Surface Nanometer‐Scale Patterning in Realizing Large‐Scale Ordered Arrays of Metallic Nanoshells with Well‐Defined Structures and Controllable Properties

Surface patterns of nanoshell arrays play an important role in diverse applications including surface‐enhanced Raman scattering (SERS) sensors, lithium‐ion batteries, solar cells, and optical devices. This paper describes an innovative surface nanopatterning technique for realizing large‐scale ordered arrays of metallic spherical nanoshells with well‐defined structures. Ag nanoshell arrays are prepared using polystyrene sphere templates by an electrophoretic process in Ag colloidal solutions. The fabricated Ag nanoshell arrays have a high controllability of the structural parameters, including the diameter, the surface roughness, and the intershell spacing, giving rise to the tunable properties of nanoshell arrays. As an example, tunable SERS and localized surface plasmon resonance of the nanoshell arrays are demonstrated by controlling the structural parameters. The surface nanopatterning technique shown in this paper is a general fabrication process in achieving not only metallic nanoshell arrays, but also nanoshell arrays of semiconductors and metallic oxides.     

Self‐Assembled SERS Substrates with Tunable Surface Plasmon Resonances

The fabrication of surface‐enhanced Raman spectroscopy (SERS) substrates that are optimized for use with specific laser wavelength–analyte combinations is addressed. In order to achieve large signal enhancement, temporal stability, and reproducibility over large substrate areas at low cost, only self‐assembly and templating processes are employed. The resulting substrates consist of arrays of gold nanospheres with controlled diameter and spacing, properties that dictate the optical response of the structure. Tunability of the extended surface plasmon resonance is observed in the range of 520–1000 nm. It is demonstrated that the enhancement factor is maximized when the surface plasmon resonance is red‐shifted with respect to the SERS instrument laser line. Despite relying on self‐organization, site‐to‐site enhancement factor variations smaller than 10% are obtained.     

Standing‐Wave‐Assisted Creation of Nanopillar Arrays with Vertically Integrated Nanogaps for SERS‐Active Substrates

An optical method is used to create multi‐dimensional metal structures with three distinct periodicities for surface‐enhanced Raman scattering (SERS). Periodic arrays of nanopillars are formed by phase‐shift interference lithography on sub‐micrometer length scales. With the help of a standing wave, each nanopillar is made to be a disk‐stacking structure consisting of a series of 20‐nm‐thick metal nanogaps; the nanopillars consequently resemble a pagoda. The vertically integrated metal nanogaps of the metal‐deposited pagoda‐like nanopillars enable strong localization of an electromagnetic field and effective enhancement of Raman signals for molecules adsorbed on the metal surface. Moreover, the nanopillars are arranged in a regular lattice, which results in a low spatial variation of the SERS intensity and provides high reproducibility in measurements. Arrays of the nanopillars can be further micropatterned to have a periodicity ranging from tens of micrometers to a millimeter by subsequently employing photo‐lithography. The nanopillar arrays promote the wetting of sample fluids, which enables the selective confinement of fluids on the array regions of the micropatterns without spreading. Consequently, numerous fluid samples can be separately deposited, enabling SERS‐based analysis of multiple samples using a single substrate.     

Fabrication and characterization of silver deposited micro fabricated quartz arrays for surface enhanced Raman spectroscopy (SERS)

In this work microfabricated silver coated two-dimensional quartz gratings are developed for the use as plasmonic arrays for surface enhanced Raman spectroscopy (SERS). The SERS technique provides enormous signal intensity and fingerprint specificity and is a powerful tool in chemical and biological applications. However, the acceptance and the employment of the SERS technique for (bio)analytical devices depends on the availability of suitable substrates with homogenous field enhancement properties. Here, the fabrication and optimization process of the SERS array with an enhancement factor between 10⁵ and 10⁶ is introduced.     

Real‐Time Probing Nanopore‐in‐Nanogap Plasmonic Coupling Effect on Silver Supercrystals with Surface‐Enhanced Raman Spectroscopy

Nanopore structures have displayed attractive prospects in diverse important applications such as nanopore‐based biosensors and enhanced spectroscopy. However, on the one hand, the fabrication techniques to obtain sub‐10 nm sized nanopores so far is very limited. On the other hand, the electromagnetic enhancement of nanopores is still relatively low. In this work, using a facile chemical etching strategy on 2D plasmonic Ag nanoparticle supercrystals, fine nanopore arrays with sub‐10 nm pore size have been successfully fabricated and a “nanopore‐in‐nanogap” hybrid plasmon mode has been investigated. An in situ etching and surface‐enhanced Raman spectroscopy (SERS) detection indicate that novel hybrid plasmon structure may create an enhanced electromagnetic coupling and increase SERS signal at ≈10× magnification. The breaking of plasmon bonding dipolar mode and generation of antibonding‐like plasmon mode contribute to this enhanced electromagnetic coupling. The facile etching strategy, as a common approach, may open the doors for the fabrication of nanopores in various compositions for numerous applications.     

