Template‐Confined Dewetting Process to Surface Nanopatterns: Fabrication,Structural Tunability,and Structure‐Related Properties

Metallic surface nanopatterns are prepared by a template‐confined dewetting process with multiple structural controllabilities. The morphology of the building blocks is homogeneous throughout the surface nanopatterns, as the dewetting process proceeds separately in each bowl. The features of the building units in the surface patterns are highly dependent on the annealing temperature. Importantly, the size and composition of the nanoparticles in the surface nanopatterns can be pre‐calculated and designed by manipulating the thickness of the evaporated metallic films. The heating temperature and composition of the building units influence the surface‐enhanced Raman scattering (SERS) and plasmonic properties, thus tuning the localized surface plasmon resonance peaks over a broad range (from visible to near infrared). The introduction of silver in the gold surface nanopatterns enhances the SERS performance dramatically. This work not only provides a powerful route to fabricate surface nanopatterns, but also supplies a platform to study the mechanism of the complicated dewetting processes of metals.     

Synthesis and Properties of Plasmonic Boron‐Hyperdoped Silicon Nanoparticles

Electronic properties of silicon, the most important semiconductor material, are controlled through doping. The range of achievable properties can be extended by hyperdoping, i.e., doping to concentrations beyond the nominal equilibrium solubility of the dopant. Here, hyperdoping is achieved in a laser pyrolysis reactor capable of providing nonequilibrium conditions, where doping is governed by kinetics rather than thermodynamics. High resolution scanning transmission electron microscopy (TEM) with energy‐dispersive X‐ray spectroscopy shows that the boron atom distribution in the hyperdoped nanoparticles is relatively uniform. The hyperdoped nanoparticles demonstrate tunable localized surface plasmon resonance (LSPR) and are stable in air for periods of at least one year. The hyperdoped nanoparticles are also stable upon annealing at temperatures up to 600 °C. Furthermore, boron hyperdoping does not change the diamond cubic crystal structure of silicon, as demonstrated in detail by high flux synchrotron X‐ray diffraction and pair distribution function (PDF) analysis, supported by high‐resolution TEM analysis.     

Optical Properties and Growth Aspects of Silver Nanoprisms Produced by a Highly Reproducible and Rapid Synthesis at Room Temperature

A rapid and readily reproducible seed‐based method for the production of high quality silver nanoprisms in high yield is presented. The edge‐length and the position of the main plasmon resonance of the nanoprisms can be readily controlled through adjustment of reaction conditions. From UV‐vis spectra of solutions of the nanoprisms, the inhomogeneously broadened line width of the in‐plane dipole plasmon resonance is measured and trends in the extent of plasmon damping as a function of plasmon resonance energy and nanoprism size have been elucidated. In addition, an in‐depth analysis of the lamellar defect structure of silver nanoprisms is provided that confirms that the defects can lead to a transformation of the crystal structure in the vicinity of the defects. These defects can combine give rise to lamellar regions, thicker than 1 nm, that extend across the crystal, where the silver atoms are arranged in a continuous hexagonal‐close‐packed (hcp) structure. This hcp structure has a periodicity of 2.50 Å, thus explaining the 2.50 Å lattice fringes that are commonly observed in 〈111〉 oriented flat‐lying nanoprisms. A new understanding of the mechanisms behind anisotropic growth in silver nanoprisms is presented.     

Investigation of Optical and Structural Stability of Localized Surface Plasmon Mediated Light‐Emitting Diodes by Ag and Ag/SiO2 Nanoparticles

Localized surface plasmon (LSP) effects due to Ag and Ag/SiO₂ nanoparticles (NPs) deposited on GaN/InGaN multiquantum well (MQW) light‐emitting diode (LED) structures are studied. The colloidal NPs are synthesized by a sol‐gel method and drop‐cased on the LED structures. The surface density of NPs its controlled by the concentration of the NP solution. Theoretical modeling is performed for the emission spectrum and the electric field distribution of LSP resonance for Ag/SiO₂ NPs. Enhanced photoluminescence (PL) efficiency is observed in the LED structures and the amount of PL enhancement increases with increasing the surface density of Ag and Ag/SiO₂ NPs. These effects are attributed to resonance coupling between the MQW and LSP in the NPs. It is also shown that the PL enhancement attainable with Ag NPs and Ag/SiO₂ NPs is comparable, but the latter displays a much higher stability with respect to long‐term storage and annealing due to a barrier for NP agglomeration, Ag oxidation, and impurity diffusion provided by the SiO₂ shell.     

