Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C--O--C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C--O--C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.     

The effects of strain on STM lithography on HS-ssDNA/Au (1 1 1) surface

Scanning tunneling microscopy (STM) lithography was utilized to investigate a 12-mer HS-ssDNA self-assembled Au (1 1 1) surface. Under low sample bias and high tunneling current, the repeated scanning resulted in the growth of nanostripes. The stripe orientation, the stripe width, and the spacer width between adjacent nanostripes were found to be dependent on their relative locations from dislocation points where two adjacent gold terraces overlap. The stripe and the spacer width also vary with the distance from these points. The results indicate that such stripes may reflect the strain distributions and the release pathway along the Au surfaces. The results also suggest that the presence of HS-ssDNA molecules enhances the lithography processes on the gold surface by acting as force transmitters.     

Fabrication of nanostructures on Si(1 0 0) and GaAs(1 0 0) by local anodic oxidation

Atomic force microscopes have become useful tools not only for observing surface morphology and nanostructure topography but also for fabrication of various nanostructures itself. In this paper, the application of AFM for fabrication of nanostructures by local anodic oxidation (LAO) of Si(1 0 0) and GaAs(1 0 0) surfaces is presented. A special attention is paid to finding relations between the size of oxide nanolines (height and half-width) and operational parameters as tip-sample voltage and tip writing speed. It was demonstrated that the formation of silicon oxide lines obeys the Cabrera-Mott theory, i.e. the height of the lines grow, linearly with tip-sample voltage and is inversely proportional to logarithm of tip writing speed. As for GaAs substrates, the oxide line height grows linearly with tip-sample voltage as well but LAO exhibits a certain deviation from this theory. It is shown that the selective chemical etching of Si or GaAs ultrathin films processed by LAO makes it possible to use these films as nanolithographic masks for further nanotechnologies, e.g. fabrication of metallic nanostructures by ion-beam bombardment. The ability to control LAO and tip motion can be utilized in fabrication of complex nanostructures finding their applications in nanoelectronic devices, nanophotonics and other high-tech areas.     

Effects of organic modifiers on the size-controlled synthesis of hydroxyapatite nanorods

Size-controlled synthesis of hydroxyapatite nanorods were carried out by chemical precipitation method using polyethylene glycol (MW 600), Tween 20, trisodium citrate, and d-sorbitol as organic modifiers and starting from calcium nitrate, phosphoric acid, and ammonia solution. The influence of the organic modifiers on the sizes of the resultant HAP nanorods was investigated under different synthesis temperatures. It was found that polyethylene glycol was beneficial to the formation of HAP nanorods with a larger aspect ratio (average length/average diameter) at high synthesis temperature, Tween 20 and trisodium citrate favored the formation of small-sized HAP nanorods, and d-sorbitol helped the formation of HAP nanorods with long length at low synthesis temperatures.     

Preparation of surfactant-stabilized gold nanoparticle–peptide nucleic acid conjugates

A simple, two-step method of producing stable and functional peptide nucleic acid (PNA)-conjugated gold nanoparticles using a surfactant stabilization step is presented. PNA are DNA analogs with superior chemical stability and target discrimination, but their use in metallic nanoparticle systems has been limited by the difficulty of producing stable colloids of nanoparticle–PNA conjugates. In this work, the nonionic surfactant Tween 20 (polyoxyethylene (20) sorbitan monolaurate) was used to sterically shield gold surfaces prior to the addition of thiolated PNA, producing conjugates which remain dispersed in solution and retain the ability to hybridize to complementary nucleic acid sequences. The conjugates were characterized using transmission electron microscopy, dynamic light scattering, and UV–visible absorbance spectroscopy. PNA attachment to gold nanoparticles was confirmed with an enzyme-linked immunoassay, while the ability of nanoparticle-bound PNA to hybridize to its complement was demonstrated using labeled DNA.     

