Surface plasmon-quantum dot coupling from arrays of nanoholes

The coupling of semiconductor quantum dots (QDs) to the surface plasmon (SP) modes of nanohole arrays in a metal film was demonstrated for the first time, showing enhancement in the spontaneous emission by 2 orders of magnitude. The SP-enhanced transmission resonances of the nanohole arrays were tuned around the photoluminescence (PL) peak of polystyrene-b-poly(acrylic acid) (PS-b-PAA)-stabilized cadmium sulfide (CdS) quantum dots (QDs) in contact with the arrays. As a result the overall PL from the SP-QD system was enhanced by 2 orders of magnitude, even after excluding the enhanced transmission of the nanohole array without the QDs. The maximum enhancement occurred when the resonance from the nanohole array matched the QD PL spectrum. Time-resolved PL measurements were used to estimate the relative contribution of different physical mechanisms to the enhanced spontaneous emission. The increased spontaneous emission in the SP-QD system is promising for prospective plasmonic light-emitting devices incorporating QDs.     

Probing the protein orientation on charged self-assembled monolayers on gold nanohole arrays by SERS

In this work, surface-enhanced Raman scattering (SERS) was applied to probe the orientation of cytochrome c (Cyt-c) on gold nanohole arrays functionalized with self-assembled monolayers (SAMs) of alkane thiols with positively (-NH2) and negatively (-COOH) charged terminal groups. Square grid gold nanohole arrays with a nanohole diameter of 270 nm and a grating of 350 nm were fabricated by electron beam lithography (EBL) and were used as the SERS substrates. The SERS intensities of the nontotally symmetric mode (B(1g) mode nu(11)) and the totally symmetric mode (A(1g) mode nu(4)) and their ratios were used to determine the orientation of Cyt-c on surfaces. The results indicate that the heme group is close and perpendicular to the negatively charged surface but is far from and oriented at an angle to the positively charged surface. Cyt-c has a random or more flat orientation on the bare Au nanoholes surface.     

Generation of 30-50 nm structures using easily fabricated,composite PDMS masks

This communication demonstrates an approach to generate simple nanostructures with critical dimensions down to 30 nm over cm2-sized areas using composite PDMS masks. These masks were patterned with feature sizes down to 100 nm. When used in phase-shifting lithography, these masks generated arrays of structures in photoresist with line widths as small as 30 nm, slots in metal with features down to 40 nm, and wells in epoxy with diameters as small as 100 nm. The wells were used to prepare arrays of uniformly sized nanocrystals of salts.     

Periodic one-dimensional nanostructured arrays based on colloidal templates,applications, and devices

A novel approach to fabricate periodic one-dimensional (1D) nanostructured arrays is developed using monolayer colloidal crystals as templates or masks. This approach is more flexible and less costly than traditional lithographic techniques. The morphology and structural parameters of periodic arrays can be easily controlled, further resulting in optimized properties. Herein we introduce recent work to create periodic 1D nanostructured arrays by combining colloidal templates with other techniques, such as solution techniques, electrodeposition, wet chemical etching, reactive ion etching (RIE), pulsed laser deposition (PLD), and sputtering. These periodic 1D nanostructured arrays with controllable morphology and structural parameters have extensive applications in areas such as nanophotonics, field emitters, solar cells, light-emitting diodes, and microfluidic devices.     

Tunable SERS from aluminium nanohole arrays in the ultraviolet region

Ordered Al nanohole arrays for tunable UV-SERS are theoretically proposed and simulated by using FDTD method. The properly designed Al nanohole arrays produce stable and predictable Raman enhancement under the deep UV laser illumination. The SERS enhancement factor as high as 5 to 6 orders of magnitude is attained in the optimal geometry. The correlation between the SERS and EOT is studied in detail.     

Correlated AFM and SERS imaging of the transition from nanotriangle to nanohole arrays

Mapping the transition of Ag nanotriangle to nanohole arrays revealed that the optimal SERS response was obtained near the transition. Correlated AFM and Raman imaging provided novel experimental proof that hot spots are located on Ag islands for nanotriangle arrays and in the core area of the hole for nanohole arrays, which is in agreement with previous theoretical predictions.     

Large-scale fabrication of periodic nanostructured materials by using hexagonal non-close-packed colloidal crystals as templates

This letter reports a versatile nonlithographic technique for mass fabricating three types of technologically important materials-polymer microwell arrays, 2D-ordered magnetic nanodots, and semiconductor nanopillar arrays, each with high crystalline qualities and wafer-scale sizes. Spin-coated hexagonal non-close-packed silica colloidal crystals embedded in a polymer matrix are used as starting templates to create 2D polymeric microwell arrays. These through-hole arrays can then be used as second-generation templates to make periodic magnetic nanodots and semiconductor nanopillars. This self-assembly approach is compatible with standard semiconductor microfabrication, and complex micropatterns can be created for potential device applications. The wafer-scale technique may find important applications in biomicroanalysis, high-density magnetic recording media, and microphotonics.     