DNA‐Directed Self‐Assembly of Core‐Satellite Plasmonic Nanostructures: A Highly Sensitive and Reproducible Near‐IR SERS Sensor

The excitation of surface plasmons in metallic nanostructures provides an opportunity to localize light at the nanoscale, well below the scale of the wavelength of the light. The high local electromagnetic field intensities generated in the vicinity of the nanostructures through this nanofocusing effect are exploited in surface enhanced Raman spectroscopy (SERS). At narrow interparticle gaps, so‐called hot‐spots, the nanofocusing effect is particularly pronounced. Hence, the engineering of substrates with a consistently high density of hot‐spots is a major challenge in the field of SERS. Here, a simple bottom‐up approach is described for the fabrication of highly SERS‐active gold core‐satellite nanostructures, using electrostatic and DNA‐directed self‐assembly. It is demonstrated that well‐defined core‐satellite gold nanostructures can be fabricated without the need for expensive direct‐write nanolithography tools such as electron‐beam lithography (EBL). Self‐assembly also provides excellent control over particle distances on the nanoscale. The as‐fabricated core‐satellite nanostructures exhibit SERS activities that are superior to commercial SERS substrates in signal intensity and reproducibility. This also highlights the potential of bottom‐up self‐assembly strategies for the fabrication of complex, well‐defined functional nanostructures with future applications well beyond the field of sensing.     

Triplex Au–Ag–C Core–Shell Nanoparticles as a Novel Raman Label

Monodispersed, readily‐grafted, and biocompatible surface‐enhanced Raman spectroscopic (SERS) tagging materials are developed; they are composed of bimetallic Au@Ag nanoparticles (NPs) for optical enhancement, a reporter molecule for spectroscopic signature, and a carbon shell for protection and bioconjugation. A controllable and convenient hydrothermal synthetic route is presented to synthesize the layer‐by‐layer triplex Au–Ag–C core–shell NPs, which can incorporate the Raman‐active label 4‐mercapto benzoic acid (4‐MBA). The obtained gold seed–silver coated particles can be coated further with a thickness‐controlled carbon shell to form colloidal carbon‐encapsulated Au_core/Ag_shell spheres with a monodisperse size distribution. Furthermore, these SERS‐active spheres demonstrated interesting properties as a novel Raman tag for quantitative immunoassays. The results suggest such SERS tags can be used for multiplex and ultrasensitive detection of biomolecules as well as nontoxic, in vivo molecular imaging of animal or plant tissues.     

3D Microfluidic Surface‐Enhanced Raman Spectroscopy (SERS) Chips Fabricated by All‐Femtosecond‐Laser‐Processing for Real‐Time Sensing of Toxic Substances

A novel all‐femtosecond‐laser‐processing technique is proposed for the fabrication of 2D periodic metal nanostructures inside 3D glass microfluidic channels, which have applications to real‐time surface‐enhanced Raman spectroscopy (SERS). In the present study, 3D glass microfluidic channels are fabricated by femtosecond‐laser‐assisted wet etching. This is followed by the space‐selective formation of Cu‐Ag layered thin films inside the microfluidic structure via femtosecond laser direct writing ablation and electroless metal plating. The Cu‐Ag films are subsequently nanostructured by irradiation with linearly polarized beams to form periodic surface structures. This work demonstrates that a double exposure to laser beams having orthogonal polarization directions can generate arrays of layered Cu‐Ag nanodots with dimensions as small as 25% of the laser wavelength. The resulting SERS microchip is able to detect Rhodamine 6G, exhibiting an enhancement factor of 7.3 × 10⁸ in conjunction with a relative standard deviation of 8.88%. This 3D microfluidic chip is also found to be capable of the real‐time SERS detection of Cd²⁺ ions at concentrations as low as 10 ppb in the presence of crystal violet. This technique shows significant promise for the fabrication of high performance microfluidic SERS platforms for the real‐time sensing of toxic substances with ultrahigh sensitivity.     

Anisotropic Optical Properties of Semitransparent Coatings of Gold Nanocaps

An ordered array of cap‐shaped gold nanoparticles has been prepared by vapor deposition onto polystyrene nanospheres supported on a glass substrate. The method of fabrication used imparts a significant anisotropy to the geometric and optical properties of the coating. The optical‐absorption properties of these deposits have been measured using UV‐vis spectrometry and simulated using a code based on the discrete dipole approximation. Because the nanocaps are not interconnected, they interact with incident light as individual particles with a plasmon resonance that depends upon wavelength and the polarization vector of the light. The resulting extinction peaks manifest in the upper visible and near‐infrared regions of the electromagnetic spectrum. Surprisingly, varying the angle of incidence of the light (for a fixed polarization) has no effect on the optical properties of individual nanocaps. Calculations show that these phenomena may be readily interpreted in terms of dipole resonances excited across the longitudinal, transverse, and short‐transverse directions of the nanocaps. Coatings comprised of arrays of these particles have the potential to serve as angularly and spectrally selective filters.     

