Controlled DNA-templated metal deposition: towards ultra-thin nanowires

In this paper, we report the metallization of a dsDNA template using a novel photography-derived two-step strategy in which dsDNA is first complexed with Ag(I) ions and then irradiated with UV light at 254 nm. The nucleobases act as light harvesters and sensitizers, triggering the photoreduction of the complexed silver ions. This process yields a silver nanoparticles blueprint along the DNA strand. The silver latent image is then developed by depositing metallic nickel through an electroless plating process. This photography-derived procedure generates very homogeneous and evenly distributed strings of silver-core/nickel-shell nanoparticles. Although still discontinuous, we believe that such chains can serve as the base for obtaining continuous metal nanowires. Furthermore, this process can most likely be extended to other plating metals, resulting in a broadly general procedure for metallizing DNA with a variety of different materials. Because of the intrinsic simplicity in using light as the key step, this methodology might be amenable to large-scale development, eventually leading to a very efficient molecular-photolithography process.     

Smooth and conductive DNA-templated Cu₂O nanowires: growth morphology, spectroscopic and electrical characterization

DNA strands have been used as templates for the self-assembly of smooth and conductive cuprous oxide (Cu?O) nanowires of diameter 12-23 nm and whose length is determined by the template (16 μm for λ-DNA). A combination of spectroscopic, diffraction and probe microscopy techniques showed that these nanowires comprise single crystallites of Cu?O bound to the DNA molecules which fused together over time in a process analogous to Ostwald ripening, but driven by the free energy of interaction with the template as well as the surface tension. Electrical characterization of the nanowires by a non-contact method, scanned conductance microscopy and by contact mode conductive AFM showed the wires are electrically conductive. The conductivity estimated from the AFM cross section and the zero-bias conductance in conductive AFM experiments was 2.2-3.3 S cm?1. These Cu?O nanowires are amongst the thinnest reported and show evidence of strong quantum confinement in electronic spectra.     

DNA-templated copper nanowire fabrication by a two-step process involving electroless metallization

Here, we report a new fabrication method of DNA-templated copper nanowires. The copper nanowires were fabricated via two-step reactions. First, Pd(II) ions were electrostatically adsorbed onto negatively charged DNA molecules immobilized on the substrate surfaces and reduced chemically. As a result, palladium nanowires with a diameter of approximately 6 nm were obtained. Second, the palladium nanowires were dipped into a copper electroless plating bath. Electroless deposition of copper proceeded specifically on the palladium nanowires. The diameters of the copper nanowires were controlled by the plating time.     

Highly porous CdO nanowires: preparation based on hydroxy- and carbonate-containing cadmium compound precursor nanowires, gas sensing and optical properties

Highly porous cadmium oxide (CdO) nanowires have been prepared by calcining the hydroxy-?and carbonate-containing cadmium compound precursor nanowires. The large-scale precursor nanowires were synthesized through a hydrothermal method. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize and analyze the as-synthesized precursor nanowires as well as the calcined products. It was revealed that the wire-like morphology of the precursor was fundamentally retained during the process of calcination and the CdO nanowires obtained were polycrystalline with highly porous structures. In order to illustrate the formation mechanism of the porous structures, the morphology and composition evolutions of the precursor nanowires under different stages of the calcining process were further investigated via SEM, x-ray diffraction (XRD) and infrared (IR) absorbance spectroscopy. Gas sensing has been explored for the sensor device fabricated with highly porous CdO nanowires, which demonstrates that it has good response owing to its special structures and great selectivity to NO(x). Furthermore, the UV-visible and photoluminescence spectra of highly porous CdO nanowires have also been investigated.     

Vertically aligned nanowires from boron-doped diamond

Vertically aligned diamond nanowires with controlled geometrical properties like length and distance between wires were fabricated by use of nanodiamond particles as a hard mask and by use of reactive ion etching. The surface structure, electronic properties, and electrochemical functionalization of diamond nanowires were characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) as well as electrochemical techniques. AFM and STM experiments show that diamond nanowire etched for 10 s have wire-typed structures with 3-10 nm in length and with typically 11 nm spacing in between. The electrode active area of diamond nanowires is enhanced by a factor of 2. The functionalization of nanowire tips with nitrophenyl molecules is characterized by STM on clean and on nitrophenyl molecule-modified diamond nanowires. Tip-modified diamond nanowires are promising with respect to biosensor applications where controlled biomolecule bonding is required to improve chemical stability and sensing significantly.     

