Microwell‐Directed Self‐Assembly of Vertical Nanowire Arrays

Vertical arrays of anisotropic particles are desired for many applications including solar cells, battery electrodes, and lasers. Partially etched nano­wires (PENs) are hybrid silica nanotube/nanowires with partial metallic cores. These particles spontaneously form vertical arrays in which on average 70% of the particles are oriented perpendicular to the underlying substrate. Here, we perform PEN self‐assembly on lithographically prepared substrates patterned with square microwells having dimensions comparable to the length of the particles. Particle self‐assembly is observed both in the microwells and on the intervening surfaces. PENs both directly deposit into a well and diffuse across the surface between microwells until falling into a well. Assembly occurs as the local concentration of PENs in a well increases by these two mechanisms. Microwells provide a way to control array location on a surface and improve standing percentages up to 100% when the edge dimensions are decreased to a size approximately equal to the nanowire length. Micro­wells also protect against array disruption during sample drying.     

Synthesis of core–shell nanoparticles with a Pt nanoparticle core and a silica shell

A method to prepare a core–shell structure consisting of a Pt metal core coated with a silica shell (Pt(in)SiO₂) is described herein. A silica shell was grown on poly(vinylpyrrolidone) (PVP)-stabilized Pt nanoparticles 2–3 nm in size through hydrolysis and condensation reactions of tetraethyl orthosilicate (TEOS) in a water/ethanol mixture with ammonia as a catalyst. This process requires precise control of the reaction conditions to avoid the formation of silica particles containing multiple Pt cores and core-free silica. The length of PVP molecules, water content, concentration of ammonia and Pt nanoparticles in solution were found to significantly influence the core–shell structure. By optimizing these parameters, it was possible to prepare core–shell particles each containing a single Pt nanoparticle with a silica layer coating approximately 10 nm thick.     

Colloidal Core–Satellite Supraparticles via Preprogramed Burst of Nanostructured Micro‐Raspberry Particles

Colloidal molecules, or more general supraparticles, i.e., particles which are themselves assembled of smaller nanoparticles in a defined way, are known to be synthesizable via bottom‐up assembly techniques in colloidal dispersion. The amount of synthesizable particles is mostly limited to milligrams. Herein, a bottom‐up‐programed, triggerable top‐down process is reported to obtain core–satellite supraparticles, i.e., particles composed of a larger core particle surrounded by smaller satellite particles. The key is to prepare a nanostructured, microparticulate powder into which defined burst behavior is preprogramed. Once the system is mechanically triggered, it bursts into well‐defined nanosized core–satellite supraparticles. Scale‐up is easily feasible and several hundred grams per batch can be demonstrated. The product is a ready‐to‐use and flexibly processible powder. Upon simple mixing with a polymer, it disintegrates into the preprogramed core–satellite supraparticles, thus forming a highly sophisticated nanocomposite with the polymer matrix. A pure silica nanoparticle system and a silica–iron oxide nanoparticle hybrid system are presented to demonstrate the versatility of the approach. Enhanced mechanical and unexpected magneto‐optical properties with the particle system are found. The disintegration of the microparticles into individual core–satellite colloidal supraparticles is confirmed via in situ liquid cell transmission electron microscopy.     

Optomechanically Assisted Assembly of Surface‐Functionalized Zeolite‐L‐Based Hybrid Soft Matter

Nanoporous particles are particularly interesting for the assembly of functional nano‐ and microsystems because they provide hierarchical supramolecular organization of a large variety of guest molecules. In this work, arbitrary nanoarchitectures consisting of nanoporous zeolite‐L crystals are assembled by combining holographic optical tweezers (HOT) with polymer brush functionalized particles to overcome the limitations of 1D and restricted self‐assembly of zeolite‐L crystals. Readily prepared and functionalized polymer shells allow for controlled, instant, and highly efficient particle–particle and particle–surface adhesion without the need for an external trigger. In contrast to earlier studies, these assemblies remain permanently stable after release out of the HOT system. This novel strategy can be used to fabricate either motile units or locally grounded 1D, 2D, and 3D microconstructions, which can be further utilized as microtools in microfluidic and nanophotonic applications.     

Convenient preparation of ITO nanoparticles inks for transparent conductive thin films

We synthesized Pt and Ag nanowires using a mesoporous silica, SBA-15, as templates. The obtained nanowires are a few micrometers (~4???m) long and 7?nm in diameter. The nanowires are free from bundling and, thus, can be separated as single nanowires. The successful synthesis of such nanowires requires a few considerations. In general, SBA-15 has microchannels on the walls through which the mesopores are interconnected when synthesized at 100?°C or higher. We, therefore, synthesized SBA-15 at a low temperature (80?°C) to eliminate the microchannels. Impregnation of the metal precursors and reduction of them into metals forms metal particles outside the pores in addition to the desired metal nanowires inside the pores. Surface alkylation of SBA-15 prohibits the nucleation of metal on the external surface and exclusively forms the nanowires. Finally, the introduction of surface passivating agent, an alkylthiol, during the removal of the template keeps the nanowires from interacting with one another. The Pt and Ag nanowires so-synthesized were characterized by electron microscopy.     

