The color of finely dispersed nanoparticles

We discuss the dependence of the color of low-concentrated nanoparticle systems on particle size and mass concentration for Ag, Au and TiN nanoparticles, which exhibit a surface plasmon polariton resonance in extinction spectra. Comparison is made with color data obtained for Ag and Au colloidal suspensions. When particles lump into aggregates, the splitting of the surface plasmon resonance into new resonances affects the extinction of light and, hence, the color of the particle assembly. This is demonstrated for aggregated colloidal suspensions of Ag and Au nanoparticles. Finally, for highly concentrated assemblies such as pigment films, we discuss the dependence of the color in diffuse reflectance and transmittance according to Kubelka and Munk (P. Kubelka, F. Munk: Z. Techn. Phys. 12, 593 (1931)), and extend this model by using optical properties of aggregates of spheres. Received: 2 July 2001 / Published online: 10 October 2001     

Effect of the material of metal nanoparticles on local field intensification in copper phthalocyanine

For spherical Cu, Ag, and Au nanoparticles with a radius of 1–3 nm in copper phthalocyanine (CuPc), with allowance for internal size effects, we calculate the scattering efficiency factor in the near zone, the extinction efficiency factor due to scattering and absorption of incident radiation, and the efficiency of the increase in absorption by the matrix material. This occurs in the CuPc absorption bands, as well as in the weak absorption region of CuPc, where, owing to surface plasmon resonance, an additional absorption band arises for nanoparticles of all three materials. For Ag nanoparticles, the increase in absorption is twice as high as for Cu and Au nanoparticles; for these it differs inconsiderably.     

电场辅助溶解法实现玻璃表面金纳米粒子的形貌控制

贵金属纳米粒子由于其非常独特的光学特性和表面活性, 在光子学、 催化和生物标识等方面都有非常重要的应用. 采用离子溅射和后续热处理相结合的方法在玻璃表面形成了尺寸大约为60-80 nm的单分散的球形金纳米粒子. 在适当的温度条件下, 采用步进式增加的强直流电场, 实现了金纳米粒子的电场辅助溶解过程. 在玻璃表面的不同颜色区域, 初始球形的金纳米粒子溶解成月蚀状形貌. 结合不同颜色区域内金纳米粒子的表面等离子体共振吸收性质和扫描电镜照片, 研究了实验条件对金纳米粒子性质的影响. 结合电场辅助溶解实验过程中的电流-电压特性, 分析了金纳米粒子在强直流电场辅助下溶解的物理过程: 金粒子中动出的电子向阳极的隧穿过程作为开始, 随后是金阳离子向玻璃基体中的传输过程和阴极提供的电子与带有正电荷的金粒子相结合的过程. 详细讨论了电场辅助溶解法实现金纳米粒子形貌控制的物理机制.     

1-Hexadecylamine as both reducing agent and stabilizer to synthesize Au and Ag nanoparticles and their SERS application

1-Hexadecylamine (HDA)-capped Au and Ag nanoparticles (NPs) have been successfully prepared by a one-pot solution growth method. The HDA is used as both reducing agent and stabilizer in the synthetic process is favorable for investigating the capping mechanism of Au and Ag NPs’ surface. The growth process and characterization of Au and Ag NPs are determined by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). Experimental results demonstrate that the HDA-capped Au and Ag NPs are highly crystalline and have good optical properties. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 2-thionaphthol are obtained on the Au and Ag NPs modified glass surface, respectively, indicating that the as-synthesized noble metal NPs have potentially high sensitive optical detection application.     

Surface plasmon assisted photoemission from Au nanoparticles on graphite

The resonant multiple excitation of collective modes in metallic nanoparticles using ultrashort laser pulses leads to an enhanced multiphoton photoemission from the particles. This effect is here demonstrated for the surface-plasmon resonance of Au nanoparticles on graphite. The shape of the photoemission spectra is explained by multiphoton photo-assisted thermionic emission from the nanoparticles and resonant emission via the image-potential state on graphite. Tuning the photon energy between 1.7 eV and 3.2 eV allows the identification of an enhancement of the photoemission yield at 2.1±0.1-eV photon energy that is attributed to the resonant excitation of the surface plasmon in the Au nanoparticles. This identification of the surface-plasmon excitation in this energy range is also supported by electron energy loss spectroscopy. Received: 8 August 2001 / Revised version: 13 September 2001 / Published online: 10 October 2001     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

Quantum spins in Mackay icosahedral gold nanoparticles

We report on the direct observation of the intrinsic magnetization behavior of Mackay icosahedral Au nanoparticles. The spin arrangements in 3.5-nm icosahedral Au particles are found to be ferrimagnetic-like, where the core and surface moments point in opposite directions, with a net spontaneous magnetic moment of 16 μ_B per particle. The unpaired spins behave as J = 1/2 quantum spins. The average level separation is found to be a factor of ~1.53 larger than that estimated according to the Kubo formula for spherical Au particles. This reflects the fact that there are considerably fewer atoms packed in a particle with an icosahedral geometry than with a spherical one.     

