting monodispersity of Au-Ag hollow nanoparticles & their enhanced applications

In this present work, we have redesigned the well-known Turkevich protocol for promoting versatile galvanic replacement, resulting in the synthesis of hollow Au nanostructures by the sacrificial reduction of HAuCl₄ on the as-prepared Ag nanoparticles in the presence of slight excess NaCl in order to dictate their core size to cavity ratio in a highly reproducible manner. The significance of chloride ion interaction in tuning the size/shape control was corroborated with the contrasting effect of other halide ions, namely bromine and iodine. The structure-property functional relationship of these artificial hollow metal nanostructures were not only established using the systematic optical absorption and TEM measurements, but also through enhanced spectroscopy measurements such as SEIRA and SERS, elucidating the dynamic advantage of hollow nanostructures over and above their solid monometallic counterparts. Further, the familiar 4-NA to p-PDA catalytic reduction kinetics demonstrate the unusual zeroth order characteristics in the presence of hollow metal nanostructures, unequivocally distinguishing it from the common first order characteristics associated with the corresponding solid metal nanoparticles, essentially attributed to the morphology tuned accessible higher total surface area, thus exemplifying the aesthetic compliance for future technological applications.     

Galvanic synthesis of hollow non-precious metal nanoparticles using aluminum nanoparticle template and their catalytic applications

Aluminum nanoparticles, owing to the large negative redox potential, are demonstrated to be an efficient template material to synthesize nanomaterials using the galvanic replacement reaction. The new nanoparticle template has lead to the production of hollow non-precious metal nanoparticles including nickel and cobalt. These hollow nanoparticles are characterized by electron microscopy (SEM and TEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and BET measurements. When used as catalysts for hydrogen generation from sodium borohydride hydrolysis reaction, these hollow nanoparticles show improved catalytic properties over their solid counterparts due to their large surface area.     

Optimal design of gold nanoshells for optical imaging and photothermal therapy

Gold nanoshells are of great interest in optical imaging based on their light scattering properties and photothermal therapy due to their light absorption properties. Strong light scattering is essential for optical imaging, while effective photothermal therapy requires high light absorption. In this article, the optimal core radii and shell thicknesses of silica–gold and hollow gold nanoshells, possessing maximal light scattering and absorption at wavelengths between 700 and 1100 nm, are obtained using the Mie theory of a coated sphere. The results show that large-sized gold nanoshells of high aspect ratios (the aspect ratio is defined as the ratio of core radius to shell thickness) are the efficient contrast agents for optical imaging, while smaller gold nanoshells of high aspect ratios are the ideal therapeutic agents for photothermal therapy. From the comparison of the numerical results for silica–gold and hollow gold nanoshells, the latter are seen to offer a little superior light scattering and absorption at smaller particle size. Fitting expressions for the optimal core radii and shell thicknesses are also obtained, which can provide design guidelines for experimentalists to optimize the synthetic process of gold nanoshells.     

Non-equilibrium cation distribution and enhanced spin disorder in hollow CoFe2O4 nanoparticles

We present magnetic properties of hollow and solid CoFe(2)O(4) nanoparticles that were obtained by annealing of Co(33)Fe(67)/CoFe(2)O(4) (core/shell) nanoparticles. Hollow nanoparticles were polycrystalline whereas the solid nanoparticles were mostly single crystal. Electronic structure studies were performed by photoemission which revealed that particles with hollow morphology have a higher degree of inversion compared to solid nanoparticles and the bulk counterpart. Electronic structure and the magnetic measurements show that particles have uncompensated spins. Quantitative comparison of saturation magnetization (M(S )), assuming bulk Néel type spin structure with cationic distribution, calculated from quantitative XPS analysis, is presented. The thickness of uncompensated spins is calculated to be significantly large for particles with hollow morphology compared to solid nanoparticles. Both morphologies show a lack of saturation up to 7 T. Moreover magnetic irreversibility exists up to 7 T of cooling fields for the entire temperature range (10-300 K). These effects are due to the large bulk anisotropy constant of CoFe(2)O(4) which is the highest among the cubic spinel ferrites. The effect of the uncompensated spins for hollow nanoparticles was investigated by cooling the sample in large fields of up to 9 T. The magnitude of horizontal shift resulting from the unidirectional anisotropy was more than three times larger than that of solid nanoparticles. As an indication signature of uncompensated spin structure, 11% vertical shift for hollow nanoparticles is observed, whereas solid nanoparticles do not show a similar shift. Deconvolution of the hysteresis response recorded at 300 K reveals the presence of a significant paramagnetic component for particles with hollow morphology which further confirms enhanced spin disorder.     

