Jamie Scott Quinton

Optimizing surfactant concentrations for dispersion of single-walled carbon nanotubes in aqueous solution.

The sonication-centrifugation technique is commonly used for dispersing single-walled carbon nanotubes (SWCNTs) in aqueous surfactant solutions. However, the methodologies and materials used for this purpose are widely varied, and few dispersive agents have been studied systematically. This work describes a systematic study into the ability of some well-known (and some less common) surfactants and polymers to disperse SWCNTs fabricated by two different techniques. UV-vis-NIR absorbance spectra of their supernatant solutions showed that the smaller ionic surfactants were generally more effective dispersants, with larger polymer and surfactant molecules exhibiting a reduced performance for ensembles of carbon nanotubes of smaller average diameter. Optimal surfactant concentrations were established for dispersions of carbon nanotubes produced by the electric arc method in aqueous solutions of sodium dodecylbenzene sulfonate, sodium deoxycholate, Triton X-405, Brij S-100, Pluronic F-127, and polyvinylpyrrolidone. This optimum value was determined as the point at which the relative concentration of nanotubes dispersed is maximized, before flocculation-inducing attractive depletion interactions begin to dominate. The aggregation state of carbon nanotubes dispersed in sodium dodecylbenzene sulfonate was probed by AFM at different stages of rebundling, showing the length dependence of these effects.

Direct attachment of well-aligned single-walled carbon nanotube architectures to silicon (100) surfaces : a simple approach for device assembly

A new approach for the attachment of vertically-aligned shortened carbon nanotube architectures to a silicon (100) substrate by chemical anchoring directly to the surface has been demonstrated for the first time. The ordered assembly of single-walled carbon nanotubes (SWCNTs) was accomplished by hydroxylating the silicon surface followed by a condensation reaction with carboxylic acid functionalised SWCNTs. This new nanostructure has been characterised by X-ray photoelectron, Raman and Fourier transform infrared (FTIR) spectroscopy as well as scanning electron and atomic force microscopy. The assembly behaviour of SWCNTs onto the silicon surface shows a fast initial step producing isolated functionalised carbon nanotubes or nanotube bundles anchored to the silicon surface followed by a slower step where the adsorbed nanotubes grow into larger aggregates via van der Waals interactions between adsorbed and solvated nanotubes. The electrochemical and optical properties of the SWCNTs directly attached to silicon have also been investigated. These new nanostructures are excellent electrochemical electrodes. They also fluoresce in the wavelength range 650-800 nm. The successful attachment of the SWCNTs directly to silicon provides a simple, new avenue for fabrication and development of silicon-based nanoelectronic, nano-optoelectronic and sensing devices. Compared to existing techniques, this new approach has several advantages including low operating temperature, low cost and the possibility of further modification.

Adsorption of organosilanes on iron and aluminium oxide surfaces

Thin films of a simple organosilane, propyltrimethoxysilane (PTMS), on polycrystalline aluminium and iron oxide substrates have been investigated using XPS. Comparison of the adsorption isotherms for the two substrates reveals significant differences between them. Although PTMS on iron oxide exhibits a Langmuir-like isotherm, PTMS on aluminium oxide shows an unexpected decrease in adsorption at intermediate exposures. The results demonstrate that even for the simplest organosilanes and single-component surfaces the formation of silane coatings on metals is complex and strongly dependent upon the nature of the surface. The implication of the results to silane coupling events (SCAs) is discussed briefly.

Conformational dynamics of γ-APS on the iron oxide surface: an adsorption kinetic study using XPS and ToF-SIMS

The formation and structure of thin films of γ-aminopropyltriethoxysilane (y-APS) on mechanically polished iron oxide surfaces have been investigated. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been used to study the time dependence of the surface interaction and the subsequent film structure, following adsorption from the liquid phase. It is shown, for the first time, that γ-APS exhibits the phenomenon of oscillatory adsorption, whereby the surface coverage of the silane species oscillates as a function of time. By analysing the time dependence of the known bonding moieties of the γ-APS molecule, the dominant molecular orientation of the adsorbate is shown to change as a function of time. A model of possible adsorbate conformations is presented and used to describe the observed adsorption behaviour.

Highly conductive interwoven carbon nanotube and silver nanowire transparent electrodes

Abstract Electrodes fabricated using commercially available silver nanowires (AgNWs) and single walled carbon nanotubes (SWCNTs) produced sheet resistances in the range 4–24 Ω □−1 with specular transparencies up to 82 %. Increasing the aqueous dispersibility of SWCNTs decreased the bundle size present in the film resulting in improved SWCNT surface dispersion in the films without compromising transparency or sheet resistance. In addition to providing conduction pathways between the AgNW network, the SWCNTs also provide structural support, creating stable self-supporting films. Entanglement of the AgNWs and SWCNTs was demonstrated to occur in solution prior to deposition by monitoring the transverse plasmon resonance mode of the AgNWs during processing. The interwoven AgNW/SWCNT structures show potential for use in optoelectronic applications as transparent electrodes and as an ITO replacement.