Protein recognition via surface molecularly imprinted polymer nanowires

In this paper, we present a technique for the preparation of polymer nanowires with the protein molecule imprinted and binding sites at surface. These surface imprinting nanowires exhibit highly selective recognition for a variety of template proteins, including albumin, hemoglobin, and cytochrome c. This recognition may be through a multistep adsorption, with the specificity conferred by hydrogen bonding and shape selectivity. Due to the protein imprinted sites are located at, or close to, the surface; these imprinted nanowires have a good site accessibility toward the target protein molecules. Furthermore, the large surface area of the nanowires results in large protein molecule binding capacity of the imprinted nanowires.     

DNA-directed synthesis of zinc oxide nanowires on carbon nanotube tips

This paper describes a class of three component hybrid nanowires templated by DNA directed self-assembly. Through the modification of carbon nanotube (CNT) termini with synthetic DNA oligonucleotides, gold nanoparticles are delivered, via DNA hybridization, to CNT tips that then serve as growth sites for zinc oxide (ZnO) nanowires. The structures we have generated using DNA templating represent an advance toward building higher order sequenced one dimensional nanostructures with rational control.     

Mechanical properties of microwave hydrothermally synthesized titanate nanowires

In this investigation titanate nanowires were synthesized by a microwave hydrothermal process and their nanomechanical characterization was carried out by a compression experiment via buckling instability using a nanomanipulator inside a scanning electron microscope. Nanowires of diameters 120-150?nm and length tens of microns can be synthesized by keeping a commercial nanoparticle inside a microwave oven at 350?W and 210?°C for 5?h. The nanowire was clamped between two cantilevered AFM tips attached to two opposing stages of the manipulator for nanomechanical characterization. The elasticity coefficients of the titanate nanowires were measured by applying a continuously increasing load and observing the buckling instability of the nanowires. The buckling behavior of a nanowire was analyzed from the series of SEM images of displacement of the cantilever attached to the nanowire due to application of load. The critical loads for different sized titanate nanowires were determined and their corresponding Young's modulus was computed with the Euler pinned-fixed end model. The Young's modulus of these microwave hydrothermal process synthesized titanate nanowires were determined to be approximately in the range 14-17?GPa. This investigation confirms the capability of the nanomanipulator via the buckling technique as a constructive device for measuring the mechanical properties of nanoscale materials.     

Toward wafer-scale patterning of freestanding intermetallic nanowires

Individual metal alloy nanowires of constant diameter and high aspect ratio have previously been self-assembled at selected locations on atomic force microscope (AFM) probes by the method reported in Yazdanpanah et al (2005 J. Appl. Phys. 98 073510). This process relies on the room temperature crystallization of an ordered phase of silver-gallium. A parallel version of this method has been implemented in which a substrate, either an array of micromachined tips (similar to tips on AFM probes) or a lithographically patterned planar substrate, is brought into contact with a continuous, nearly planar film of melted gallium. In several runs, freestanding wires are fabricated with diameters of 40-400 nm, lengths of 4-80 μm, growth rates of 80-170 nm s( - 1) and, most significantly, with yields of up to 97% in an array of 422 growth sites. These results demonstrate the feasibility of developing a batch manufacturing process for the decoration of wafers of AFM tips and other structures with selectively patterned freestanding nanowires.     

Gold/silicon nanocomposites: synthesis,characterization, and application in detection of dopamine

Silicon nanowires (SiNWs) with the length of several hundreds of micrometers and an average diameter of 15 nm were successfully synthesized via a thermal-evaporation oxide-assisted process. Then, a convenient method was applied to metallize the SiNWs just by dipping them into an aqueous deposition solution. During the metallization process, which is a redox reaction, gold nanoparticles (NPs) were prepared on SiNWs surface to confine the particle size and prevent agglomeration during the preparation and utilization of gold NPs. The synthesized SiNWs decorated with gold NPs were utilized to modify the glassy carbon electrode. Electrochemical measurements displayed that the modified electrode showed high sensitivity for dopamine (DA) detection.     