An investigation of the surface-enhanced Raman scattering (SERS) effect from laser irradiation of Ag nanoparticles prepared by trisodium citrate reduction method

By irradiating a Ag colloid solution, produced by trisodium citrate reduction method, employing the active Quanta Ray Nd:YAG laser system, λ = 1064 nm, we prepared relatively small, spherical Ag nanoparticles with a narrow size distribution. The irradiated particles not only improve the configuration, but also the spectroscopy properties to some extent. The influence of the laser fluence on the irradiated energy was studied, via transmission electron micrograph (TEM) images, surface plasmon absorption (SPA) spectra, and surface-enhanced Raman scattering (SERS) spectra. Those benefit to understanding the spectroscopy properties of irradiated particles to obtain precise understanding of the mechanism. And probably the reasonable explanations are given.     

Metal-on-oxide nanoparticles produced using laser ablation of microparticle aerosols

A continuous aerosol process has been studied for producing nanoparticles of oxides that were decorated with smaller metallic nanoparticles and are free of organic stabilizers. To produce the oxide carrier nanoparticles, an aerosol of 3–6 μm oxide particles was ablated using a pulsed excimer laser. The resulting oxide nanoparticle aerosol was then mixed with 1.5–2.0 μm metallic particles and this mixed aerosol was exposed to the laser for a second time. The metallic micron-sized particles were ablated during this second exposure, and the resulting nanoparticles deposited on the surface of the oxide nanoparticles producing an aerosol of 10–60 nm oxide nanoparticles that were decorated with smaller 1–5 nm metallic nanoparticles. The metal and oxide nanoparticle sizes were varied by changing the laser fluence and gas type in the aerosol. The flexibility of this approach was demonstrated by producing metal-decorated oxide nanoparticles using two oxides, SiO₂ and TiO₂, and two metals, Au and Ag.     

Surface characteristics of Ag‐doped Au nanoparticles probed by Raman scattering spectroscopy

We have examined the surface characteristics of Ag‐doped Au nanoparticles (below 5 mol% of Ag) by means of the surface‐enhanced Raman scattering (SERS) of 2,6‐dimethylphenylisocyanide (2,6‐DMPI) and 4‐nitrobenzenethiol (4‐NBT). When Ag was added to Au to form ∼35‐nm‐sized alloy nanoparticles, the surface plasmon resonance band was blue‐shifted linearly from 523 to 517 nm in proportion to the content of Ag up to 5%. In the SERS spectra of 2,6‐DMPI, the N‐C stretching peak also shifted almost linearly from 2184 to 2174 cm⁻¹ when the Ag content was 5 mol% or less; the peak then remained the same as that of the pure Ag film. The potential variation of the SERS spectrum of 2,6‐DMPI in an electrochemical environment, as well as the effect of organic vapor, also showed a similar tendency. From the SERS of 4‐NBT, we confirmed the occurrence of a surface‐induced photoreaction converting 4‐NBT to 4‐aminobenzenethiol, when Ag was added to Au to form alloy nanoparticles. The photoreaction induction ability also increased linearly with the Ag content, reaching a plateau level at 5 mol% of Ag. All these observations suggest that the surface content of Ag should increase almost linearly as a function of the overall mole fraction of Ag and, once the Au/Ag nanoparticles reach 5 mol% of Ag, their surfaces are fully covered with Ag, showing the same surface characteristics of pure Ag nanoparticles. Copyright © 2011 John Wiley & Sons, Ltd.     

