High-fidelity optofluidic on-chip sensors using well-defined gold nanowell crystals

Recent advances in nanofabrication techniques have enabled the creation of various metallic nanostructures in order to engineer the location and properties of electromagnetic hot spots in a controlled manner. However, most previous methods usually require complicated and time-consuming techniques, and the integration of metallic nanostructures into simple, low-cost devices for chemical or biological sensing is still challenging. Here, we report a promising new strategy for the fabrication of large-area gold nanowell arrays with novel geometric features that makes use of the trapping of self-assembled colloidal particles on a polymer surface. Through both systematic experimental and theoretical analysis, we confirm that the strong plasmon resonances of the proposed nanowell structures are associated with localized surface plasmon resonance (LSPR) on the brims of the nanoholes in the top gold films as well as in the bottom gold disks. In addition, we demonstrate a novel optofluidic platform with built-in subwavelength nanowell arrays that exhibits strong plasmon resonances within microfluidic chips. In our optofluidic systems, the plasmon coupling between the brims and the disks of nanowells makes the plasmon resonance more sensitive to surrounding materials. The dependence of the plasmon resonance on the refractive index of the surrounding medium is found to be as high as 570 nm RIU(-1) (refractive index units). These data lead to a figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 4.1.     

Circularly symmetric light scattering from nanoplasmonic spirals

In this paper, we combine experimental dark-field imaging, scattering, and fluorescence spectroscopy with rigorous electrodynamics calculations in order to investigate light scattering from planar arrays of Au nanoparticles arranged in aperiodic spirals with diffuse, circularly symmetric Fourier space. In particular, by studying the three main types of Vogel's spirals fabricated by electron-beam lithography on quartz substrates, we demonstrate polarization-insensitive planar light diffraction in the visible spectral range. Moreover, by combining dark-field imaging with analytical multiparticle calculations in the framework of the generalized Mie theory, we show that plasmonic spirals support distinctive structural resonances with circular symmetry carrying orbital angular momentum. The engineering of light scattering phenomena in deterministic structures with circular Fourier space provides a novel strategy for the realization of optical devices that fully leverage on enhanced, polarization-insensitive light-matter coupling over planar surfaces, such as thin-film plasmonic solar cells, plasmonic polarization devices, and optical biosensors.     

Plasmon hybridization in stacked double crescents arrays fabricated by colloidal lithography

We apply colloidal lithography to construct stacked nanocrescent dimer structures with an exact vertical alignment and a separation distance of approximately 10 nm. Highly ordered, large arrays of these nanostructures are accessible using nonclose-packed colloidal monolayers as masks. Spatially separated nanocrescent dimers are obtained by application of spatially distributed colloids. The polarization dependent optical properties of the nanostructures are investigated in detail and compared to single crescents. The close proximity of the nanocrescents leads to a coupling process that gives rise to new optical resonances which can be described as linear superpositions of the individual crescents' plasmonic modes. We apply a plasmon hybridization model to explain the spectral differences of all polarization dependent resonances and use geometric arguments to explain the respective shifts of the resonances. Theoretical calculations are performed to support the hybridization model and extend it to higher order resonances not resolved experimentally.     

Self-organized silver nanoparticles for three-dimensional plasmonic crystals

Metal nanostructures that support surface plasmons are compelling as plasmonic circuit elements and as the building blocks for metamaterials. We demonstrate here the spontaneous self-assembly of shaped silver nanoparticles into three-dimensional plasmonic crystals that display a frequency-selective response in the visible wavelengths. Extensive long-range order mediated by exceptional colloid monodispersity gives rise to optical passbands that can be tuned by particle volume fraction. These metallic supercrystals present a new paradigm for the fabrication of plasmonic materials, delivering a functional, tunable, completely bottom-up optical element that can be constructed on a massively parallel scale without lithography.     