The SERS and TERS effects obtained by gold droplets on top of Si nanowires

We show that hemispherical gold droplets on top of silicon nanowires when grown by the vapor-liquid-solid (VLS) mechanism, can produce a significant enhancement of Raman scattered signals. Signal enhancement for a few or even just single gold droplets is demonstrated by analyzing the enhanced Raman signature of malachite green molecules. For this experiment, trenches (approximately 800 nm wide) were etched in a silicon-on-insulator (SOI) wafer along <110> crystallographic directions that constitute sidewalls ({110} surfaces) suitable for the growth of silicon nanowires in <111> directions with the intention that the gold droplets on the silicon nanowires can meet somewhere in the trench when growth time is carefully selected. Another way to realize gold nanostructures in close vicinity is to attach a silicon nanowire with a gold droplet onto an atomic force microscopy (AFM) tip and to bring this tip toward another gold-coated AFM tip where malachite green molecules were deposited prior to the measurements. In both experiments, signal enhancement of characteristic Raman bands of malachite green molecules was observed. This indicates that silicon nanowires with gold droplets atop can act as efficient probes for tip-enhanced Raman spectroscopy (TERS). In our article, we show that a nanowire TERS probe can be fabricated by welding nanowires with gold droplets to AFM tips in a scanning electron microscope (SEM). TERS tips made from nanowires could improve the spatial resolution of Raman spectroscopy so that measurements on the nanometer scale are possible.     

Diamond-modified AFM probes: from diamond nanowires to atomic force microscopy-integrated boron-doped diamond electrodes

In atomic force microscopy (AFM), sharp and wear-resistant tips are a critical issue. Regarding scanning electrochemical microscopy (SECM), electrodes are required to be mechanically and chemically stable. Diamond is the perfect candidate for both AFM probes as well as for electrode materials if doped, due to diamond's unrivaled mechanical, chemical, and electrochemical properties. In this study, standard AFM tips were overgrown with typically 300 nm thick nanocrystalline diamond (NCD) layers and modified to obtain ultra sharp diamond nanowire-based AFM probes and probes that were used for combined AFM-SECM measurements based on integrated boron-doped conductive diamond electrodes. Analysis of the resonance properties of the diamond overgrown AFM cantilevers showed increasing resonance frequencies with increasing diamond coating thicknesses (i.e., from 160 to 260 kHz). The measured data were compared to performed simulations and show excellent correlation. A strong enhancement of the quality factor upon overgrowth was also observed (120 to 710). AFM tips with integrated diamond nanowires are shown to have apex radii as small as 5 nm and where fabricated by selectively etching diamond in a plasma etching process using self-organized metal nanomasks. These scanning tips showed superior imaging performance as compared to standard Si-tips or commercially available diamond-coated tips. The high imaging resolution and low tip wear are demonstrated using tapping and contact mode AFM measurements by imaging ultra hard substrates and DNA. Furthermore, AFM probes were coated with conductive boron-doped and insulating diamond layers to achieve bifunctional AFM-SECM probes. For this, focused ion beam (FIB) technology was used to expose the boron-doped diamond as a recessed electrode near the apex of the scanning tip. Such a modified probe was used to perform proof-of-concept AFM-SECM measurements. The results show that high-quality diamond probes can be fabricated, which are suitable for probing, manipulating, sculpting, and sensing at single digit nanoscale.     