介孔氧化铝组装金纳米颗粒阵列及其光学性质

采用真空蒸镀的方法在多孔氧化铝模板表面得到薄金膜,随后在真空管式炉中进行热处理,热处理中发生的热去湿过程使得金膜在多孔氧化铝表面形成有序的金纳米颗粒阵列。同时还研究了多孔氧化铝模板制备过程中二次氧化的作用,发现一次氧化对二次氧化进行具有一定指导作用;另外,研究了扩孔时间对模板孔径的影响,一定条件下,扩孔时间与孔径成正比例关系;最后研究了镀膜厚度对金纳米颗粒的影响,结果中可以看到,金膜的厚度直接影响金纳米颗粒阵列的形成。最后在分光光度计上的光学测量吸收光谱的结果中,出现了表面等离子体作用引起的很强的吸收峰。     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

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.     

高填充因子微透镜阵列的快速制备及特性分析

微透镜阵列是一种被广泛应用于光信息处理、光传感、光计算、光通信和高灵敏度成像等领域的精密光学元器件之一。通过一些先进的制造技术已经可以制造出不同几何形状、轮廓和光学特性的微透镜阵列。然而,由于三维微制造工艺的难度,使得高填充因子微透镜阵列中的微透镜很难实现紧密排列。提出了一种快速、低成本的微流体操纵技术,用于制备高填充因子微透镜阵列,且对其制备工艺进行了初步的演示。这种易于操作的制造技术适用于微透镜阵列的大批量生产,极大地提高了生产效率。通过预先制备出的三种不同尺寸(微柱直径分别为300、500、700 μm)的微柱,实现了与其对应不同形状和尺寸的微透镜阵列的制备,并搭建了一套光学成像系统以对这些微透镜阵列进行成像性能的评估。主要对微透镜阵列的焦距、成像精度和每个微透镜阵列中各个微透镜子单元成像的均一性进行测试,利用所提出的微流体操控技术制备的微透镜阵列具有良好的成像性能,有望能够被应用到三维成像、光均匀化等诸多应用中。     

Inside Front Cover: Three‐Dimensionally Ordered Gold Nanocrystal/Silica Superlattice Thin Films Synthesized via Sol–Gel Self‐Assembly (Adv. Funct. Mater. 7/2006)

The synthesis of three‐dimensionally ordered, transparent gold‐nanocrystal (NC)/silica superlattice thin films using the self‐assembly (by spin‐coating) of water‐soluble gold nanocrystal micelles and soluble silica is reported by Fan and co‐workers on p. 891. The robust, 3D NC/silica superlattice films are of interest for the development of collective optical and electronic phenomena, and, importantly, for the integration of NC arrays into device architectures. Nanocrystals and their ordered arrays hold many important applications in fields such as catalysis, surface‐enhanced Raman spectroscopy based sensors, memory storage, and electronic and optical nanodevices. Herein, a simple and general method to synthesize ordered, three‐dimensional, transparent gold nanocrystal/silica superlattice thin films by self‐assembly of gold nanocrystal micelles with silica or organosilsesquioxane by spin‐coating is reported. The self‐assembly process is conducted under acidic sol–gel conditions (ca. pH 2), ensuring spin‐solution homogeneity and stability and facilitating the formation of ordered and transparent gold nanocrystal/silica films. The monodisperse nanocrystals are organized within inorganic host matrices as a face‐centered cubic mesostructure, and characterized by transmission electron spectroscopy and X‐ray diffraction.     

Nanogap Plasmonic Structures Fabricated by Switchable Capillary‐Force Driven Self‐Assembly for Localized Sensing of Anticancer Medicines with Microfluidic SERS

Nanogap plasmonic structures, which can strongly enhance electromagnetic fields, enable widespread applications in surface‐enhanced Raman spectroscopy (SERS) sensing. Although the directed self‐assembly strategy has been adopted for the fabrication of micro/nanostructures on open surfaces, fabrication of nanogap plasmonic structures on complex substrates or at designated locations still remains a grand challenge. Here, a switchable self‐assembly method is developed to manufacture 3D nanogap plasmonic structures by combining supercritical drying and capillary‐force driven self‐assembly (CFSA) of micropillars fabricated by laser printing. The polymer pillars can stay upright during solvent development via supercritical drying, and then can form the nanogap after metal coating and subsequent CFSA. Due to the excellent flexibility of this method, diverse patterned plasmonic nanogap structures can be fabricated on planar or nonplanar substrates for SERS. The measured SERS signals of different patterned nanogaps in fluidic environment show a maximum enhancement factor ≈8 × 10⁷. Such nanostructures in microchannels also allow localized sensing for anticancer drugs (doxorubicin). Resulting from the marriage of top‐down and self‐assembly techniques, this method provides a facile, effective, and controllable approach for creating nanogap enabled SERS devices in fluidic channels, and hence can advance applications in precision medicine.     