Growth and use of metal nanocrystal assemblies on high-density silicon nanowires formed by chemical vapor deposition

In this paper, we describe the growth and potential application of metal nanocrystal assemblies on metal-catalyzed, CVD-grown silicon nanowires (SiNWs). The nanowires are decorated by chemical assembly of closely spaced (1–5 nm) Ag (30–100 nm diameter) and Au (5–25 nm diameter) nanocrystals formed from solutions of AgNO₃ and NaAuCl₄·2H₂O, respectively. The formation and growth of metal nanocrystals is believed to involve the galvanic reduction of metal ions from solution and the subsequent oxidation of available Si-hydride sites on the surfaces of the nanowires. A native oxide layer suppresses formation of metal nanocrystals; adding HF to the ionic solutions significantly increases the density of nanocrystals on the surfaces of the nanowires. The nanocrystals coating the nanowires were characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction. Ag nanocrystals on the nanowires afford sensitive detection of Rhodamine 6G (R6G) molecules in the 100 picomolar–micromolar range by surface enhanced Raman spectroscopy. In addition, Au nanocrystals formed on selected surfaces of a substrate of arbitrary shape can serve as effective nuclei for localized nanowire growth. PACS 81.07.b; 81.15.Gh     

Correlation between structure and optoelectronic properties in a two‐dimensional nanoparticle assembly

The optical properties of two‐dimensional assemblies of metal nanoparticles are strongly influenced by the morphological configuration of the metal particles in the layer. Therefore, we correlate the structural and optical properties of two‐dimensional, hexagonal gold nanoparticle arrays. We characterize the structure of the arrays using grazing‐incidence small angle X‐ray scattering (GISAXS). From the GISAXS pattern, we determine the size of the gold particles as well as the lattice spacing of the hexagonal assembly. Based upon these parameters we calculate the dielectric function of the gold particle array using the Maxwell–Garnett effective medium theory. We further deduce the absorption spectrum which closely follows the measured absorption and photoconductance spectrum. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stabilization of Pt nanoparticles by single stranded DNA and the binary assembly of Au and Pt nanoparticles without hybridization

The non-specific interaction between single stranded DNA (ssDNA) and 12 nm Pt nanoparticles is investigated in this work. The data show a strong and non-specific interaction between the two which can be exploited for the stabilization of Pt nanoparticles in aqueous solutions. Based on the experimental findings, a non-hybridization based protocol to assemble 17 nm Au and Pt nanoparticles (12 nm cubic and 3.6 nm spherical) by single-stranded DNA was developed. Transmission electron microscopy (TEM) and UV–visible spectroscopy confirmed that Au and Pt nanoparticles could be assembled by the non-specific interaction in an orderly manner. The experimental results also caution against the potential pitfalls in using DNA melting point analysis to infer metal nanoparticle assembly by DNA hybridization.     

Metal Nanoparticle Coating of Oxide Nanospheres for Core‐Shell Structures

A low‐temperature route for coating oxide nanospheres with metal nanoparticles to achieve core‐shell structures is introduced. First results indicating a dense coverage of silica nanospheres of about 300 nm size with regularly arranged Ag and Au nanoparticles deposited by a modified incipient wetness impregnation procedure are presented. This synthesis works completely without external reducing agents or media, adhesive aids or functionalizing agents. Metal particles of only a few nanometers in size may serve as seeds for continuous metal coating of the oxide spheres by complementary processes. Structural characterization of the materials by transmission electron microscopy reveals a nearly spherical shape of the metal particles, the structure of which ranges from single crystalline to single twinned and multiply twinned configurations.     

Heterogeneous Nanoassembling: Microfluidically Prepared Poly(methyl methacrylate) Nanoparticles on Ag Microrods and ZnO Microflowers

The heterogeneous assembly of colloidal polymer particles on the nano‐ and microstructures of a metal is a versatile platform for adjusting the mechanical and electrical properties simultaneously. The assemblies of silver (Ag) microrods and flower‐like zinc oxide (ZnO) microparticles with poly(methyl methacrylate) (PMMA) nanospheres are presented to prepare advanced composite materials. PMMA nanoparticles are prepared via the emulsion polymerization technique using a microfluidic preparation step in the presence of cationic surfactant. The surface charge of PMMA particles determines the binding interaction strength with inorganic constituents. Ag microrods and ZnO microparticles are prepared in a batch and in a continuous flow process, respectively. The assembling process can be explained by a particle–particle binding process due to the electrostatic interaction for both types of nanoassemblies. The observed binding pattern reveals certain lateral mobility of the small polymer particles at the surface of larger metal particle. The particle ratios in the nanoassemblies can be tuned over a wide range by changing the reaction parameters.     

