Benjamin S. Flavel

Ruthenium Porphyrin Functionalized Single-Walled Carbon Nanotube Arrays-A Step Toward Light Harvesting Antenna and Multibit Information Storage

Ruthenium porphyrin functionalized single-walled carbon nanotube arrays have been prepared using coordination of the axial position of the metal ion onto 4-aminopyridine preassembled single-walled carbon nanotubes directly anchored to a silicon(100) surface (SWCNTs-Si). The formation of these ruthenium porphyrin functionalized single-walled carbon nanotube array electrodes (RuTPP-SWCNTs-Si) has been monitored using infrared spectroscopy (IR), differential pulse voltammetry (DPV), atomic force microscopy (AFM), laser desorption time-of-flight mass spectroscopy (LDI-TOF-MS), UV-vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. Electrochemical results show two successive one-electron reversible redox waves. The surface concentration of the ruthenium porphyrin molecules is 3.44 x 10 (-8) mol cm (-2). Optical results indicate that the immobilization of ruthenium porphyrin enhances the light absorption of SWCNTs-Si surfaces in the visible light region. Moreover mixed assembly of ferrocene/porphyrin onto carbon nanotube arrays has been achieved by altering the ratio of two redox-active species in the deposition solution. These results suggest the ruthenium porphyrin modified electrodes are excellent candidates for molecular memory devices and light harvesting antennae.

Separation of Single-Walled Carbon Nanotubes with a Gel Permeation Chromatography System

A gel permeation chromatography system is used to separate aqueous sodium dodecyl sulfate suspensions of single-walled carbon nanotubes (SWCNTs). This automated procedure requires no precentrifugation, is scalable, and is found to yield monochiral SWCNT fractions of semiconducting SWCNTs with a purity of 61-95%. Unsorted and resulting monochiral fractions are characterized using optical absorption and photoluminescence spectroscopy.

Separation of single-walled carbon nanotubes by 1-dodecanol-mediated size-exclusion chromatography.

A simple, single-column, high-throughput fractionation procedure based on size-exclusion chromatography of aqueous sodium dodecyl sulfate suspensions of single-walled carbon nanotubes (SWCNTs) is presented. This procedure is found to yield monochiral or near monochiral SWCNT fractions of semiconducting SWCNTs. Unsorted and resulting monochiral suspensions are characterized using optical absorption and photoluminescence spectroscopy.

Reaction of gold substrates with diazonium salts in acidic solution at open-circuit potential.

The reaction of gold substrates with p-nitrobenzene diazonium tetrafluoroborate (NBD) in 0.1 M H(2)SO(4) at open-circuit potential (OCP) is demonstrated to proceed by electron transfer from gold to the NBD cation. Electrochemical, atomic force microscopy, and X-ray photoelectron spectroscopy analyses reveal the formation of multilayer films with the same composition as electrografted films. The film growth characteristics (surface concentration and film thickness vs time) also follow those observed during electrografting, consistent with electron transfer from the substrate to the diazonium cation. The OCP of the gold substrate increases during the period of film growth ( approximately 60 min) and then decreases to close to its initial value. The increase corresponds to accumulation of positive charge as electrons are transferred to NBD; the discharge process is tentatively attributed to slow oxidation of adventitious impurities in the reaction solution. Films formed at OCP or by electrografting from aqueous acid solution are markedly less stable to sonication in acetonitrile than are those electrografted from acetonitrile. Increased amounts of physisorbed material in films prepared in aqueous media or bonding of aryl groups to different gold sites in the two media are tentatively proposed to account for the different stabilities.

A Simple Approach to Patterned Protein Immobilization on Silicon via Electrografting from Diazonium Salt Solutions

A highly versatile method utilizing diazonium salt chemistry has been developed for the fabrication of protein arrays. Conventional ultraviolet mask lithography was used to pattern micrometer sized regions into a commercial photoresist on a highly doped p-type silicon (100) substrate. These patterned regions were used as a template for the electrochemical grafting of the in situ generated p-aminobenzenediazonium cation to form patterns of aminophenyl film on silicon. Immobilization of biomolecules was demonstrated by coupling biotin to the aminophenyl regions followed by reaction with fluorescently labeled avidin and visualization with fluorescence microscopy. This simple patterning strategy is promising for future application in biosensor devices.

