SERS Detection of Biomolecules by Highly Sensitive and Reproducible Raman-Enhancing Nanoparticle Array.

This paper describes the preparation of nanoarrays composed of silver nanoparticles (AgNPs: 20-50 nm) for use as surface-enhanced Raman scattering (SERS) substrates. The AgNPs were grown on porous anodic aluminum oxide (AAO) templates by electrochemical plating, and the inter-channel gap of AAO channels is between 10 and 20 nm. The size and interparticle gap of silver particles were adjusted in order to achieve optimal SERS signals and characterized by scanning electron microscopy, atomic force microscopy, and Raman spectroscopy. The fluctuation of SERS intensity is about 10-20% when measuring adenine solutions, showing a great reproducible SERS sensing. The nanoparticle arrays offer a large potential for practical applications as shown by the SERS-based quantitative detection and differentiation of adenine (A), thymine (T), cytosine (C), guanine (G), ß-carotene, and malachite green. The respective detection limits are <1 ppb for adenine and <0.63 ppm for ß-carotene and malachite green, respectively. Uniform and reproducible Raman enhancement enabled by Ag nanoparticle array embedded in anodic aluminum oxide differentiates and helps quantify DNA canonical nucleobases (adenine, thymine, cytosine, and guanine).

Looking into meta-atoms of plasmonic nanowire metamaterial.

Nanowire-based plasmonic metamaterials exhibit many intriguing properties related to the hyperbolic dispersion, negative refraction, epsilon-near-zero behavior, strong Purcell effect, and nonlinearities. We have experimentally and numerically studied the electromagnetic modes of individual nanowires (meta-atoms) forming the metamaterial. High-resolution, scattering-type near-field optical microscopy has been used to visualize the intensity and phase of the modes. Numerical and analytical modeling of the mode structure is in agreement with the experimental observations and indicates the presence of the nonlocal response associated with cylindrical surface plasmons of nanowires.

Custom-designed arrays of anodic alumina nanochannels with individually tunable pore sizes.

We demonstrate a process to selectively tune the pore size of an individual nanochannel in an array of high-aspect-ratio anodic aluminum oxide (AAO) nanochannels in which the pore sizes were originally uniform. This novel process enables us to fabricate arrays of AAO nanochannels of variable sizes arranged in any custom-designed geometry. The process is based on our ability to selectively close an individual nanochannel in an array by using focused ion beam (FIB) sputtering, which leads to redeposition of the sputtered material and closure of the nanochannel with a capping layer of a thickness depending on the energy of the FIB. When such a partially capped array is etched in acid, the capping layers are dissolved after different time delays due to their different thicknesses, which results in differences in the time required for the following pore-widening etching processes and therefore creates an array of nanochannels with variable pore sizes. The ability to fabricate such AAO templates with high-aspect-ratio nanochannels of tunable sizes arranged in a custom-designed geometry paves the way for the creation of nanophotonic and nanoelectronic devices.

A novel vertical fan-out platform based on an array of curved anodic alumina nanochannels.

Focused ion beam lithography and a two-step anodization have been combined to fabricate a vertical fan-out platform containing an array of unique probes. Each probe comprises three anodic alumina nanochannels with a fan-out arrangement. The lithography is used to pattern an aluminum sheet with a custom-designed array of triangular 'cells' whose apexes are composed of nanoholes. The nanoholes grow into straight nanochannels under proper voltage in the first-step anodization. The second step uses a doubled voltage to induce lateral repulsion among the nanochannels' growth fronts originating in the same cell. Therefore, the fronts fan out. The repulsion roots in the inter-front distance being shorter than the naturally favoured length, which increases with anodization voltage. The fan-out evolution continues until the growth fronts originating in all the cells evolve into a close-packed two-dimensional hexagonal lattice whose spacing is identical to the favoured one. The chemical and physical mechanisms behind the fan-out fabrication are discussed. This novel fan-out platform facilitates probing and handling of many signals from different areas on a sample's surface and is therefore promising for applications in detection and manipulation at the nanoscale level.

Development of Ohmic nanocontacts via surface modification for nanowire-based electronic and optoelectronic devices: ZnO nanowires as an example.

We demonstrated a nanocontacting scheme using a focus ion beam (FIB) system without further heat treatment for ZnO nanowires. This scheme includes Ga ion surface modification and direct-write Pt deposition induced by Ga ion, leading to an Ohmic nanocontact with a specific contact resistance as low as 2.5 × 10(-6)Ω cm(2). Temperature-dependent measurements show that the transport of the FIB-Pt contact on the ZnO nanowire with local surface modification is governed by field emission tunneling. Taking advantage of area-selected and room-temperature processes, Ga ion surface modification and direct-write Pt deposition using a FIB system demonstrates a feasible Ohmic scheme.

Periodic Si nanopillar arrays by anodic aluminum oxide template and catalytic etching for broadband and omnidirectional light harvesting.

Large-area, periodic Si nanopillar arrays (NPAs) with the periodicity of 100 nm and the diameter of 60 nm were fabricated by metal-assisted chemical etching with anodic aluminum oxide as a patterning mask. The 100-nm-periodicity NPAs serve an antireflection function especially at the wavelengths of 200~400 nm, where the reflectance is decreased to be almost tenth of the value of the polished Si (from 62.9% to 7.9%). These NPAs show very low reflectance for broadband wavelengths and omnidirectional light incidence, attributed to the small periodicity and the stepped refractive index of NPA layers. The experimental results are confirmed by theoretical calculations. Raman scattering intensity was also found to be significantly increased with Si NPAs. The introduction of this industrial-scale self-assembly methodology for light

Functionalized arrays of Raman-enhancing nanoparticles for capture and culture-free analysis of bacteria in human blood.