Solution templating of Au and Ag nanoparticles by linear poly[2-(diethylamino)ethyl methacrylate]

Abstract  

Linear poly[2-(diethylamino)ethyl methacrylate], poly(DEAMA), is an uncommon example of a homopolymer that can reduce salts of Au and Ag in solution to yield stable dispersions of nanoparticles (5–25 nm typical size). Poly(DEAMA)-stabilized Au and Ag nanoparticles were prepared in a mixture of water and 2-butoxyethanol, an amphiphilic organic solvent. The “loading ratio” (mole ratio of metal atoms to amines), a key parameter influencing particle size and clustering, was systematically varied. The size distribution and clustering of the nanoparticles were characterized by transmission electron microscopy and small-angle X–ray scattering. The maximum loading ratio achievable without inducing precipitation was approximately 0.3 for Au, but the maximum loading ratio for Ag was only about 0.04. The preparation of both Au and Ag nanoparticles in solution with a linear polymeric template illustrates that dendritic or hyperbranched architecture of the polymer is not a prerequisite for obtaining stable, non-aggregated dispersions. From a practical standpoint, poly(DEAMA) is an inexpensive template material that is readily immobilized on silica, which could facilitate development of novel, nanoparticle-based heterogeneous catalysts.     

金/银纳米颗粒对Eu掺杂薄膜发光特性影响的研究

本文将三种金属纳米颗粒(球形银纳米颗粒、三角形银纳米薄片和三角形金纳米薄片)分别置于Eu(TTFA)3掺杂的Su8薄膜上研究了它们对铕配合物薄膜发光的影响.结果显示,金属纳米颗粒的局域等离子体共振(LSPR)谱对薄膜发光有很好的调控作用.对于LSPR谱分别与铕配合物激发谱和辐射谱重叠较好的球形和三角形两种银颗粒,相比于未放置颗粒时薄膜的发光,放置有颗粒的发光有明显的增强,其中球形银颗粒的样品的发光增强效果更为明显.而对于LSPR谱与铕配合物激发谱和辐射谱都不重叠的三角形片状金颗粒,该颗粒对样品的发光则起到了猝灭作用.     

Determination of size and concentration of copper nanoparticles dispersed in glasses using spectroscopic ellipsometry

For the generation of particular optical properties the melt of a commercially manufactured glass is doped with copper compounds. The glass obtained is opaque black at the usual thickness and looks dark red after making it into bulbs of incandescent lamps. It is generally assumed that copper particles cause this colouring. A proof in a spectrophotometric way fails due to the very high absorbance even for a sample thickness below 20 μm. It will be shown that in these cases spectroscopic ellipsometry is a suitable method of investigation. The pseudo-optical constants of this material were determined as a function of wavelength in the range from 350 nm to 700 nm by ellipsometric measurements. They can be reproduced very well by those of a model that consists of a roughness layer situated on a substrate of glass containing spherical copper particles with a Gaussian size distribution with =6.5 nm and σ=0.24 and a volume concentration of 2.4×10^-3. For this modelling the dielectric function of the roughness layer was approximated by Bruggeman effective-medium theory and that of the copper-containing glass substrate was calculated on the basis of the theory of Gans and Happel. The results were verified by transmission electron microscope investigations. Received: 1 July 2001 / Published online: 10 October 2001     

Depth profiles of Ag nanoparticles in silicate glass

Silver nanoparticle composite glass has been synthesized by ion exchange and a subsequent thermal treatment method. Transmission electron microscopy (TEM) and ultraviolet-visible spectrometry were used to study the depth profiles of Ag nanoparticles in silicate glass. Results indicate that Ag nanoparticles are nearly spherical in shape with a single-crystalline structure. Also, the volume fraction of Ag nanoparticles is very high in the surface layer of 5 μm, and then decreases slowly across the depth of 30 μm, thereafter the volume fraction reduces quickly to zero at the depth of 100 μm. The plasmon resonance bi-absorptions in the surface layer of the annealed specimen at 600 °C can be attributed to bi-modal distributions of Ag nanoparticles in the layer. The bi-modal distributions can be explained by the Ostwald ripening theory. PACS 81.05.Pj; 81.07.-b; 68.37.Lp     

Electromagnetic energy transport via linear chains of silver nanoparticles

We propose the idea of a subwavelength-sized light guide represented by a linear chain of spherical metal nanoparticles in which light is transmitted by electrodynamic interparticle coupling. The light-transport properties of this system are investigated by use of model calculations based on generalized Mie theory. Considering Ag particles of 50-nm diameter, we find optimum guiding conditions for an interparticle spacing of 25 nm, and a corresponding 1/e signal-damping length of 900 nm is evaluated. The proposed principle of optical energy transport may be useful for subwavelength transmission lines within integrated optics circuits and for near-field optical microscopy.     