Double‐Walled Carbon Nanotube Processing

Single-walled carbon nanotubes (SWCNTs) have been the focus of intense research, and the body of literature continues to grow exponentially, despite more than two decades having passed since the first reports. As well as extensive studies of the fundamental properties, this has seen SWCNTs used in a plethora of applications as far ranging as microelectronics, energy storage, solar cells, and sensors, to cancer treatment, drug delivery, and neuronal interfaces. On the other hand, the properties and applications of double-walled carbon nanotubes (DWCNTs) have remained relatively under-explored. This is despite DWCNTs not only sharing many of the same unique characteristics of their single-walled counterparts, but also possessing an additional suite of potentially advantageous properties arising due to the presence of the second wall and the often complex inter-wall interactions that arise. For example, it is envisaged that the outer wall can be selectively functionalized whilst still leaving the inner wall in its pristine state and available for signal transduction. A similar situation arises in DWCNT field effect transistors (FETs), where the outer wall can provide a convenient degree of chemical shielding of the inner wall from the external environment, allowing the excellent transconductance properties of the pristine nanotubes to be more fully exploited. Additionally, DWCNTs should also offer unique opportunities to further the fundamental understanding of the inter-wall interactions within and between carbon nanotubes. However, the realization of these goals has so far been limited by the same challenge experienced by the SWCNT field until recent years, namely, the inherent heterogeneity of raw, as-produced DWCNT material. As such, there is now an emerging field of research regarding DWCNT processing that focuses on the preparation of material of defined length, diameter and electronic type, and which is rapidly building upon the experience gained by the broader SWCNT community. This review describes the background of the field, summarizing some relevant theory and the available synthesis and purification routes; then provides a thorough synopsis of the current state-of-the-art in DWCNT sorting methodologies, outlines contemporary challenges in the field, and discusses the outlook for various potential applications of the resulting material.

Micropatterned Arrays of Porous Silicon: Toward Sensory Biointerfaces

We describe the fabrication of arrays of porous silicon spots by means of photolithography where a positive photoresist serves as a mask during the anodization process. In particular, photoluminescent arrays and porous silicon spots suitable for further chemical modification and the attachment of human cells were created. The produced arrays of porous silicon were chemically modified by means of a thermal hydrosilylation reaction that facilitated immobilization of the fluorescent dye lissamine, and alternatively, the cell adhesion peptide arginine-glycine-aspartic acid-serine. The latter modification enabled the selective attachment of human lens epithelial cells on the peptide functionalized regions of the patterns. This type of surface patterning, using etched porous silicon arrays functionalized with biological recognition elements, presents a new format of interfacing porous silicon with mammalian cells. Porous silicon arrays with photoluminescent properties produced by this patterning strategy also have potential applications as platforms for in situ monitoring of cell behavior.

Waveguide-Integrated Light-Emitting Carbon Nanotubes

We demonstrate how light from an electrically driven carbon nanotube can be coupled directly into a photonic waveguide architecture. Waferscale, broadband sources are realized integrated with nanophotonic circuits allowing for propagation of light over centimeter distances. Moreover, we show that the spectral properties of the emitter can be controlled directly on chip with passive devices using Mach-Zehnder interfero-meters and grating structures.

Patterning of metal, carbon, and semiconductor substrates with thin organic films by microcontact printing with aryldiazonium salt inks.

Surface modification through reduction of aryldiazonium salts to give covalently attached layers is a widely investigated procedure. However, realization of potential applications of the layers requires development of patterning methods. Here, we demonstrate that microcontact printing with poly(dimethylsiloxane) stamps inked with aqueous acid solutions of aryldiazonium salts gives stable organic layers on gold, copper, silicon, and graphitic carbon surfaces. Depending on the substrate-diazonium salt combination, the layers range from relatively irregular multilayers to smooth films with close to monolayer thickness. After printing, surface attached aminophenyl and carboxyphenyl groups retain their usual reactivity toward amide bond formation with solution species, and hence, the method is a simple route to patterned, covalently attached, reactive tether layers. Multicomponent patterned films can be prepared by printing a second modifier onto a film-coated surface. Microcontact printing using aryldiazonium salt inks is experimentally very simple and is applicable to the broad range of substrates capable of spontaneously reducing aryldiazonium salts.

Single- and double- sided chemical functionalization of bilayer graphene

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X-ray photoelectron spectroscopy. Single- and double-sided chemical functionalization are found to give very different results: single-sided modified bilayers show relatively high mobility (200-600 cm(2) V(-1) s(-1) at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double-sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single-sided modification of bilayers) for sensors and transistors and new graphene-derivatives materials (through double-sided modification).