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.     

Three‐Dimensionally Ordered Gold Nanocrystal/Silica Superlattice Thin Films Synthesized via Sol–Gel Self‐Assembly

Nanocrystals and their ordered arrays hold many important applications in fields such as catalysis, surface‐enhanced Raman spectroscopy based sensors, memory storage, and electronic and optical nanodevices. Herein, a simple and general method to synthesize ordered, three‐dimensional, transparent gold nanocrystal/silica superlattice thin films by self‐assembly of gold nanocrystal micelles with silica or organosilsesquioxane by spin‐coating is reported. The self‐assembly process is conducted under acidic sol–gel conditions (ca. pH 2), ensuring spin‐solution homogeneity and stability and facilitating the formation of ordered and transparent gold nanocrystal/silica films. The monodisperse nanocrystals are organized within inorganic host matrices as a face‐centered cubic mesostructure, and characterized by transmission electron spectroscopy and X‐ray diffraction.     

大阵列数光阵列发生器研究

研究了产生大阵列数的光阵列发生器的设计与加工,设计并加工产生一维64点阵和二维4096点阵的光阵列发生器。     

Femto‐Second Laser‐Based Free Writing of 3D Protein Microstructures and Micropatterns with Sub‐Micrometer Features: A Study on Voxels,Porosity, and Cytocompatibility

Femto‐second laser‐based free‐writing of complex protein microstructures and micropatterns, with sub‐micrometer features and controllability over voxel dimension, morphology, and porosity, is reported. Protein voxels including lines, spots, and micropillars are fabricated. Laser power, exposure time, z‐position, protein and photosensitizer concentrations, but not scanning speed, are important controlling parameters. A lateral fabrication resolution of ≈200 nm is demonstrated in 2D line voxels. 3D spot voxels are ellipsoids with 400 nm lateral and 1.5 μm axial dimensions. An ascending z‐stack scanning method to verify the theoretical axial optical resolution, delineate and enhance the axial fabrication resolution of 3D structures, including square prism and cylinder micropillars, is also reported. The micropillar array presents a simple “write‐and‐seed” and table platform for cell niche studies. Fibroblasts attach to, grow on, and express adhesion to molecules on micropillar arrays without the need of matrix coating. They exhibit a more “3D” morphology comparing with that in 2D monolayer cultures and physiological functions such as matrix deposition. This work presents an important milestone in engineering complex protein microstructures and micropatterns with sub‐micrometer topological features to mimic the native matrix niche for cell‐matrix interaction studies.     

Self‐Organization of Inkjet‐Printed Organic Semiconductor Films Prepared in Inkjet‐Etched Microwells

The high‐precision deposition of highly crystalline organic semiconductors by inkjet printing is important for the production of printed organic transistors. Herein, a facile nonconventional lithographic patterning technique is developed for fabricating banks with microwell structures by inkjet printing solvent droplets onto a polymer layer, thereby locally dissolving the polymer to form microwells. The semiconductor ink is then inkjet‐printed into the microwells. In addition to confining the inkjet‐printed organic semiconductor droplets, the microwells provide a platform onto which organic semiconductor molecules crystallize during solvent evaporation. When printed onto the hydrophilic microwells, the inkjet‐printed 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS_PEN) molecules undergo self‐organization to form highly ordered crystalline structures as a result of contact line pinning at the top corner of the bank and the outward hydrodynamic flow within the drying droplet. By contrast, small crystallites form with relatively poor molecular ordering in the hydrophobic microwells as a result of depinning of the contact line along the walls of the microwells. Because pinning in the hydrophilic microwells occurred at the top corner of the bank, treating the surfaces of the dielectric layer with a hydrophobic organic layer does not disturb the formation of the highly ordered TIPS_PEN crystals. Transistors fabricated on the hydrophilic microwells and the hydrophobic dielectric layer exhibit the best electrical properties, which is explained by the solvent evaporation and crystallization characteristics of the organic semiconductor droplets in the microwell. These results indicate that this technique is suitable for patterning organic semiconductor deposits on large‐area flexible substrates for the direct‐write fabrication of high‐performance organic transistors.