Improved microstructure and magnetic properties of iron-cobalt nanowire via an ac electrodeposition with a multistep voltage

Highly ordered porous alumina templates prepared by a two-step anodization are widely utilized as the matrix to assemble nanowires. Usually, an ac electrodeposition with a constant voltage is employed to deposit the metal nanowires on the porous alumina template due to its simple electrodeposition process. However, the nanowires deposited under a constant voltage include many defects in the microstructure, e.g. the hole to weaken its physical properties. Recently, we used an ac electrodeposition with a multistep voltage to deposit a cobalt nanowire with less microstructure defects to enhance its magnetic properties. In this letter, we further investigate the microstructure and magnetic properties of the iron-cobalt nanowire via an ac electrodeposition with a multistep voltage on the porous alumina template. Such a FeCo nanowire has the more uniform crystalline microstructure than that of deposited under a constant voltage and thus the magnetic properties are improved. Our results indicate that an ac electrodeposition with a multistep voltage is an effective way to fabricate the nanowires on the porous alumina template.     

Ferromagnetism driven by oxygen vacancies in SnO2 nanowires

Room temperature ferromagnetism has been observed in SnO2 nanowires synthesized by a chemical vapor deposition using Au layers as catalyst. The nanowires are homogeneous and single-crystalline grown along the [101] direction, with diameters ranging from 25 to 100 nm and length greater than 20 microm. The special magnetization reaches 0.114 emu/g for the nanowires with diameter of approximately 25 nm and reduces with increasing diameters. Branched SnO2 nanowires were prepared via a two-step vapor-liquid-solid approach, and an enhanced magnetization was obtained. To the contrary, the nanowires annealed at 1300 degrees C in air were completely transformed into the particles and exhibit weakened magnetization. These results demonstrate that the ferromagnetic properties of the samples depend on the surface-to-volume ratio of nanowires. With a combined study of photoluminescence, our results reveal that the oxygen vacancies at the surface of nanowires contribute to the ferromagnetism of SnO2 nanowires. This argument is further confirmed by a sequential annealing in a rich-oxygen atmosphere, then in a low vacuum condition.     

Wafer-scale fabrication of nanofluidic arrays and networks using nanoimprint lithography and lithographically patterned nanowire electrodeposition gold nanowire masters

Wafer scale (cm(2)) arrays and networks of nanochannels were created in polydimethylsiloxane (PDMS) from a surface pattern of electrodeposited gold nanowires in a master-replica process and characterized with scanning electron microscopy (SEM), atomic force microscopy (AFM), and fluorescence imaging measurements. Patterns of gold nanowires with cross-sectional dimensions as small as 50 nm in height and 100 nm in width were prepared on silica substrates using the process of lithographically patterned nanowire electrodeposition (LPNE). These nanowire patterns were then employed as masters for the fabrication of inverse replica nanochannels in a special formulation of PDMS. SEM and AFM measurements verified a linear correlation between the widths and heights of the nanowires and nanochannels over a range of 50 to 500 nm. The PDMS replica was then oxygen plasma-bonded to a glass substrate in order to create a linear array of nanofluidic channels (up to 1 mm in length) filled with solutions of either fluorescent dye or 20 nm diameter fluorescent polymer nanoparticles. Nanochannel continuity and a 99% fill success rate was determined from the fluorescence imaging measurements, and the electrophoretic injection of both dye and nanoparticles in the nanochannel arrays was also demonstrated. Employing a double LPNE fabrication method, this master-replica process was also used to create a large two-dimensional network of crossed nanofluidic channels.     

Synthesis,characterization and growth mechanism of ZnO nanowires on NiCl<Subscript>2</Subscript>-coated Si substrates

Well-crystallized ZnO nanowires have been successfully synthesized on NiCl₂-coated Si substrates via a carbon thermal reduction deposition process. The pre-deposited Ni nanoparticles by dipping the substrates into NiCl₂ solution can promote the formation of ZnO nuclei. The as-synthesized nanowires were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectrum. The results demonstrate that the as-fabricated nanowires with about 60 nm in diameter and several tens of micrometers in length are preferentially arranged along [0001] direction with (0002) as the dominate surface. Room temperature PL spectrum illustrates that the ZnO nanowires exist a UV emission peak and a green emission peak, and the peak centers locate at 387 and 510 nm. Finally, the growth mechanism of the nanowires is briefly discussed.     