Plasmonic films based on colloidal lithography

This paper reviews recent advances in the field of plasmonic films fabricated by colloidal lithography. Compared with conventional lithography techniques such as electron beam lithography and focused ion beam lithography, the unconventional colloidal lithography technique with advantages of low-cost and high-throughput has made the fabrication process more efficient, and moreover brought out novel films that show remarkable surface plasmon features. These plasmonic films include those with nanohole arrays, nanovoid arrays and nanoshell arrays with precisely controlled shapes, sizes, and spacing. Based on these novel nanostructures, optical and sensing performances can be greatly enhanced. The introduction of colloidal lithography provides not only efficient fabrication processes but also plasmonic films with unique nanostructures, which are difficult to be fabricated by conventional lithography techniques.     

胶体刻蚀——纳米结构化表面的构筑与应用

综述了近年来胶体刻蚀领域的研究进展, 分别讨论了基于胶体微粒和胶体晶体为模板的可控沉积与可控刻蚀及在固体平面基质、曲面基质和气液界面等不同基质上构筑结构化表面的方法. 同时还探讨了利用胶体刻蚀方法形成的微纳结构在光、电、磁以及表面润湿和生物学等方面的应用.     

Block copolymer micelles as switchable templates for nanofabrication

Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structuring of the underlying material to form either pillars or holes depending on the switching state is demonstrated.     

EOT or Kretschmann configuration? Comparative study of the plasmonic modes in gold nanohole arrays

The debate is still ongoing on the optimal mode of interrogation for surface plasmon resonance (SPR) sensors. Comparative studies previously demonstrated that nanoparticles exhibiting a localized SPR (LSPR) have superior sensitivity to molecular adsorption processes while thin Au film-based propagating SPR is more sensitive to bulk refractive index. In this paper, it is demonstrated that nanohole arrays (1000 nm periodicity, 600 nm diameter and 125 nm depth), which support both LSPR and propagating SPR modes, exhibited superior sensitivity to bulk refractive index and improved detection limits for IgG sensing by using the Kretschmann configuration. The greater sensitivity to IgG detection in the Kretschmann configuration was obtained despite the shorter penetration depth of nanohole arrays excited in the enhanced optical transmission (EOT) configuration. The decay length of the electromagnetic field in EOT mode was estimated to be approximately 140 nm using a layer-by-layer deposition technique of polyelectrolytes (PAH and PSS) and was confirmed with 3D FDTD simulations, which was lengthen by almost a factor of two in the Kretschmann configuration. Spectroscopic data and field depth were correlated with RCWA and FDTD simulations, which were in good agreement with the experimental results. Considering these analytical parameters, it is advantageous to develop sensors based on nanohole arrays in the Kretschmann configuration of SPR.     

Colloidal lithographic nanopatterning via reactive ion etching

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.     

Templated fabrication of sub-100 nm periodic nanostructures

Periodic polymer nanoposts and metal nanohole arrays with tunable size have been fabricated by templating from spin-coated two-dimensional non close-packed colloidal crystal-polymer nanocomposites.     

Chemical modification of colloidal masks for nanolithography

A method is presented to tune the holes in colloidal masks used for nanolithography. Using a simple wet-chemical method, a thin layer of silica is grown on masks of silica particles. The size of the holes is controlled by the amount of tetraethoxysilane (TEOS) added. More accurate tuning of the hole size is possible in the presence of a calibrated seed dispersion of silica colloids. We demonstrate modified masks that were used to create arrays of metal nanoparticles with a size ranging from 400 nm, for unmodified masks, down to tens of nanometers. The method is easy-to-use, fast, and inexpensive.     

Fabrication of size-tunable gold nanoparticles array with nanosphere lithography, reactive ion etching, and thermal annealing

Two-dimensional ordered arrays of gold (Au) nanoparticles were fabricated using two different variants of the nanosphere lithography technique. First, ordered arrays of polystyrene nanospheres on Si substrate were used as deposition masks through which gold films were deposited by electron beam evaporation. After the removal of the nanospheres, an array of triangular Au nanodisks was left on the Si substrate. After thermal annealing at increasing temperature, systematic shape transition of the nanostructures from original triangular Au nanodisks to rounded nanoparticles was observed. This approach allows us to systematically vary the size and morphology of the particles. In the second and novel technique, we made use of reactive ion etching to simultaneously reduce the dimension of the masking nanospheres and create arrays of nanopores on the substrate prior to the deposition of the Au films. These samples were subsequently annealed, which resulted in size-tunable and ordered Au nanoparticle arrays with the nanoparticles nested in the nanopores of the templated substrate. With the nanoparticles anchored in the nanopores, the substrate could be useful as a template for growth of other nanomaterials.     