Arrays of Cone‐Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface‐Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls

A new, highly sensitive and uniform three‐dimensional (3D) hybrid surface‐enhanced Raman scattering (SERS) substrate has been achieved via simultaneously assembling small Ag nanoparticles (Ag‐NPs) and large Ag spheres onto the side surface and the top ends of large‐scale vertically aligned cone‐shaped ZnO nanorods (ZnO‐NRs), respectively. This 3D hybrid substrate manifests high SERS sensitivity to rhodamine and a detection limit as low as 10^?11 M to polychlorinated biphenyl (PCB) 77—a kind of persistent organic pollutants as global environmental hazard. Three kinds of inter‐Ag‐NP gaps in 3D geometry create a huge number of SERS “hot spots” that mainly contribute to the high SERS sensitivity. Moreover, the supporting chemical enhancement effect of ZnO‐NRs and the better enrichment effect ascribed to the large surface area of the substrate also help to achieve a lower detection limit. The arrays of cone‐shaped ZnO‐NRs decorated with Ag‐NPs on their side surface and large Ag spheres on the top ends have potentials in SERS‐based rapid detection of trace PCBs.     

Solid‐State Pyrolysis of Polyphenylene–Metal Complexes: A Facile Approach Toward Carbon Nanoparticles

Novel polyphenylene–metal complexes with discotic, linear, and dendritic geometries are synthesized by using a facile approach consisting of reactions between Co₂(CO)₈ and ethynyl functionalities in dichloromethane. Various carbon nanoparticles (CNPs), including graphitic carbon nanotubes (CNTs), graphitic carbon rods, and carbon–metal hybrid particles are obtained from the solid‐state pyrolysis of these complexes. The ultimate structures of the CNPs are found to be dependant on the structure and composition of the starting compounds. Precursors containing graphenes always result in graphitic CNTs in high yield, whereas dendritic precursors give rodlike carbon materials. Alternatively, linear oligo(arylethylene) precursors afford mostly carbon–metal hybrids with large amounts of amorphous carbon. Furthermore, the CNP structures could be controlled by adjusting the carbon/metal ratio, the type and position of the metal incorporated into the precursor, and the mode of pyrolysis. These results provide further chances toward understanding the mechanism of CNP formation.     

Hierarchically Ordered Arrays of Noncircular Silicon Nanowires Featured by Holographic Lithography Toward a High‐Fidelity Sensing Platform

A novel, highly uniform and tunable hybrid plasmonic array is created via ion‐milling, catalytic wet‐etching and electron‐beam evaporation, using a holographically featured structure as a milling mask. A simple and low‐cost prism holographic lithography (HL) technique is applied to create an unprecedentedly coordinated array of elliptic gold (Au) holes, which act as the silicon (Si) etching catalyst in the reaction solution used to fabricate an elliptic silicon nanowire (SiNW) array; here, the SiNWs are arrayed hierarchically in such a way that three SiNWs are triangularly coordinated, and the triangles are arranged hexagonally. After removing the polymeric mask and metal thin film, the highly anisotropic thick Au film is deposited on the SiNW arrays. This hybrid substrate shows tunable optical properties in the near‐infrared (NIR) region from 875 nm to 1030 nm and surface‐enhanced Raman scattering (SERS) activities; these characteristics depend on the catalytic wet etching time, which changes the size of the vertical gap between the Au thick films deposited separately on the SiNWs. In addition, lateral interparticle coupling induces highly intensified SERS signals with good homogeneity. Finally, the Au‐capped elliptical SiNW arrays can be hierarchically patterned by combining prism HL and conventional photolithography, and the highly enhanced fluorescence intensity associated with both the structural effects and the plasmon resonances is investigated.     