原子尺度金属纳米线的结构和性质

当物质尺度减少到几层原子时,形成超细的纳米结、纳米线、或者纳米团簇,原有凝聚态物质的结构和物理性质将不再保持,而呈现出许多令人惊奇的奇异特性。本文重点讨论直径大约3 nm以下,具有足够长度的、原子结构往往不同于体材料的准一维金属纳米结构,我们称之为原子尺度金属纳米线或超细金属纳米线(也称为金属原子线)。近年来实验上已经制备和表征出在超高真空中悬挂在两个顶针尖端的Au、Pt、Cu等金属纳米线和纳米管,金属线直径达到1 nm以下而长度为6 nm以上。通过高分辩电子显微镜观察,它们是同轴圆管(或壳)组成的、类似纳米碳管的单壳或多壳结构,管由绕着线轴的螺旋原子绳构成。理论工作围绕这种新奇结构形态的形成机制、奇异的物理性质和可能的应用前景而同时展开。这是一个崭新的纳米世界,无论是对基础的低维物理还是未来分子电子设备的应用,都将产生深远的影响,有许多奇妙的现象正等待人们去发现。本文将对最近几年原子尺度金属纳米线研究工作的主要进展和发展趋势作一个概述,并重点介绍本组有关的具有螺旋结构的纳米线的各类新奇结构和物理性质。     

原子尺度金属纳米线的结构和性质

当物质尺度减少到几层原子时，形成超细的纳米结、纳米线、或者纳米团簇，原有凝聚态物质的结构和物理性质将不再保持，而呈现出许多令人惊奇的奇异特性。本文重点讨论直径大约3nm以下，具有足够长度的、原子结构往往不同于体材料的准一维金属纳米结构，我们称之为原子尺度金属纳米线或超细金属纳米线（也称为金属原子线）。近年来实验上已经制备和表征出在超高真空中悬挂在两个顶针尖端的Au、Pt、Cu等金属纳米线和纳米管，金属线直径达到1nm以下而长度为6nm以上。通过高分辩电子显微镜观察，它们是同轴圆管（或壳）组成的、类似纳米碳管的单壳或多壳结构，管由绕着线轴的螺旋原子绳构成。理论工作围绕这种新奇结构形态的形成机制、奇异的物理性质和可能的应用前景而同时展开。这是一个崭新的纳米世界，无论是对基础的低维物理还是未来分子电子设备的应用，都将产生深远的影响，有许多奇妙的现象正等待人们去发现。本文将对最近几年原子尺度金属纳米线研究工作的主要进展和发展趋势作一个概述，并重点介绍本组有关的具有螺旋结构的纳米线的各类新奇结构和物理性质。     

Targeted deposition of Au aerosol nanoparticles on vertical nanowires for the creation of nanotrees

Complex tree-like nanostructures with controlled morphology are becoming increasingly important for the development of nanoscale devices. The position of branches on III–V semiconductor nanotrees is determined by the distribution of Au seed particles. Here we report the dependence of the distribution of Au aerosol nanoparticles on nanowires on parameters including distance between wires, particle size, wire length, wire diameter, III–V material and particle charge. It was observed that different wire lengths and separation distances as well as different particle polarities have a significant effect on the resulting particle distribution while different wire diameters, particle diameters, materials and deposition voltages do not.     

Formation of superconductivity through interparticle interactions in ferrimagnetic-like Sn nanoparticle assemblies

We report on the observation of the development of superconductivity through interparticle interactions in 3, 5, 7, and 23 nm ferrimagnetic-like Sn nanoparticle assemblies. The Sn nanoparticles are fabricated using the gas condensation method. Each sample consists of a macroscopic amount of individual Sn nanoparticles without a capping molecule. Ferrimagnetism is found but no sign of superconductivity can be detected when the 3 nm particles are very loosely assembled. A reduction in the mean particle moment results when the packing fraction of the assembly is increased. Superconductivity occurs when a critical packing fraction is reached. Beyond this, the superconducting transition temperature T _C continues to increase and noticeably exceeds that of the bulk T _C. The enhancement of superconductivity by interparticle interactions has also been observed in 5, 7, and 23 nm particle assemblies, with the effect becoming less significant in larger particles. We attribute these observations to the transfer of electrons between the surface and the core regions of the nanoparticles triggered by finite size effects and interparticle interactions.     