Parallel Preparation of Densely Packed Arrays of 150‐nm Gold‐Nanocrescent Resonators in Three Dimensions

Metallic nanostructures show interesting optical properties due to their plasmonic resonances, and when arranged in three‐dimensional (3D) arrays hold promise for optical metamaterials with negative refractive index. Towards this goal a simple, cheap, and parallel method to fabricate large‐area, ordered arrays of 150‐nm gold nanocrescents supporting plasmonic resonances in the near‐infrared spectral range is demonstrated. In this process hexagonally ordered monolayers of monodisperse colloids are prepared by a simple floating technique, and subsequently the individual particles are size‐reduced in a plasma process and used as a shadow mask with the initial lattice spacing. The resulting two‐dimensional array of plasmonic resonators is coated with a transparent silica layer, which serves as a support for a second layer prepared by the identical process. The mutual orientation of the nanostructures between the individual layers can be freely adjusted, which determines the polarization‐dependent absorption of the array and opens the possibility to introduce chirality in this type of 3D metamaterial. The iteration of this simple and efficient methodology yields 3D arrays with optical features as sharp as those of the individual nanocrescents, and shows strong potential for large‐scale production of high‐quality optical metamaterials.     

Single-step direct fabrication of pillar-on-pore hybrid nanostructures in anodizing aluminum for superior superhydrophobic efficiency

Conventional electrochemical anodizing processes of metals such as aluminum typically produce planar and homogeneous nanopore structures. If hydrophobically treated, such 2D planar and interconnected pore structures typically result in lower contact angle and larger contact angle hysteresis than 3D disconnected pillar structures and, hence, exhibit inferior superhydrophobic efficiency. In this study, we demonstrate for the first time that the anodizing parameters can be engineered to design novel pillar-on-pore (POP) hybrid nanostructures directly in a simple one-step fabrication process so that superior surface superhydrophobicity can also be realized effectively from the electrochemical anodization process. On the basis of the characteristic of forming a self-ordered porous morphology in a hexagonal array, the modulation of anodizing voltage and duration enabled the formulation of the hybrid-type nanostructures having controlled pillar morphology on top of a porous layer in both mild and hard anodization modes. The hybrid nanostructures of the anodized metal oxide layer initially enhanced the surface hydrophilicity significantly (i.e., superhydrophilic). However, after a hydrophobic monolayer coating, such hybrid nanostructures then showed superior superhydrophobic nonwetting properties not attainable by the plain nanoporous surfaces produced by conventional anodization conditions. The well-regulated anodization process suggests that electrochemical anodizing can expand its usefulness and efficacy to render various metallic substrates with great superhydrophilicity or -hydrophobicity by directly realizing pillar-like structures on top of a self-ordered nanoporous array through a simple one-step fabrication procedure.     

Fabrication of mid-infrared frequency-selective surfaces by soft lithography

We describe the fabrication of large areas (4 cm(2)) of metallic structures or aperture elements that have ~100-350-nm linewidths and act as frequency-selective surfaces. These structures are fabricated with a type of soft lithography-near-field contact-mode photolithography-that uses a thin elastomeric mask having topography on its surface and is in conformal contact with a layer of photoresist. The mask acts as an optical element to create minima in the intensity of light delivered to the photoresist. Depending on the type of photoresist used, lines of, or trenches in, photoresist are formed on the substrate by exposure, development, and lift-off. These surfaces act as bandpass or bandgap filters in the infrared.     

Fabrication and morphological control of ion-induced zinc nanostructures

An efficient method for the fabrication of zinc (Zn) nanostructures (nanoneedles and nanofibers) of controllable density and morphology without any catalyst, hazardous chemicals or external heat supply has been investigated. By varying the ion irradiation time and the ion current density, morphological control and the density of Zn nanostructures were successfully achieved using a fast and viable ion irradiation technique. Scanning (SEM) and transmission electron microscopy (TEM) results revealed that the sputtered surface was almost entirely covered with densely distributed conical and needle-like protrusions with linear shaped (sometimes curved) nanostructures (such as nanoneedles and nanofibers) with diameters and lengths of about 20-50 nm and several hundred nanometers, respectively. Detailed analysis of selected area electron diffraction (SAED) patterns with TEM analysis indicates that the Zn nanofibers were polycrystalline in nature. A possible mechanism of the formation of Zn nanostructures is briefly discussed. These aligned arrays of Zn nanoneedles/nanofibers could be a promising material for the fabrication of zinc oxide nanostructures by subsequent oxidation of Zn nanostructures and their future application in nanodevices. Thus, it is believed that this ion irradiation technique could open up a new approach for the fabrication of many kinds of nanomaterials of controllable density.     

