Electroless formation of silver nanoaggregates: an experimental and molecular dynamics approach

The ability to manipulate matter to create non-conventional structures is one of the key issues of material science. The understanding of assembling mechanism at the nanoscale allows us to engineer new nanomaterials, with physical properties intimately depending on their structure.

This paper describes new strategies to obtain and characterise metal nanostructures via the combination of a top-down method, such as electron beam lithography, and a bottom-up technique, such as the chemical electroless deposition. We realised silver nanoparticle aggregates within well-defined patterned holes created by electron beam lithography on silicon substrates. The quality characteristics of the nanoaggregates were verified by using scanning electron microscopy and atomic force microscopy imaging. Moreover, we compared the experimental findings to molecular dynamics simulations of nanoparticles growth. We observed a very high dependence of the structure characteristics on the pattern nanowell aspect ratio. We found that high-quality metal nanostructures may be obtained in patterns with well aspect ratio close to one, corresponding to a maximum diameter of 50 nm, a limit above which the fabricated structures become less regular and discontinuous. When regular shapes and sizes are necessary, as in nanophotonics, these results suggest the pattern characteristics to obtain isolated, uniform and reproducible metal nanospheres.     

Polarization effects in nanoaggregates of silver caused by local and nonlocal nonlinear-optical responses

A theoretical and experimental study is made into the combined manifestation of local and nonlocal optical responses in a cubic nonlinear isotropic medium such as an aggregated colloidal silver solution. The phenomenological treatment of polarization effects is performed for the general case with due regard for the frequency dispersion of both local and nonlocal nonlinearities and for the noncollinear propagation of pump and probe light waves. The inverse Faraday effect, the optical Kerr effect, and the self-rotation of the polarization ellipse in a fractal-disordered nonlinear medium are observed for the first time. The tensor components of the local and nonlocal cubic nonlinearities of colloidal silver solutions are measured for different degrees of aggregation. It is demonstrated that, as the size of silver aggregate increases, the nonlocal nonlinear response increases much more strongly than the local one. An inference is made that the mechanical motion of metal nanoparticles because of their dynamic interaction with the light wave field can contribute to the nonlinear polarization effects.     

Surface-enhanced absorption by self-organized silver films with aciniform-like nanoaggregates at elevated temperatures

Morphological evolution of silver nanocomposite films prepared by the wet colloidal route and surface-enhanced phenomena on aggregate nanostructures evolved during annealing were investigated. Dramatic changes in morphologies of particles and pores incurred by rearragement, coarsening, premelting, and dewetting of the silver clusters at different concentrations (i.e., mass thicknesses). At a higher mass thickness, the morphological transitions from self-organized nanoaggregates with aciniform pattern at 300 °C to elongated and coarsened particles with circular holes at 400 °C to island clusters at 500 °C occurred in the films. The peculiar absorption with a much redder and broader surface plasmon feature, which gone far beyond the theoretical prediction, induced by the formation of aciniform nanoaggregates embedded in the porous polymer matrix at a critical mass thickness of 9.6 nm during partial degradation of the PVP polymer and rearrangement of silver clusters at 300 °C. The surface-enhanced absorption was dramatically reduced by the elemination of the aggregate nanostructures and the spontaneous formation of the silver nanoisland film at the dewetting temperature of 500 °C.     

Stable optical trapping based on optical binding forces

Various trapping configurations have been realized so far, either based on the scattering force or the gradient force. In this Letter, we propose a new trapping regime based on the equilibrium between a scattering force and optical binding forces only. The trap is realized from the interaction between a single plane wave and a series of fixed small particles, and is efficient at trapping multiple free particles. The effects are demonstrated analytically upon computing the exact scattering from a collection of cylindrical particles and calculating the Lorentz force on each free particle via the Maxwell stress tensor.     