Enhanced fluorescence from arrays of nanoholes in a gold film

Arrays of sub-wavelength holes (nanoholes) in gold films were used as a substrate for enhanced fluorescence spectroscopy. Seven arrays of nanoholes with distinct periodicities (distances between the holes) were fabricated. The arrays were then spin-coated with polystyrene films containing different concentrations of the fluorescent dye oxazine 720. The dye was excited via resonant extraordinary transmission of the laser source through the nanoholes. Enhanced fluorescence was observed when the geometric characteristics of the arrays allowed for an enhancement in the transmitted excitation. This enhancement occurred via surface plasmon excitation by the laser and a consequential increase in the local electromagnetic field in a sub-wavelength region at the metal-film interface. It was demonstrated that the sensitivity of the fluorescence measurement (change in signal vs change in dye concentration in the polymer film) is significantly larger at the surface plasmon resonance conditions than that obtained from equivalent films on glass substrates. Enhancement factors for the fluorescence emission were calculated for each array, with a maximum enhancement of close to 2 orders of magnitude as compared to the emission of films on glass. The results presented here indicate that arrays of nanoholes are interesting substrates for the development of fluorescence sensors based on surface plasmon resonance, as they provide a platform that allows both spatial confinement and enhancement of excitation light. Moreover, the collinear characteristics of the present optical setup, due to the resonant extraordinary transmission through the nanohole arrays, are more conducive to miniaturization and chip integration than more traditional experimental geometries.     

Generation of submicrometer structures by photolithography using arrays of spherical microlenses

This paper describes the fabrication of arrays of spherical microlenses by self-assembly of microspheres and the use of these arrays for nearfield photolithography to generate repetitive microstructures in photoresist. We used these arrays of microspheres to fabricate two types of elastomeric membranes: (i) membranes that have microspheres embedded in their surface and (ii) membranes that have hemispherical wells in their surface. Both types of membranes act as amplitude masks that pattern the intensity of illumination in the near field incident on the photoresist. Microspheres in the first type of membrane act as convergent lenses that generate recessed microstructures in positive photoresist. Hemispherical wells in the second type of membrane act as divergent lenses that produce protrusive microstructures in positive photoresist. This method can generate dense, regular arrays of microstructures with a variety of profiles--circular or hexagonal holes, circular posts, hollow posts, and cones--depending on the sizes and refractive indices of the spherical lenses and the distance between the lenses and the photoresist. This technique provides a simple route to large areas (>4 cm2) of repetitive, simple microstructures.     

Nanostructured optical fibre arrays for high-density biochemical sensing and remote imaging

Optical fibre bundles usually comprise a few thousand to tens of thousands of individually clad glass optical fibres. The ordered arrangement of the fibres enables coherent transmission of an image through the bundle and therefore enables analysis and viewing in remote locations. In fused bundles, this architecture has also been used to fabricate arrays of various micro to nano-scale surface structures (micro/nanowells, nanotips, triangles, etc.) over relatively large areas. These surface structures have been used to obtain new optical and analytical capabilities. Indeed, the imaging bundle can be thought of as a “starting material” that can be sculpted by a combination of fibre drawing and selective wet-chemical etching processes. A large variety of bioanalytical applications have thus been developed, ranging from nano-optics to DNA nanoarrays. For instance, nanostructured optical surfaces with intrinsic light-guiding properties have been exploited as surface-enhanced Raman scattering (SERS) platforms and as near-field probe arrays. They have also been productively associated with electrochemistry to fabricate arrays of transparent nanoelectrodes with electrochemiluminescent imaging properties. The confined geometry of the wells has been loaded with biosensing materials and used as femtolitre-sized vessels to detect single molecules. This review describes the fabrication of high-density nanostructured optical fibre arrays and summarizes the large range of optical and bioanalytical applications that have been developed, reflecting the versatility of this ordered light-guiding platform.     

Large-scale plasmonic microarrays for label-free high-throughput screening

Microarrays allowing simultaneous analysis of thousands of parameters can significantly accelerate screening of large libraries of pharmaceutical compounds and biomolecular interactions. For large-scale studies on diverse biomedical samples, reliable, label-free, and high-content microarrays are needed. In this work, using large-area plasmonic nanohole arrays, we demonstrate for the first time a large-scale label-free microarray technology with over one million sensors on a single microscope slide. A dual-color filter imaging method is introduced to dramatically increase the accuracy, reliability, and signal-to-noise ratio of the sensors in a highly multiplexed manner. We used our technology to quantitatively measure protein-protein interactions. Our platform, which is highly compatible with the current microarray scanning systems can enable a powerful screening technology and facilitate diagnosis and treatment of diseases.     

Large oriented arrays and continuous films of TiO(2)-based nanotubes

We report for the first time a one-step, templateless method to directly prepare large arrays of oriented TiO2-based nanotubes and continuous films. These titania nanostructures can also be easily prepared as conformal coatings on a substrate. The nanostructured films were formed on a Ti substrate seeded with TiO2 nanoparticles. SEM and TEM results suggested that a folding mechanism of sheetlike structures was involved in the formation of the nanotubes. The oriented arrays of TiO2 nanotubes, continuous films, and coatings are expected to have potentials for applications in catalysis, filtration, sensing, photovoltaic cells, and high surface area electrodes.