Monolayer Graphene Coupled to a Flexible Plasmonic Nanograting for Ultrasensitive Strain Monitoring

Plasmonically coupled graphene structures have shown great promise for sensing applications. Their complex and cumbersome fabrication, however, has prohibited their widespread application and limited their use to rigid, planar surfaces. Here, a plasmonic sensor based on gold nanowire arrays on an elastomer with an added graphene monolayer is introduced. The stretchable plasmonic nanostructures not only significantly enhance the Raman signal from graphene, but can also be used by themselves as a sensor platform for 2D strain sensing. These nanowire arrays on an elastomer are fabricated by template‐stripping based nanotransfer printing, which enables a simple and fast production of stable nanogratings. The ultrasmooth surfaces of such transferred structures facilitate reliable large‐area transfers of graphene monolayers. The resulting coupled graphene‐nanograting construct exhibits ultrahigh sensitivity to applied strain, which can be detected by shifts in the plasmonic‐enhanced Raman spectrum. Furthermore, this sensor enables the detection of adsorbed molecules on nonplanar surfaces through graphene‐assisted surface enhanced Raman spectroscopy (SERS). The simple fabrication of the plasmonic nanowire array platform and the graphene‐coupled devices have the potential to trigger widespread SERS applications and open up new opportunities for high‐sensitivity strain sensing applications.     

Conductive Polymer-Coated 3D Printed Microneedles: Biocompatible Platforms for Minimally Invasive Biosensing Interfaces

Conductive polymeric microneedle (MN) arrays as biointerface materials show promise for the minimally invasive monitoring of analytes in biodevices and wearables. There is increasing interest in microneedles as electrodes for biosensing, but efforts have been limited to metallic substrates, which lack biological stability and are associated with high manufacturing costs and laborious fabrication methods, which create translational barriers. In this work, additive manufacturing, which provides the user with design flexibility and upscale manufacturing, is employed to fabricate acrylic-based microneedle devices. These microneedle devices are used as platforms to produce intrinsically-conductive, polymer-based surfaces based on polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS). These entirely polymer-based solid microneedle arrays act as dry conductive electrodes while omitting the requirement of a metallic seed layer. Two distinct coating methods of 3D-printed solid microneedles, in situ polymerization and drop casting, enable conductive functionality. The microneedle arrays penetrate ex vivo porcine skin grafts without compromising conductivity or microneedle morphology and demonstrate coating durability over multiple penetration cycles. The non-cytotoxic nature of the conductive microneedles is evaluated using human fibroblast cells. The proposed fabrication strategy offers a compelling approach to manufacturing polymer-based conductive microneedle surfaces that can be further exploited as platforms for biosensing.     

Nanoembossed polymer substrates for biomedical surface interaction studies

Biomedical devices are moving towards the incorporation of nanostructures to investigate the interactions of biological species with such topological surfaces found in nature. Good optical transparency and sealing properties, low fabrication cost, fast design realization times, and biocompatibility make polymers excellent candidates for the production of surfaces containing such nanometric structures. In this work, a method for the production of nanostructures in free-standing sheets of different thermoplastic polymers is presented, with a view to using these substrates in biomedical cell-surface applications where optical microscopy techniques are required. The process conditions for the production of these structures in poly(methyl methacrylate), poly(ethylene naphthalate), poly(lactic acid), poly(styrene), and poly(ethyl ether ketone) are given. The fabrication method used is based on a modified nanoimprint lithography (NIL) technique using silicon based moulds, fabricated via reactive ion etching or focused ion beam lithography, to emboss nanostructures into the surface of the biologically compatible thermoplastic polymers. The method presented here is designed to faithfully replicate the nanostructures in the mould while maximising the mould lifetime. Examples of polymer replicas with nanostructures of different topographies are presented in poly(methyl methacrylate), including nanostructures for use in cell-surface interactions and nanostructure-containing microfluidic devices.     