Tailoring repulsive optical forces in nanophotonic waveguides

We describe a mechanism and propose design strategies to selectively tailor repulsive-gradient-optical forces between parallel, nanophotonic waveguides via morphology augmented by slow-light band-edge modes. We show that at small separation lengths, the repulsive force can be made nearly 2 orders of magnitude larger than that of standard dielectric waveguides with a square cross section. The increased coupling interactions should enable a wider dynamic range of optomechanical functionality for potential applications in sensing, switching, and nanoelectromechanical systems.     

功能光学纳米Ag薄膜的制备及其光学特性研究

对以热蒸发法制备的超薄Ag薄膜,扫描电子显微镜结果显示其呈纳米尺度的颗粒状,由透射谱测量发现其具有表面等离子体激元特征.检测到不同条件制备纳米Ag薄膜的表面等离子体共振吸收峰的位移规律,且纳米Ag材料具有选择性的透过、反射特性.通过不同的制备条件,得到了在长波范围内透过率超过90％、在表面等离子体共振峰值位置处反射率接近50％且峰位可调的光学薄膜材料.这种薄膜材料有望成为应用在薄膜太阳电池中间层中具有潜在性光管理功能的光学薄膜材料. 关键词： 热蒸发 纳米Ag薄膜 表面等离子体激元 光管理     

Novel optical lithography using silver superlens

This work has demonstrated that with silver superlens,the resolution of conventional optical lithography can be improved significantly.Experimental and simulative results are given to verify the facts that the resolution and the pattern fidelity are sensitive to the contact tightness between layers.     

Disorder in optical metamaterials made of silver nanospirals

We report on a numerical study of the optical properties of silver square nanospirals. The resonant modes of the nanospirals presented current distributions similar to those of U-shaped resonators. The resonance frequencies of the ‘electric’ modes were relatively insensitive to coupling, except for the shortest distance, whereas for the ‘magnetic’ modes they steadily increased with coupling. Aperiodicity in the strong coupling regime did not modify the strength and resonance frequency of all modes as compared to the case of periodic arrays.     

Reverse optical forces in negative index dielectric waveguide arrays

Nonconservative optical forces acting on dipolar particles are considered in longitudinally invariant optical fields. We demonstrate that the orientation of these forces is strictly dictated by the propagation vector associated with such field configurations. As a direct consequence of this, it is impossible to achieve a reversal of optical forces in homogeneous media. We show instead that translation invariant optical tractor fields can in fact be generated in the negative index environment produced in a special class of fully dielectric waveguide arrays.     

银团簇纳米颗粒的制备及其光吸收谱性质

 采用自悬浮定向流技术制备银团簇纳米颗粒，理论分析了银团簇的成核机理与影响因素，实验研究了制备条件和工艺。结果表明：惰性气体的冷却效率、气体流速和压强、金属熔球的温度和大小是控制颗粒尺寸大小及分布的关键条件，制备粒径小于10 nm的团簇颗粒须采用氦气为载流气体；团簇颗粒流速越大，颗粒粒径越小，尺寸分布越窄，但颗粒生成数量越少。性能表征说明：制备的颗粒呈较规则的球形，为面心立方结构，分散均匀，表面纯净无氧化，粒径分布窄。理论与实验研究了银团簇纳米颗粒的光学吸收谱性质，证明表面等离子共振吸收峰与颗粒的尺寸有很强的相关性，随着颗粒尺寸的减小，由于量子尺寸效应，吸收峰将发生宽化和蓝移。     

Calculation of axial optical forces exerted on medium-sized particles by optical trap

Optical trapping has become an efficient technique of trapping and manipulating micrometer and sub-micrometer dimension particles. Particles in the range between the applicable regime of ray optics theory (ROT) and the Rayleigh regime (so-called medium-sized particles) are focused on. By using ROT and the generalized Lorenz–Mie theory (GLMT), axial optical forces and their dependences on particle sizes and beam waists are presented. Furthermore, by comparing the numerical results of these two theories, the applicability of the GLMT to particles of arbitrary size and the limit of ROT in the region of small particles are analyzed. A new criterion of the applicable region of ROT is obtained, i.e. the relative particle size β=2πa/λ20, where a is the particle radius and λ is the wavelength of light. The theoretical results will be of great help to the design and optimization of the most efficient optical trap.     