Infrared imaging of single nanoparticles via strong field enhancement in a scanning nanogap

We demonstrate nanoscale resolved infrared imaging of single nanoparticles employing near-field coupling in the nanoscopic gap between the metal tip of a scattering-type near-field optical microscope and the substrate supporting the particles. Experimental and theoretical evidence is provided that highly reflecting or polariton-resonant substrates strongly enhance the near-field optical particle contrast. Using Si substrates we succeeded in detecting Au particles as small as 8 nm (相似文献   

Surface effects in nanoparticles: application to maghemite -Fe O

We present a microscopic model for nanoparticles, of the maghemite (-Fe₂O₃) type, and perform classical Monte Carlo simulations of their magnetic properties. On account of M?ssbauer spectroscopy and high-field magnetisation results, we consider a particle as composed of a core and a surface shell of constant thickness. The magnetic state in the particle is described by the anisotropic classical Dirac-Heisenberg model including exchange and dipolar interactions and bulk and surface anisotropy. We consider the case of ellipsoidal (or spherical) particles with free boundaries at the surface. Using a surface shell of constant thickness ( nm) we vary the particle size and study the effect of surface magnetic disorder on the thermal and spatial behaviors of the net magnetisation of the particle. We study the shift in the surface “critical region” for different surface-to-core ratios of the exchange coupling constants. It is also shown that the profile of the local magnetisation exhibits strong temperature dependence, and that surface anisotropy is responsible for the non saturation of the magnetisation at low temperatures. Received 1 September 1999 and Received in final form 3 November 1999     

A study of phase transfer processes of Ag nanoparticles

With the protection of sodium oleate, Ag nanoparticles are produced through the reduction of AgNO₃ with NaBH₄ in an aqueous solution. The possible mechanism of phase transfer of the Ag nanoparticles was discussed. At a suitable concentration of sodium oleate, after adding NaH₂PO₄, the oleic acid molecule can change its position on the surface of Ag nanoparticles under the effects of water and toluene and become amphipathic. So most of the nanoparticles form a film between water/toluene. For the case of a higher concentration of sodium oleate, excess sodium oleate will form a closed monolayer film on the surface of the Ag nanoparticles. After adding NaH₂PO₄, the oleic acid molecule cannot move on the Ag nanoparticles surface, thus the colloid particles are hydrophobic but not amphipathic. So most of the particles transfer to the organic phase. UV–Vis spectra, TEM and conventional metallographic microscopy are used to characterize the Ag nanoparticles and nanoparticles films.     

Optical Properties of Plasmon Resonances with Ag/SiO2/Ag Multi-Layer Composite Nanoparticles

Optical properties of plasmon resonance with Ag/SiO2/Ag multi-layer nanoparticles are studied by numerical simulation based on Green＇s function theory. The results show that compared with single-layer Ag nanoparticles, the multi-layer nanoparticles exhibit several distinctive optical properties, e.g. with increasing the numbers of the multi-layer nanoparticles, the scattering efficiency red shiRs, and the intensity of scattering enhances accordingly. It is interesting to find out that slicing an Ag-layer into multi-layers leads to stronger scattering intensity and more ＂hot spots＂ or regions of stronger field enhancement. This property of plasmon resonance of surface Raman scattering has greatly broadened the application scope of Raman spectroscopy. The study of metal surface plasmon resonance characteristics is critical to the further understanding of surface enhanced Raman scattering as well as its applications.     

Theory of spectral hole burning for the study of ultrafast electron dynamics in metal nanoparticles

In order to study the ultrafast relaxation dynamics of surface plasmon excitation in metal nanoparticles in the presence of inhomogeneous line broadening and investigate the influence of the reduced dimensions on the dephasing time T₂ in the size regime below about 10 nm, we have recently demonstrated a novel technique based on persistent spectral hole burning [1]. Here, we describe a theoretical model that has been developed for evaluation of the experimental data and precise determination of T₂ for particles of different size and shape. Comparison of the model to experimental data for Ag nanoparticles on sapphire shows that the theoretical treatment does not only reproduce the shape of the generated holes but also the dependence of their widths on the applied laser fluence. As a result, we have a reliable and versatile tool at hand making possible systematic studies of the ultrafast electron dynamics in small metal particles, and the dependence of the femtosecond dephasing time on their size, shape and surrounding dielectric. Received: 12 September 2001 / Published online: 15 October 2001