Shaping Metallic Nanolattices: Design by Microcontact Printing from Wrinkled Stamps

A method for the fabrication of well‐defined metallic nanostructures is presented here in a simple and straightforward fashion. As an alternative to lithographic techniques, this routine employs microcontact printing utilizing wrinkled stamps, which are prepared from polydimethylsiloxane (PDMS), and includes the formation of hydrophobic stripe patterns on a substrate via the transfer of oligomeric PDMS. Subsequent backfilling of the interspaces between these stripes with a hydroxyl‐functional poly(2‐vinyl pyridine) then provides the basic pattern for the deposition of citrate‐stabilized gold nanoparticles promoted by electrostatic interaction. The resulting metallic nanostripes can be further customized by peeling off particles in a second microcontact printing step, which employs poly(ethylene imine) surface‐decorated wrinkled stamps, to form nanolattices. Due to the independent adjustability of the period dimensions of the wrinkled stamps and stamp orientation with respect to the substrate, particle arrays on the (sub)micro‐scale with various kinds of geometries are accessible in a straightforward fashion. This work provides an alternative, cost‐effective, and scalable surface‐patterning technique to fabricate nanolattice structures applicable to multiple types of functional nanoparticles. Being a top‐down method, this process could be readily implemented into, e.g., the fabrication of optical and sensing devices on a large scale.     

Directed three-dimensional patterning of self-assembled peptide fibrils

Molecular self-assembly is emerging as a viable "bottom-up" approach for fabricating nanostructures. Self-assembled biomolecular structures are particularly attractive, due to their versatile chemistry, molecular recognition properties, and biocompatibility. Among them, amyloid protein and peptide fibrils are self-assembled nanostructures with unique physical and chemical stability, formed from quite simple building blocks; their ability to work as a template for the fabrication of low resistance, conducting nanowires has already been demonstrated. The precise positioning of peptide-based nanostructures is an essential part of their use in technological applications, and their controlled assembly, positioning, and integration into microsystems is a problem of considerable current interest. To date, their positioning has been limited to their placement on flat surfaces or to the fabrication of peptide arrays. Here, we propose a new method for the precise, three-dimensional patterning of amyloid fibrils. The technique, which combines femtosecond laser technology and biotin-avidin mediated assembly on a polymeric matrix, can be applied in a wide variety of fields, from molecular electronics to tissue engineering.     

Arrays of silicon micro/nanostructures formed in suspended configurations for deterministic assembly using flat and roller-type stamps

The ability to create and manipulate large arrays of inorganic semiconductor micro/nanostructures for integration on unconventional substrates provides new possibilities in device engineering. Here, simple methods are described for the preparation of structures of single crystalline silicon in suspended and tethered configurations that facilitate their deterministic assembly using transfer-printing techniques. Diverse shapes (e.g., straight or curved edges), thicknesses (between 55 nm and 3 μm), and sizes (areas of 4000 μm(2) to 117 mm(2) ) of structures in varied layouts (regular or irregular arrays, with dense or sparse coverages) can be achieved, using either flat or cylindrical roller-type stamps. To demonstrate the technique, printing with 100% yield onto curved, rigid supports of glass and ceramics and onto thin sheets of plastic is shown. The fabrication of a printed array of silicon p(+) -i-n(+) junction photodiodes on plastic is representative of device-printing capabilities.     

Metal-enhanced fluorescence of colloidal nanocrystals with nanoscale control

Engineering the spectral properties of fluorophores, such as the enhancement of luminescence intensity, can be achieved through coupling with surface plasmons in metallic nanostructures. This process, referred to as metal-enhanced fluorescence, offers promise for a range of applications, including LEDs, sensor technology, microarrays and single-molecule studies. It becomes even more appealing when applied to colloidal semiconductor nanocrystals, which exhibit size-dependent optical properties, have high photochemical stability, and are characterized by broad excitation spectra and narrow emission bands. Other approaches have relied upon the coupling of fluorophores (typically organic dyes) to random distributions of metallic nanoparticles or nanoscale roughness in metallic films. Here, we develop a new strategy based on the highly reproducible fabrication of ordered arrays of gold nanostructures coupled to CdSe/ZnS nanocrystals dispersed in a polymer blend. We demonstrate the possibility of obtaining precise control and a high spatial selectivity of the fluorescence enhancement process.     

Deterministic Assembly of Single Sub-20 nm Functional Nanoparticles Using a Thermally Modified Template with a Scanning Nanoprobe

A deterministic assembly technique for single sub-20 nm functional nanoparticles is developed based on nanostructured templates fabricated by hot scanning nanoprobes. With this technique, single nanoparticles including quantum dots, polystyrene fluorescent nanobeads, and gold nanoparticles are successfully assembled into 2D arrays with high yields. Experimental and theoretical analyses show that the key for the high yields is the hot-probe-based template fabrication technique, which creates geometrical nanotraps and modifies their surface energy simultaneously. In addition to single nanoparticle patterning, further experiments demonstrate that this technique is also capable of building complex nanostructures, such as nanoparticle clusters with well-defined shapes and heterogeneously integrated nanostructures consisting of quantum dots and silver nanowires. It opens the door to many important applications.     