Electronic and structural studies of immobilized thiol-derivatized cobalt porphyrins on gold surfaces

The immobilisation of thiol-derivatized cobalt porphyrins on gold surfaces has been studied in detail by means of combined scanning tunnelling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). S-thioacetyl has been used as a protective group for the thiol. Different routes for deprotection of the acetyl groups were performed in acidic and in basic conditions. The results show the formation of monolayer films for the different preparation schemes. The immobilisation of the molecules on the gold surface takes place through the thiol-linkers by the formation of multiple thiolate bonds. In the case of layers formed with protected porphyrins approximately 60% of the linkers are bonded to the gold surface whereas for deprotected layers the amount of bonded linkers is increased up to about 80%. STM measurements revealed that the molecules arrange in a disordered overlayer and do not exhibit mobility on the gold surface. Annealing experiments have been performed in order to test the stability of the porphyrin layers. Disordered patterns have been observed in the STM images after annealing at T = 400 °C. XPS revealed that the sulphur content disappeared completely after annealing at T = 180 °C and that the molecules did undergo significant modifications.     

Atomic force microscopy studies of chemical–mechanical processes on silicon(100) surfaces

Atomic force microscopy (AFM) is used to examine chemical–mechanical processes on Si(100) surfaces. The AFM tip serves as a single asperity contact to exert tribological forces as well as an imaging tool. By scanning in chemically aggressive solutions, material removal can be observed directly. In the silicon system, high-force scans are used to remove oxide and initiate etching in selected locations, followed by low-force scans to image the resulting surfaces. Material removal rates were measured as a function of applied load, number of scans, solution composition, and time. In basic solution, places where the underlying silicon is exposed etch rapidly, producing structures 100 nm or less in size. Although the surface roughness initially increases during etching, the final surfaces are smooth. The oxide is extremely sensitive to applied stress: even very light scanning accelerates oxide dissolution. Once the oxide is removed, chemical etching proceeds through the underlying silicon with or without AFM scanning; but the silicon etches more rapidly if AFM scanning is continued, due to true chemical–mechanical (tribochemical) effects.     

Probing the diffusion of vacuum ultraviolet (λ = 172 nm) induced oxidants by nanoparticles immobilization

Vacuum ultraviolet (VUV, λ = 172 nm) patterning of alkyl monolayer on silicon surface has been demonstrated with emphasis on the diffusion of VUV induced oxygen-derived active species, which are accountable for the pattern broadening. The VUV photons photo-dissociates the atmospheric oxygen and water molecules into the oxygen-derived active species (oxidants). These oxidants photo-oxidize the hexadecyl (HD) monolayer in VUV irradiated regions (Khatri et al., Langmuir. 24 (2008) 12077), as well as the little concentration of oxidants diffuses towards the masked areas. In this study, we performed VUV patterning at a vacuum pressure of 10 Pa to track the diffusion pathways for the oxidants with help of gold nanoparticles (AuNPs; ? = 10 nm) immobilization. At VUV irradiated sites AuNPs are found as uniformly distributed, but adjacent to the pattern boundary we observed quasi-linear arrays of AuNPs, which are determined by diffusion pathways of the oxidants. The diffusion of oxidants plays vital role in pattern broadening. The site selective anchoring of AuNPs demonstrates the utility of VUV photons for the construction of functional materials with microstructural architecture.     

Adsorption and deposition of anthraquinone-2-carboxylic acid on alumina studied by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy

The adsorption state of anthraquinone-2-carboxylic acid (AQ-2-COOH) deposited from acetone solutions (0.01-1.00 mg/ml) on native oxide surfaces of Al films was characterized by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy. The oxide was prepared on evaporated Al films at room temperature in an oxygen-dc glow discharge. The morphology of the deposited AQ-2-COOH on the oxide surfaces was observed and analyzed by atomic force microscopy. These surface analyses showed that AQ-2-COOH is adsorbed predominantly as a uniform nanometer-scale film of carboxylate anions on the oxide surfaces deposited from solutions with concentrations lower than or equal to 0.02 mg/ml. It was found that AQ-2-COOH is adsorbed as both a uniform film of anions and as micron-sized particles of neutral molecules with heights of a few tens of nanometers when AQ-2-COOH is deposited from solutions with concentrations higher than 0.02 mg/ml. A comparison of the results obtained by these surface analytical techniques clearly shows the features and advantages of these analytical techniques.     