Accurate measurement of Atomic Force Microscope cantilever deflection excluding tip-surface contact with application to force calibration

Considerable attention has been given to the calibration of AFM cantilever spring constants in the last 20 years. Techniques that do not require tip-sample contact are considered advantageous since the imaging tip is not at risk of being damaged. Far less attention has been directed toward measuring the cantilever deflection or sensitivity, despite the fact that the primary means of determining this factor relies on the AFM tip being pressed against a hard surface, such as silicon or sapphire; which has the potential to significantly damage the tip. A recent method developed by Tourek et al. in 2010 involves deflecting the AFM cantilever a known distance from the imaging tip by pressing the cantilever against a sharpened tungsten wire. In this work a similar yet more precise method is described, whereby the deflection of the cantilever is achieved using an AFM probe with a spring constant much larger than the test cantilever, essentially a rigid cantilever. The exact position of loading on the test cantilever was determined by reverse AFM imaging small spatial markers that are milled into the test cantilever using a focussed ion beam. For V shaped cantilevers it is possible to reverse image the arm intersection in order to determine the exact loading point without necessarily requiring FIB milled spatial markers, albeit at the potential cost of additional uncertainty. The technique is applied to tip-less, beam shaped and V shaped cantilevers and compared to the hard surface contact technique with very good agreement (on average less than 5% difference). While the agreement with the hard surface contact technique was very good the error on the technique is dependent upon the assumptions inherent in the method, such as cantilever shape, loading point distance and ratio of test to rigid cantilever spring constants. The average error ranged between 2 to 5% for the majority of test cantilevers studied. The sensitivity derived with this technique can then be used to calibrate the cantilever spring constant using the thermal noise method, allowing complete force calibration to be accurately performed without tip-sample contact.

Calibration of atomic force microscope cantilevers using standard and inverted static methods assisted by FIB-milled spatial markers.

Static methods to determine the spring constant of AFM cantilevers have been widely used in the scientific community since the importance of such calibration techniques was established nearly 20 years ago. The most commonly used static techniques involve loading a trial cantilever with a known force by pressing it against a pre-calibrated standard or reference cantilever. These reference cantilever methods have a number of sources of uncertainty, which include the uncertainty in the measured spring constant of the standard cantilever, the exact position of the loading point on the reference cantilever and how closely the spring constant of the trial and reference cantilever match. We present a technique that enables users to minimize these uncertainties by creating spatial markers on reference cantilevers using a focused ion beam (FIB). We demonstrate that by combining FIB spatial markers with an inverted reference cantilever method, AFM cantilevers can be accurately calibrated without the tip of the test cantilever contacting a surface. This work also demonstrates that for V-shaped cantilevers it is possible to determine the precise loading position by AFM imaging the section of the cantilever where the two arms join. Removing tip-to-surface contact in both the reference cantilever method and sensitivity calibration is a significant improvement, since this is an important consideration for AFM users that require the imaging tip to remain in pristine condition before commencing measurements. Uncertainties of between 5 and 10% are routinely achievable with these methods.

Formation of N719 Dye Multilayers on Dye Sensitized Solar Cell Photoelectrode Surfaces Investigated by Direct Determination of Element Concentration Depth Profiles

The structure of the dye layer adsorbed on the titania substrate in a dye-sensitized solar cell is of fundamental importance for the function of the cell, since it strongly influences the injection of photoelectrons from the excited dye molecules into the titania substrate. The adsorption isotherms of the N719 ruthenium-based dye were determined both with a direct method using the depth profiling technique neutral impact collision ion scattering spectroscopy (NICISS) and with the standard indirect solution depletion method. It is found that the dye layer adsorbed on the titania surface is laterally inhomogeneous in thickness and there is a growth mechanism already from low coverage levels involving a combination of monolayers and multilayers. It is also found that the amount of N719 adsorbed on the substrate depends on the titania structure. The present results show that dye molecules in dye-sensitized solar cells are not necessarily, as presumed, adsorbed as a self-assembled monolayer on the substrate.

Single‐Walled Carbon Nanotube/Polyaniline/n‐Silicon Solar Cells: Fabrication, Characterization, and Performance Measurements

Carbon nanotube-silicon solar cells are a recently investigated photovoltaic architecture with demonstrated high efficiencies. Silicon solar-cell devices fabricated with a thin film of conductive polymer (polyaniline) have been reported, but these devices can suffer from poor performance due to the limited lateral current-carrying capacity of thin polymer films. Herein, hybrid solar-cell devices of a thin film of polyaniline deposited on silicon and covered by a single-walled carbon nanotube film are fabricated and characterized. These hybrid devices combine the conformal coverage given by the polymer and the excellent electrical properties of single-walled carbon nanotube films and significantly outperform either of their component counterparts. Treatment of the silicon base and carbon nanotubes with hydrofluoric acid and a strong oxidizer (thionyl chloride) leads to a significant improvement in performance.

Influence of surface electrokinetics on organosilane adsorption

The time-dependent adsorption of propyltrimethoxysilane (PTMS) in aqueous solution on four substrates (aluminium, zinc, iron and chromium oxide) has been investigated using x-ray photoelectron spectroscopy. Oscillations in the adsorption isotherm as a function of adsorption time in solution have been observed for all of the substrates studied. The adsorption of PTMS is shown to depend strongly upon the isoelectric point of the surface oxide. The closer the isoelectric point is to the solution pH, the more rapid is the initial adsorption rate of silane on the surface. Models are proposed to explain the influence that the electrokinetics of the surface has upon the adsorption mechanism.