Synthesis of CdS nanoparticles based on DNA network templates

CdS nanoparticles have been successfully synthesized by using DNA networks as templates. The synthesis was carried out by first dropping a mixture of cadmium acetate and DNA on a mica surface for the formation of the DNA network template and then transferring the sample into a heated thiourea solution. The Cd(2+) reacted with thiourea at high temperature and formed CdS nanoparticles on the DNA network template. UV-vis spectroscopy, photoluminescence, x-ray diffraction and atomic force microscopy (AFM) were used to characterize the CdS nanoparticles in detail. AFM results showed that the resulted CdS nanoparticles were directly aligned on the DNA network templates and that the synthesis and assembly of CdS nanoparticles was realized in one step. CdS nanoparticles fabricated with this method were smaller than those directly synthesized in a thiourea solution and were uniformly aligned on the DNA networks. By adjusting the density of the DNA networks and the concentration of Cd(2+), the size and density of the CdS nanoparticles could be effectively controlled and CdS nanoparticles could grow along the DNA chains into nanowires. The possible growth mechanism has also been discussed in detail.     

Metallic Conductive Nanowires Elaborated by PVD Metal Deposition on Suspended DNA Bundles

Metallic conductive nanowires (NWs) with DNA bundle core are achieved, thanks to an original process relying on double‐stranded DNA alignment and physical vapor deposition (PVD) metallization steps involving a silicon substrate. First, bundles of DNA are suspended with a repeatable process between 2 µm high parallel electrodes with separating gaps ranging from 800 nm to 2 µm. The process consists in the drop deposition of a DNA lambda‐phage solution on the electrodes followed by a naturally evaporation step. The deposition process is controlled by the DNA concentration within the buffer solution, the drop volume, and the electrode hydrophobicity. The suspended bundles are finally metallized with various thicknesses of titanium and gold by a PVD e‐beam evaporation process. The achieved NWs have a width ranging from a few nanometers up to 100 nm. The electrical behavior of the achieved 60 and 80 nm width metallic NWs is shown to be Ohmic and their intrinsic resistance is estimated according to different geometrical models of the NW section area. For the 80 nm width NWs, a resistance of about few ohms is established, opening exploration fields for applications in microelectronics.     

DNA hybridization on silicon nanowires

Nanowire-based detection strategies provide promising new routes to bioanalysis and indeed are attractive to conventional systems because of their small size, high surface-to-volume ratios, electronic, and optical properties. A sequence-specific detection of single-stranded oligonucleotides using silicon nanowires (SiNWs) is demonstrated. The surface of the SiNWs is functionalized with densely packed organic monolayer via hydrosilylation for covalent attachment. Subsequently, deoxyribonucleic acid (DNA) is immobilized to recognize the complementary target DNA. The biomolecular recognition properties of the nanowires are tested via hybridization with ^γP³² tagged complementary and non-complementary DNA oligonucleotides, showing good selectivity and reversibility. No significant non-specific binding to the incorrect sequences is observed. X-ray photoelectron spectroscopy, fluorescence imaging, and nanodrop techniques are used to characterize the modified SiNWs and covalent attachment with DNA. The results show that SiNWs are excellent substrates for the absorption, stabilization and detection of DNA sequences and could be used for DNA microarrays and micro fabricated SiNWs DNA sensors.     

Highly ordered uniform single-crystal Bi nanowires: fabrication and characterization

A mechanical pressure injection technique has been used to fabricate uniform bismuth (Bi) nanowires in the pores of an anodic aluminum oxide (AAO) template. The AAO template was prepared from general purity aluminum by a two-step anodization followed by heat treatment to achieve highly ordered nanochannels. The nanowires were then fabricated by an injection technique whereby the molten Bi was injected into the AAO template using a hydraulic pressure method. The Bi nanowires prepared by this method were found to be dense and continuous with uniform diameter throughout the length. Electron diffraction experiments using the transmission electron microscope on cross-sectional and free-standing longitudinal Bi nanowires showed that the majority of the individual nanowires were single crystalline, with preferred orientation of growth along the [011] zone axis of the pseudo-cubic structure. The work presented here provides an inexpensive and effective way of fabricating highly ordered single-crystalline Bi nanowires, with uniform size distributions.