Nanowire manipulation on surfaces through electrostatic self‐assembly and magnetic interactions

A method for fabricating aligned nanowire arrays on surfaces is shown. Gold and segmented Au/Ni/Au nanowires of high aspect ratio have been prepared by template electrosynthesis, and functionalized with charged short alkanethiols that can be ionized in aqueous solutions. Different distributions of funtionalized nanowires could be obtained on large surfaces from nanowire aqueous suspensions, avoiding aggregation due to electrical repulsion. Due to the high magnetic anisotropy of segmented Au/Ni/Au nanowires chaining of aligned nanowires could be obtained by applying a low magnetic field. While electrostatics favours side wire interactions due to the high aspect ratio, concurrent electrostatics and applied magnetic field yields end‐to‐end interaction and linear alignment without bifunctionalization. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Replication of mold for UV-nanoimprint lithography using AAO membrane

A simple and highly effective method to the replication of soft mold based on the anodic aluminum oxide (AAO) membrane was developed. The soft mold with nanopillar arrays was composed of the toluene diluted PDMS layer supported by the soft PDMS. A water contact angle as high as 114° was achieved. The hexagonally well-order arrays of holes of nanometer dimensions, ∼100 nm pore diameter and 125 nm center-to-center pore, could be gained over large areas by UV-nanoimprint lithography (UV-NIL) with the replicated soft PDMS mold. It is expected that the developed soft mold would find applications in light emitting diodes devices.     

Growth of boron nano-junctions

In this work, we demonstrate the synthesis of various types of boron nanowire junctions in a self-assembled manner by simple closed-tube thermal vapor transfer method. The Y-type boron nano-junctions and lateral boron-silicon alloy nano-junctions were grown on Si substrates, based on the oxide assisted VLS growth mode at a relatively low processing temperature regime and the VLS growth mode at the high processing temperature regime, respectively.     

In‐situ dispersion of ZrO2 nano‐particles coated with pentacene

Stable suspensions of pentacene functionalised ZrO₂ nano‐particles were synthesised using a microwave plasma process. The particles were dispersed in‐situ in ethylene glycol. The formation of coated particles with small cores and a well defined size in the range of 3–5 nm was shown by X‐ray diffraction. In difference to resublimed pure pentacene, suspensions of the coated nano‐particles remained stable for weeks, as confirmed by the observation of a small aggregate size in dynamic light scattering. Thin films of the particles on Si based substrates were obtained by drop‐casting. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ordered self-assembled monolayers of Peptide nucleic acids with DNA recognition capability

We report on the formation of ordered self-assembled monolayers (SAMs) of single-stranded peptide nucleic acids (ssPNA). In spite of their remarkable length (7 nm) thiolated PNAs assemble standing up on gold surfaces similarly to the SAMs of short alkanethiols. SAMs of ssPNA recognize complementary nucleic acids, acting as specific biosensors that discriminate even a point mutation in target ssDNA. These results are obtained by surface characterization techniques that avoid labeling of the target molecule: x-ray photoemission, x-ray absorption and atomic force microscopy.     

Nanostructures fabricated on metal surfaces assisted by laser with optical near-field effects

Nanostructures on metal film surfaces have been written directly using a pulsed ultraviolet laser. The optical near-field effects of the laser were investigated. Spherical silica particles (500–1000 nm in diameter) were placed on metal films. After laser illumination with a single laser shot, nanoholes were obtained at the original position of the particles. The mechanism for the formation of the nanostructure patterns was investigated and found to be the near-field optical resonance effect induced by the particles on the surface. The size of the nanohole was studied as a function of laser fluence and silica particle size. The experimental results show a good agreement with those of the relevant theoretical calculations of the near-field light intensity distribution. The method of particle-enhanced laser irradiation allows the study of field enhancement effects as well as its potentialapplications for nanolithography. Received: 10 December 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +65-777/1349, E-mail: HUANG_Sumei@dsi.a-star.edu.sg     

Control of nanogap junction resistance by imposed pulse voltage

The resistance switching effect of a simple gold nanogap junction was investigated. This device exhibits highly reproducible switching and nonvolatile characteristics. The resistance switching was developed for dependence of the resistance on the applied voltage level. Four separate ranges of resistance were repeatedly controlled by programmed sequential application of voltage pulses, including the operation of data verification.     