Patterning the tips of optical fibers with metallic nanostructures using nanoskiving

Convenient and inexpensive methods to pattern the facets of optical fibers with metallic nanostructures would enable many applications. This communication reports a method to generate and transfer arrays of metallic nanostructures to the cleaved facets of optical fibers. The process relies on nanoskiving, in which an ultramicrotome, equipped with a diamond knife, sections epoxy nanostructures coated with thin metallic films and embedded in a block of epoxy. Sectioning produces arrays of nanostructures embedded in thin epoxy slabs, which can be transferred manually to the tips of optical fibers at a rate of approximately 2 min(-1), with 88% yield. Etching the epoxy matrices leaves arrays of nanostructures supported directly by the facets of the optical fibers. Examples of structures transferred include gold crescents, rings, high-aspect-ratio concentric cylinders, and gratings of parallel nanowires.     

Hierarchical Electrohydrodynamic Structures for Surface‐Enhanced Raman Scattering

Surface enhanced Raman scattering (SERS) is a well‐established spectroscopic technique that requires nanoscale metal structures to achieve high signal sensitivity. While most SERS substrates are manufactured by conventional lithographic methods, the development of a cost‐effective approach to create nanostructured surfaces is a much sought‐after goal in the SERS community. Here, a method is established to create controlled, self‐organized, hierarchical nanostructures using electrohydrodynamic (HEHD) instabilities. The created structures are readily fine‐tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements. HEHD pattern formation enables the fabrication of multiscale 3D structured arrays as SERS‐active platforms. Importantly, each of the HEHD‐patterned individual structural units yield a considerable SERS enhancement. This enables each single unit to function as an isolated sensor. Each of the formed structures can be effectively tuned and tailored to provide high SERS enhancement, while arising from different HEHD morphologies. The HEHD fabrication of sub‐micrometer architectures is straightforward and robust, providing an elegant route for high‐throughput biological and chemical sensing.     

Flexible high-performance carbon nanotube integrated circuits

Carbon nanotube thin-film transistors are expected to enable the fabrication of high-performance, flexible and transparent devices using relatively simple techniques. However, as-grown nanotube networks usually contain both metallic and semiconducting nanotubes, which leads to a trade-off between charge-carrier mobility (which increases with greater metallic tube content) and on/off ratio (which decreases). Many approaches to separating metallic nanotubes from semiconducting nanotubes have been investigated, but most lead to contamination and shortening of the nanotubes, thus reducing performance. Here, we report the fabrication of high-performance thin-film transistors and integrated circuits on flexible and transparent substrates using floating-catalyst chemical vapour deposition followed by a simple gas-phase filtration and transfer process. The resulting nanotube network has a well-controlled density and a unique morphology, consisting of long (~10 μm) nanotubes connected by low-resistance Y-shaped junctions. The transistors simultaneously demonstrate a mobility of 35 cm(2) V(-1) s(-1) and an on/off ratio of 6 × 10(6). We also demonstrate flexible integrated circuits, including a 21-stage ring oscillator and master-slave delay flip-flops that are capable of sequential logic. Our fabrication procedure should prove to be scalable, for example, by using high-throughput printing techniques.     

ZnO microstructures and nanostructures prepared by sol-gel hydrothermal technique

Zinc oxide (ZnO) is an emerging material in large area electronic applications such as thin-film solar cells and transistors. We report on the fabrication and characterization of ZnO microstructures and nanostructures. The ZnO microstructures and nanostructures have been synthesized using sol-gel immerse technique on oxidized silicon substrates. Different precursor's concentrations ranging from 0.0001 M to 0.01 M (M=molarity) using zinc nitrate hexahydrate [Zn(NO3)2. 6H2O] and hexamethylenetetramine [C6H12N4] were employed in the synthesis of the ZnO structures. The surface morphologies were examined using scanning electron microscope (SEM) and atomic force microscope (AFM). In order to investigate the structural properties, the ZnO microstructures and nanostructures were measured using X-ray diffractometer (XRD). The optical properties of the ZnO structures were measured using photoluminescence (PL) and ultraviolet-visible (UV-Vis) spectroscopies.