Structural and Optical Properties of Gold/Silica “Mushroom” Particles Prepared by Interfacial Templating

Complex shaped nanoparticles featuring structural or surface chemical patchiness are of special interest in both fundamental and applied research areas. This study reports the preparation and optical properties of gold/silica “mushroom” nanoparticles, where a gold particle is only partially covered by the silica cap. The synthetic approach allows precise control over the particle structure. The interfacial preparation method relies on partially embedding the gold particles in a polystyrene layer that masks the immersed part of the gold particle during silica shell growth from an aqueous solution. By adjusting sacrificial polystyrene film thickness and silica growth time, precise control over the coverage and cap thickness can be achieved. Correlative electron microscopy and single particle scattering spectroscopy measurements underline the high precision and reproducibility of the method. The good agreement between the measured and simulated single particle spectra supported by near‐field calculations indicates that the observed changes in the dipolar plasmon resonance are influenced by the extent of coverage of the gold core by the silica cap. The straightforward methods readily available for gold and silica surface modification using range of different (bio)molecules make these well‐defined nanoscale objects excellent candidates to study fundamental processes of programmed self‐assembly or application as theranostic agents.     

Highly Enhanced Emission of Visible Light from Core–Dual‐Shell‐Type Hybridized Nanoparticles

Core–dual‐shell‐type hybridized nanoparticles (NPs) having Au‐core/dye‐doped silica inner shell/Au outer shell are successfully fabricated by developing a biphasic process that is a kind of so‐called “one‐pot” method. The resulting hybridized NPs exhibit evidently about 20‐fold enhancement of fluorescence intensity, increase in fluorescence quantum yield, and decrease in fluorescence lifetime. These effects depend on the metal nanostructure being optimized, compared with the reference hybridized NPs with neither a Au‐core nor a Au outer shell, due to the gap‐mode effect induced by localized surface plasmon resonance in the core–dual‐shell‐type MIM‐like nanostructure. More detailed elucidation concerning the enhancement mechanism will provide the possibility of photonic device application, for example as a high‐performance point light source, nanolaser, or sensor for bioimaging in the visible region in the near future.     

Carbon films grown on Pt(1 1 1) as supports for model gold catalysts

Carbon films were grown on a Pt(1 1 1) single crystal by ethylene decomposition at elevated temperatures (1000-1300 K). Depending on the preparation conditions, different carbon structures formed on the metal surface such as flat and curved graphitic layers, carbon particles and carbon nanowires. Although these carbon films exhibited a high density of surface defects, gold interacted only weakly with the carbon surface. CO adsorption on the Au/carbon systems was very similar to that observed for various Au/oxide systems previously studied. This finding strongly indicates that CO adsorption on gold is essentially independent of the nature of support.     

Growth of Pure Zinc Blende GaAs Nanowires: Effect of Size and Density of Au Nanoparticles

Pure zinc blende GaAs nanowires were grown by metal organic chemical vapor deposition on GaAs（111）B substrates via Au catalyzed vapor-liquid-solid mechanism. The diameter, size distribution, and density of Au particles can be changed by varying the Au film thickness. We find that the grown nanowires are of rod-like shapes and pure zinc blende structure; moreover, the growth rate depends on the density of Au particles and it is independent of its diameters. It can be concluded that the nanowire was grown with main contributions from the direct impingement of vapor species onto the Au-Ga droplets and contributions from adatom diffusion can be negligible. The results indicate that the droplet acts as a catalyst rather than an adatom collector.     

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     

Synthesis and thermal stability of gold nanowires within monolithic mesoporous silica

This paper describes the preparation, by a novel and simple method, and the thermal stability of gold nanowires within monolithic mesoporous silica, involving soaking monolithic mesoporous silica in HAuCl₄ aqueous solution, followed by drying and subsequent step-annealing. It has been shown that reduction of Au³⁺ within silica pores can occur during the drying process at 80 °C without any special reduction treatment. After initial annealing at 300 °C, Au nanowires are formed within the pores and are stable at temperatures up to 500 °C. Increasing the annealing temperature leads to a wire-to-rod-to-sphere morphological transformation of the Au nanowires. The surface-mediated reducing groups (-OH) on the silica pore are responsible for the low-temperature reduction of Au³⁺ ions, and the formation of Au nanowires is attributed to the uni-directional diffusion of Au atoms and the confinement of the pore channels. Spheroidization and breaking at some defects in the Au nanowires during annealing at elevated temperature result in the wire-to-rod-to-sphere transformation, accompanied by a blue-shift of the surface plasmon resonance over a very wide region in the optical spectrum. PACS 81.07.-b; 81.40.-z; 81.05.Rm