Nanoscale Graphene Doped with Highly Dispersed Silver Nanoparticles: Quick Synthesis,Facile Fabrication of 3D Membrane‐Modified Electrode,and Super Performance for Electrochemical Sensing

The performance of graphene‐based hybrid materials greatly depends on the dispersibility of nanoscale building blocks on graphene sheets. Here, a quick green synthesis of nanoscale graphene (NG) nanosheets decorated with highly dispersed silver nanoparticles (AgNPs) is demonstrated, and then the electrospinning technique to fabricate a novel nanofibrous membrane electrode material is utilized. With this technique, the structure, mechanical stability, biochemical functionality, and other properties of the fabricated membrane electrode material can be easily controlled. It is found that the orientations of NG and the dispersity of AgNPs on the surface of NG have significant effects on the properties of the fabricated electrode. A highly sensitive H₂O₂ biosensor is thus created based on the as‐prepared polymeric NG/AgNP 3D nanofibrous membrane‐modified electrode (MME). As a result, the fabricated biosensor has a linear detection range from 0.005 to 47 × 10^?3m (R = 0.9991) with a supralow detection limit of 0.56 × 10^?6m (S/N = 3). It is expected that this kind of nanofibrous MME has wider applications for the electrochemical detection and design of 3D functional nanomaterials in the future.     

Pattern Formation of Silver Nanoparticles in 1‐, 2‐, and 3D Microstructures Fabricated by a Photo‐ and Thermal Reduction Method

One‐, two‐, and three‐dimensional microstructures with dispersed silver nanoparticles are fabricated by a combination of photopatterning and thermal treatment from a silver salt containing photosensitive epoxy resin. Ultraviolet photo‐irradiation and subsequent thermal treatment are combined to control the rate of silver salt reduction, the size and the arrangement of nanoparticles, as well as the reticulation of the epoxy resin. This approach allows the creation of high resolution 1‐, 2‐, and 3D patterns containing silver nanoparticles, with a homogeneous distribution of nanoparticles regardless of the irradiated area.     

Exploring How to Increase the Brightness of Surface‐Enhanced Raman Spectroscopy Nanolabels: The Effect of the Raman‐Active Molecules and of the Label Size

Due to the surface‐enhanced Raman scattering (SERS) effect, SERS labels based on noble‐metal nanoparticles loaded with Raman‐active molecules are good candidates for ultrasensitive multiplexed assays and in vitro/in vivo imaging. However, understanding how to maximize the brightness of such labels is of paramount importance for their widespread application. The effective differential Raman scattering cross‐section (dσ_R/dΩ) of SERS labels made of pegylated gold nanoparticles loaded with various Raman active molecules (Raman reporters) is studied. It is found that proper choice of the Raman reporter and of nanoparticle size can enhance the dσ_R/dΩ by several orders of magnitude. The experimental results are understood by considering the molecular cross‐section for resonant Raman scattering and the local electromagnetic enhancement factor (G_SERS) in the nearby of gold nanoparticles. These results are useful to guide the design of SERS labels with improved performances and to provide a reference for the comparison of the absolute value of the dσ_R/dΩ of SERS labels based on metal nanoparticles.     

Nanoparticles: Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse PtxNi1‐x Nanoparticles (Adv. Funct. Mater. 1/2011)

Monodisperse and homogeneous Pt_xNi_1‐x alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic‐level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt‐skeleton nanostructures. The developed approach and acquired knowledge about surface structure‐property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.     

A Micellar Route to Ordered Arrays of Magnetic Nanoparticles: From Size‐Selected Pure Cobalt Dots to Cobalt–Cobalt Oxide Core–Shell Systems

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl₂ is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p_3/2 line pointing to the formation of Co₃O₄. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures pequation/tex2gif-inf-5.gif, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (pequation/tex2gif-inf-7.gif × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.