Detecting bacteria in clinical samples without using time-consuming culture processes would allow rapid diagnoses. Such a culture-free detection method requires the capture and analysis of bacteria from a body fluid, which are usually of complicated composition. Here we show that coating Ag-nanoparticle arrays with vancomycin (Van) can provide label-free analysis of bacteria via surface-enhanced Raman spectroscopy (SERS), leading to a ~1,000-fold increase in bacteria capture, without introducing significant spectral interference. Bacteria from human blood can be concentrated onto a microscopic Van-coated area while blood cells are excluded. Furthermore, a Van-coated substrate provides distinctly different SERS spectra of Van-susceptible and Van-resistant Enterococcus, indicating its potential use for drug-resistance tests. Our results represent a critical step towards the creation of SERS-based multifunctional biochips for rapid culture- and label-free detection and drug-resistant testing of microorganisms in clinical samples.

Design, fabrication and characterization of indefinite metamaterials of nanowires.

Indefinite optical properties, which are typically characterized by hyperbolic dispersion relations, have not been observed in naturally occurring materials, but can be realized through a metamaterial approach. We present here the design, fabrication and characterization of nanowire metamaterials with indefinite permittivity, in which all-angle negative refraction of light is observed. The bottom-up fabrication technique, which applies electrochemical plating of nanowires in porous alumina template, is developed and demonstrated in achieving uniform hyperbolic optical properties at a large scale. We developed techniques to improve the uniformity and to reduce the defect density in the sample. The non-magnetic design and the off-resonance operation of the nanowire metamaterials significantly reduce the energy loss of electromagnetic waves and make the broad-band negative refraction of light possible.

Identical-length nanowire arrays in anodic alumina templates.

Arrays of nanowires with identical length are fabricated by using ultrasound to remove the length fluctuation among nanowires, which are deliberately grown in burette-shaped nanochannels on an anodic anumina film. The process allows the fabrication of 10 micron Ag-nanowire arrays with length fluctuation as small as 0.09%. By integrating the process with a focused-ion-beam-based lithographic method to grow nanowires into selective nanochannels in an array, we fabricate arrays of uniform-length nanowires that are arranged in a custom-designed lateral geometry. The ability to fabricate such artificial nanomaterials paves the way for the exploitation of their unusual optical, electrical, and thermal properties.

Probing surface plasmons in individual Ag nanoparticles in the ultra-violet spectral regime.

Previous investigations of surface plasmons in Ag largely focused on their excitations in the visible spectral regime. Using scanning transmission electron microscopy with an electron beam of 0.2 nm in conjunction with electron energy-loss spectroscopy, we spectrally and spatially probe the surface plasmons in individual Ag nanoparticles (approximately 30 nm), grown on Si, in the ultra-violet spectral regime. The nanomaterials show respective sharp and broad surface-plasmon resonances at approximately 3.5 eV (approximately 355 nm) and approximately 7.0 eV (approximately 177 nm), and the correlated spectral calculations established their multipolar characteristics. The near-field distributions of the surface plasmons on the nanoparticles were also mapped out, revealing the predominant dipolar nature of the 3.5 eV excitation with obvious near-field enhancements at one end of the nano-object. The unveiled near-field enhancements have potential applications in plasmonics and molecular sensing.

Imaging visible light using anisotropic metamaterial slab lens.

It has been shown that an anisotropic metamaterial made of nanowire array can realize negative refraction of light even without a negative phase index of refraction. Such non-resonant bulk material can be fabricated by bottom-up electrochemical method. Using this material, we were able to achieve lensing action with micron-thick slab and demonstrate imaging of a slit object. The details of the focused light beam in 3-dimensional space have been mapped with near field scanning optical microscope (NSOM).

Electrochemically replicated smooth aluminum foils for anodic alumina nanochannel arrays.

A fast electrochemical replication technique has been developed to fabricate large-scale ultra-smooth aluminum foils by exploiting readily available large-scale smooth silicon wafers as the masters. Since the adhesion of aluminum on silicon depends on the time of surface pretreatment in water, it is possible to either detach the replicated aluminum from the silicon master without damaging the replicated aluminum and master or integrate the aluminum film to the silicon substrate. Replicated ultra-smooth aluminum foils are used for the growth of both self-organized and lithographically guided long-range ordered arrays of anodic alumina nanochannels without any polishing pretreatment.

High speed fabrication of aluminum nanostructures with 10 nm spatial resolution by electrochemical replication.

A high fidelity electrochemical replication technique for the rapid fabrication of Al nanostructures with 10 nm lateral resolution has been successfully demonstrated. Aluminum is electrodeposited onto a lithographically patterned Si master using a non-aqueous organic hydride bath of aluminum chloride and lithium aluminum hydride at room temperature. Chemical pretreatment of the Si surface allows a clean detachment of the replicated Al foil from the master, permitting its repetitive use for mass replication. This high throughput technique opens up new possibilities in the fabrication of Al-related nanostructures, including the growth of long range ordered anodic alumina nanochannel arrays.