Synthesis and Optical Properties of Anisotropic Metal Nanoparticles

In this paper we overview our recent studies of anisotropic noble metal (e.g. gold and silver) nanoparticles, in which a combination of theory and experiment has been used to elucidate the extinction spectra of the particles, as well as information related to their surface enhanced Raman spectroscopy. We used wet-chemical methods to generate several structurally well-defined nanostructures other than solid spheres, including silver nanodisks and triangular nanoprisms, and gold nanoshells and multipods. When solid spheres are transformed into one of these shapes, the surface plasmon resonances in these particles are strongly affected, typically red-shifting and even splitting into distinctive dipole and quadrupole plasmon modes. In parallel, we have developed computational electrodynamics methods based on the discrete dipole approximation (DDA) method to determine the origins of these intriguing optical features. This has resulted in considerable insight concerning the variation of plasmon wavelength with nanoparticle size, shape and dielectric environment, as well as the use of these particles for optical sensing applications.     

Control of morphology and dopant distribution in yttrium-doped ceria nanoparticles

The morphology and distribution of dopant in yttrium-doped ceria (YDC) nanoparticles prepared by spray pyrolysis were characterised by transmission electron microscopy and X-ray energy dispersive spectroscopy (XEDS), respectively. By combining the XEDS analysis and concentration distribution modelling, accurate yttrium dopant concentration variation from the particle center to the surface can be determined. It is shown that by appropriately selecting cerium precursors, the yttrium dopant distribution in YDC nanoparticles can be controlled. Uniform yttrium distribution in the YDC particles has been achieved, which is important to decrease probability of yttrium cluster segregation to improve oxygen ion conductivity in solid oxide fuel cell electrolytes. This control is based on the suggested mechanism of dopant distribution which proposes that hydration energies influence diffusion rates of the precursors during preparation process. In addition, the morphology (solid spherical, hollow spherical and hollow concave) formation mechanisms of the YDC particles from different cerium precursors are discussed.     

The effect of the size,shape, and structure of metal nanoparticles on the dependence of their optical properties on the refractive index of a disperse medium

The effect of the size, shape, and structure of gold and silver nanoparticles on the dependence of their extinction and integral scattering spectra on the dielectric environment has been investigated. Calculations were performed using the Mie theory for spheres and nanoshells and the T-matrix method for chaotically oriented bispheres, spheroids, and s cylinders with hemispherical ends. The sensitivity of plasmon resonances to variations in the refractive index of the environment in the range 1.3–1.7 for particles of different equivolume size, as well as to variations in the thickness of the metal layer of nanoshells, was studied. For nanoparticles with an equivolume diameter of 15 nm, the maximal shifts of plasmon resonances due to variation in the refractive index of the environment are observed for bispheres and the shifts decrease in the series nanoshells, s cylinders or spheroids, and spheres. For particles 60 nm in diameter, the largest shifts of plasmon resonances occur for nanoshells and the shifts decrease in the series bispheres, s cylinders or spheroids, and spheres. All other conditions being the same, silver nanoparticles are more sensitive to the resonance tuning due to a change in the dielectric environment.     

Spectra of resonance light scattering of gold nanoshells: Effects of polydispersity and limited electron free path

The effects of the polydispersity of the structure of gold nanoshells and of the limited electron free path in a thin metal layer on the spectra of resonance light scattering of a suspension of two-layer nanoparticles are studied theoretically and experimentally for the first time. It is shown theoretically that both factors lead to a broadening of the plasmon resonance in light scattering and to a change in its magnitude. To experimentally test the calculations, two samples of nanoshells based on gold and silicon dioxide (silica) were synthesized. Nanoshells of sample 1 have a diameter of the core of 90 nm and a broad thickness distribution of shells (with an average value of 30 nm), whereas nanoshells of sample 2 have a diameter of the core of 70 nm and a narrow thickness distribution of shells (with an average value of 12 nm). The core diameter, the shell thickness, and the polydispersity of the structure of nanoparticles are estimated by dynamic light scattering. It is shown that the simulation of the optical properties of nanoparticles with their parameters estimated from the dynamic light scattering data makes it possible to obtain good agreement between experimental and theoretical spectra of light scattering. For nanoshells of sample 1, the inhomogeneous broadening of the scattering spectrum is completely determined by the polydispersity; therefore, the bulk constants of gold can be used in simulation of the spectra of such nanoshells. The main mechanism of the broadening for nanoshells of sample 2 is connected with the limitation of the free path length of electrons, whereas the contribution from the thickness distribution of shells can be neglected.     

Optical bistability in plasmonic nanoparticles: Effect of size,shape and embedding medium

We theoretically investigate the optical bistability, which one input signal allows two possible outputs, from single spherical/cylindrical nanoparticles and also nanoshells in the frame work of quasi-static formalism. It is shown that the bistability behavior greatly depends on several parameters such as the nanoparticle size, material and the surrounding dielectric environment. We demonstrated the width of the bistability region and also the bistable threshold depends on the geometrical parameters, and can be tuned by adjusting the size of nanoparticle, the shell thickness and the dielectric constant of the embedding medium. It is also shown that the optical bistable behavior depends strongly on the shape of plasmonic nanoparticles and nanoshells. However, these dependences of optical bistability of spherical/cylindrical nanoparticles and nanoshells on changing of their geometrical parameters can be used for realize optical switching and sensing purposes.     