Giant third optical harmonic generation in island silver films

Giant third optical harmonic (TH) generation has been experimentally observed in island silver films. The TH intensity in the island silver films studied is more than two orders of magnitude higher than the value observed for the smooth surface of a homogeneous silver film. The mechanism of enhancement of the nonlinear cubic response is associated with the resonance enhancement of the local optical field at the TH wavelength, which is caused by the excitation of local surface plasmons in the ensemble of metal nanoparticles.     

Synthesis and optical properties of silver nanoparticles in ORMOCER

Experimental results on synthesis of metal nanoparticles in ORMOCER by ion implantation are presented. Silver ions were implanted into organic/inorganic matrix at an accelerating energy of 30?keV and doses in the range of 0.25?10¹⁷ to 0.75?10¹⁷?ion/cm². The silver ions form metal nanoparticles, which demonstrate surface plasmon absorption at the wavelength of 425?C580?nm. The nonlinear absorption of new composite materials is measured by Z-scan technique using 150?fs laser pulses at 780?nm wavelength. ORMOCER matrix shows two-photon nonlinear absorption, whereas ORMOCER with silver nanoparticles demonstrates saturated absorption. Some optical applications of these composite materials are discussed.     

Giant nonlinear optical activity in an aggregated silver nanocomposite

Nonlinear optical activity due to spatial dispersion is observed in a colloidal solution of silver. It is shown experimentally that the effect is substantially enhanced (by a factor of ∼10²) when the silver particles aggregate into fractal clusters. The self-rotation angle of the plane of polarization is 2 mrad at an intensity of 2 MW/cm² for λ=0.532 μm and a pulse duration of 11 ns. A method of separating the contributions of the local and nonlocal effects to the rotation of the plane of polarization is proposed and implemented. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 8, 618–622 (25 October 1998)     

Enhanced optical forces between coupled resonant metal nanoparticles

We investigate numerically the optical forces between noble metal nanoparticles sustaining localized surface plasmon resonances. Our results first point out enhanced binding optical forces compared with dielectric nanoparticles and nonresonant metallic nanoparticles. We also show that under suitable illumination conditions, short-range forces tend to make the nanoparticles cluster, leading to intense and localized hot spots in the interstices. This effect corroborates recent experimental observations of an enhanced Raman signal in trapped metal sphere ensembles.     

Intermolecular forces from optical spectra of impurities in molecular crystals

A procedure is outlined by which one can get information about the effects of electronic excitation on the interactions between molecules. The absorption and emission spectra of impurities in molecular crystals, and specifically the mean positions and widths of the lines, are required as functions of temperature. A theory of M. Lax is used to relate mean position and width to intermolecular forces. The preliminary treatment of this problem by McCarty and Robinson is evaluated and extended: their procedure is expected to be valid for very narrow lines only.     

EPR and optical spectra of Ni2+-VAg in silver chloride and silver bromide

The optical absorption and EPR spectra of Ni²⁺-V_Ag centres in the AgCl:Ni²⁺ and AgBr:Ni²⁺ systems have been investigated theoretically on the basis of the complete energy matrices including the electron–electron repulsion interaction, the ligand field interaction, the spin–orbit coupling interaction, and Zeeman interaction. Because the charge compensation forms a silver ion vacancy (V_Ag) which makes the attractive force acted on the each ligand ion different, it was determined that the Ni–X (X = Cl, Br) distance next to V_Ag is shorter than others for both AgCl:Ni²⁺ and AgBr:Ni²⁺ systems in the tetragonal symmetry. Besides, it was found that the local lattice structure of (NiX₆)^4? clusters in AgCl and AgBr crystals exhibit a compression distortion. This compression distortion may be ascribed to the fact that the Ni²⁺ ion has a smaller ionic radius and more effective charge than the Ag⁺ ion.