Gold nanostructures on chemically reinforced PDMS microwell arrays

This paper describes a facile strategy for fabricating arrays of two- and three-dimensional gold nanostructures using PDMS-infiltrated polystyrene (PS) colloidal crystals. PDMS molding of colloidal crystal, gold vapor deposition, and subsequent calcination of PS produced gold thin layers over hexagonal PDMS microwell arrays with hemispherical air-voids of approximately 140 nm on glass substrates. Vapor deposition of perfluoroalkylsilane thin layers improved the thermal stability of the colloidal template over 100 °C, providing a route to preparation of hollow architectures with gold thin layers supported by PDMS nanostructures. Surface modification of the PDMS using poly(allylamine hydrochloride) induced two-dimensional colloidal crystals of PS and PMMA spheres through electrostatic interactions. Particle aggregation of 13 nm gold nanoparticles in the PDMS microwells demonstrated a surface plasmon resonance band red-shifted to 810 nm, in comparison with that on the flat surface at 720 nm.     

Large-area silica nanotubes with controllable geometry on silicon substrates

The synthesis of a highly uniform, large-scale nanoarrays consisting of silica nanotubes above embedded nanohole arrays in silicon substrates is demonstrated. In situ anodized aluminium oxide (AAO) thin film masks on Si substrates were employed, and the nanotubes were fabricated by Ar ion milling through the masks. The geometries of the nanoarrays, including pore diameter, interpore distance and the length of both nanopores and nanotubes could be controlled by the process parameters, which included that the outer pore diameter of silica tube was tuned from ∼80 nm to ∼135 nm while the inner tube diameter from ∼40 nm to ∼65 nm, the interpore distance of the nanotube arrays was from 100 nm to 180 nm and the length of silica tube changed from ∼90 nm to ∼250 nm. The presented nanostructure fabrication method has strong potential for application in intensity and frequency adjustable high luminescence efficiency optoelectronic devices.     

The amplification effect of functionalized gold nanoparticles on the binding of anticancer drug dacarbazine to DNA and DNA bases

The promising application of functionalized gold nanoparticles to amplify the performance of biosensors and relevant biomolecular recognition processes has been explored in this paper. Our observations illustrate the apparent enhancement effect of the gold nanoparticles on the electrochemical response of the anticancer drug dacarbazine (DTIC) binding to DNA and DNA bases, indicating that these functionalized gold nanoparticles could readily facilitate the specific interactions between DTIC and DNA/DNA bases. This raises the potential valuable applications of these biocompatible nanoparticles in the promising biosensors and biomedical engineering.     

Growth mechanisms for wire-like epitaxial gold silicide islands on Si(1 1 0) surfaces

Epitaxial islands grown on various substrates are usually strained because of differences in lattice constants of the materials of the island and the substrate. Shape transition in the growth of strained islands has been proposed as a mechanism for strain relief and a way to form self-organized quantum wires. Shape transition usually leads to an elongated island growth. However, an elongated island growth may also be due to an anisotropic diffusion of material, the anisotropy being imposed by the symmetry of the substrate surface. In the present example, growth of gold silicide wire-like nanostructures on a Si(1 1 0) surface has been investigated by photoemission electron microscopy (PEEM). Growth of elongated unidirectional gold silicide islands, with an aspect ratio as large as 12:1, has been observed by PEEM following gold deposition on the Si substrate and subsequent annealing at the Au-Si eutectic temperature. Distribution of the width and the length of the gold silicide islands as a function of island area shows a feature similar to that for the shape transition. However, detailed investigations reveal that the elongated growth of gold silicide islands is rather mainly due to anisotropic diffusion of gold due to the twofold symmetry of the (1 1 0) surface of the Si substrate.