Spectroturbidimetric determination of the size,concentration, and refractive index of silica nanoparticles

A method for determining the refractive index, size, and concentration of silica nanoparticles used as cores in synthesis of gold nanoshells is described. The average refractive index of silica nanoparticles, n = 1.475 ± 0.005, is determined by a modified immersion method, which involves spectroturbidimetry data in immersion media (dimethyl sulfoxide + ethanol). Working calibrations are obtained, which allow one to determine the size and concentration of silica particles and, correspondingly, the concentration of gold nanoshells in final preparations from measured values of the wavelength exponent and optical density.     

中空结构Pt纳米粒子热稳定性和形变的分子动力学研究

不同于实心结构纳米粒子,中空结构Pt纳米粒子具有低密度、高孔隙率和大的比表面积等特点,具有特殊的物理化学性质,在催化、光电子和药物输送领域有重要的应用.纳米粒子热稳定性和形变特性对其合成、应用具有重要的影响.利用分子动力学模拟研究中空结构Pt纳米粒子结构稳定性和形变过程,对不同壳层厚度的Pt纳米粒子进行分析,结果表明:在弛豫过程,温度为0.1 K时,壳层厚度为0.5 nm的Pt纳米粒子结构将发生形变,壳层厚度为1 nm、1.5 nm、2.0 nm、2.5 nm和3 nm纳米粒子结构保持几乎不变;升温过程,中空结构Pt纳米粒子塌缩时对应的温度随着壳层厚度增加而升高;塌缩过程所经历的温度区间很窄,空心结构短时间内突变为实心结构,另外,中空结构纳米粒子塌缩后,内部原子重新排列,仍保持有序的fcc结构.     

An opto-mechanical nanoshell–polymer composite

Metal nanoshells, which are nanoparticles consisting of a dielectric core surrounded by a metal shell, have an optical response dictated by the plasmon resonance. This optical resonance leads to large extinction cross-sections, which are typically several times the physical cross-section of the particles. The wavelength at which the resonance occurs depends on the core and shell sizes, allowing nanoshells to be tailored for applications. In this paper, we demonstrate how incorporating nanoshells transforms a thermoresponsivepolymer into a photothermally responsive nanoshell–polymer composite. When the thermoresponsive polymer, co-N-isopropylacrylamide-acrylamide (NIPAAm-co-AAm), is heated, the polymer undergoes a reversible decrease in volume. Pristine NIPAAm-co-AAm does not inherently absorb visible or near infrared light. However, by incorporating metal nanoshell particles with a resonance that has been placed at 832 nm into the NIPAAm-co-Aam, nanoshell–polymer composite hydrogels are fabricated. When the composite is illuminated with a diode laser at 832 nm, the nanoshells absorb light and convert it to heat. This induces a reversible and repeatable light-driven collapse of the composite with a weight change of 90% after illumination at 1.8 Wcm^-2. Received: 18 July 2001 / Published online: 10 October 2001     

Optical properties of graded colloidal nanocrystallines with tunable structure

We propose a class of graded colloidal crystalline materials which consist of polydisperse metallodielectric nanoshells stacked in layers. We take the Lekner-Lishchuk summation method to treat the graded systems which are not tractable by conventional approach such as Ewald-Kornfeld methods. It is demonstrated that this kind of graded materials exhibit a series of sharp peaks, which merge in a broadened resonant absorption band in the optical region, in contrast to colloidal crystal containing monodisperse nanoshells or nanoparticles. Effects of various gradient profiles of the ratio of the inner/outer radii in the nanoshells and lattice geometries on the optical properties are discussed. These materials are not hard to fabricate by contemporary nanofabrication techniques and they shall be useful in the engineering of optical nanomaterials.     

Measurement of the absorption coefficient of scattering liquid media by the calorimetric method

Using the example of a number of hydrosols (gold nanorods and nanoshells, silver nanoshells, zinc phthalocyanine nanoparticles), we show that the absorption coefficient of a scattering liquid medium can be measured from its heating by a short-time laser irradiation. The degree of heating was determined from expansion of the liquid in an ampoule with a capillary (the principle of liquid thermometer). Irradiation was performed at a wavelength of 671 or 1069 nm. From the transmission of samples of hydrosols at these wave-lengths, the sum of the absorption and scattering coefficients has been determined. To measure the absorption spectra of scattering liquids by this method, a laser with a tunable radiation wavelength is required. In the case of monodisperse colloidal solutions, the method ensures the measurement of the absorption and scattering cross-section ratio of particles.