David P. Burt

Polyaniline Langmuir-Blodgett films: formation and properties

The deposition and characterisation of Langmuir-Blodgett (LB) layers of polyaniline (PAN) on solid supports is described. Langmuir films were spread as a mixture of PAN and dodecylbenzenesulfonic acid (DBSA) at the water/air interface and deposited on either glass or indium tin oxide (ITO). Mono- and multi-layer films of PAN/DBSA were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), absorption spectroscopy and cyclic voltammetry (CV). The ultrathin films produced were found to be highly uniform and very stable. Further characterisation of the films was accomplished by scanning electrochemical microscopy (SECM) in the feedback mode. It was found that the conductivity depended strongly on the pH of the solution and the number of layers deposited. Values for the pH-dependent lateral conductivity of PAN LB films are reported.

In-Situ Atomic Force Microscopy (AFM) Imaging : Influence of AFM Probe Geometry on Diffusion to Microscopic Surfaces

The effect of AFM probe geometry on diffusion to micrometer-scale reactive (electrode) interfaces is considered. A disk-shaped substrate electrode was held at a potential to reduce a species of interest (aqueous Ru(NH 3) 6 (3+)) at a diffusion-controlled rate and the current response during AFM imaging provided information on local mass transport to the interface. This approach reveals how the AFM probe influences diffusion to a reactive surface, which is of importance in more clearly delineating the conditions under which in-situ AFM can be treated as a noninvasive probe of surface processes involving mass transport (e.g., electrode reactions and crystal dissolution and growth). An assessment has been made of three types of probes: V-shaped silicon nitride contact mode probes; single beam silicon probes; and batch-fabricated scanning electrochemical-atomic force microscopy (SECM-AFM) probes. Two disk electrodes, (6.1 microm and 1.6 microm diameter) have been considered as substrates. The results indicate that conventional V-shaped contact mode probes are the most invasive and that the batch-fabricated SECM-AFM probes are the least invasive to diffusion at both of the substrates used herein. The experimental data are complemented by the development of simulations based on a simple 2D model of the AFM probe and active surface site. The importance of probe parameters such as the cantilever size, tip cone height, and cone angle is discussed, and the implications of the results for studies in other areas, such as growth and dissolution processes, are considered briefly.

Growth and morphology control of carbon nanotubes at the apexes of pyramidal silicon tips

We describe the development of catalysed chemical vapour deposition (cCVD) growth schemes suitable for the production of carbon nanotube atomic force microscopy (CNT-AFM) probes. Growth and sample processing conditions are utilized that both incorporate safety in the process, e.g. the use of ethanol (EtOH) vapour as a carbon feedstock and hydrogen at only 4% (flow proportion), and simplicity, e.g. no catalyst patterning is required. Cobalt is employed as the growth catalyst and thin films of aluminium on silicon as the substrate material. Purpose-fabricated silicon substrates containing large numbers of tip structures are used as models of AFM probes. This enables growth to be carried out on many tips at once, facilitating a thorough investigation of the effect of different growth schemes on yields. cCVD growth schemes are chosen which produce stabilizing high density networks of carbon nanotubes on the sidewalls of the pyramidal tips to aid in anchoring the apex protruding carbon nanotube(s) in place. This results in long-lasting AFM imaging tips. We demonstrate that through rational tailoring of cCVD conditions it is possible to tune the growth conditions such that CNTs which protrude straight from tip apexes can be obtained at yields of greater than or equal to 78%. Application of suitable growth schemes to CNT growth on commercially available AFM probes resulted in CNT-AFM probes which were found to be extremely useful for extended lifetime metrological profiling of complex structures.

Scanning electrochemical microscopy as a probe of Ag+ binding kinetics at Langmuir phospholipid monolayers.

A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple is reversible, the response is highly sensitive to local mass transfer of Ag+ away from the electrode, which, in turn, is governed by the interaction of Ag+ with the monolayer. The methodology has been used to determine the influence of surface pressure on the adsorption of Ag+ ions at a phospholipid (dipalmitoyl phosphatidic acid) Langmuir monolayer. It is shown that the capacity for metal ion adsorption at the monolayer increased as the density of surface adsorption sites increased (by increasing the surface pressure). A model for mass transport and adsorption in this geometry has been developed to explain and characterise the adsorption process.

Aperiodic interferometer for six degrees of freedom position measurement

We present a new class of interferometer system that is capable of simultaneous measurement of absolute position and rotation in all six degrees of freedom (DOF) with nanometer precision. This novel capability is due to the employment of a system of interference fringes that is not periodic. One of the key strengths offered by this new approach is that the absolute position of the system can be determined with a single measurement, rather than by counting fringes during displacement from a known location. The availability of a simultaneous measurement of all six DOF eliminates many problems associated with conventional interferometry.

Developments in Nanowire Scanning Electrochemical - Atomic Force Microscopy (SECM-AFM) Probes

Since its introduction, SECM-AFM has gained recognition as an extremely useful tool for a wide variety of analytical and imaging applications. We have developed a probe fabrication method that uses single-walled carbon nanotube bundles as a structural template for the formation of a nanowire at the apex of an AFM tip. Subsequent insulation of the probe and cutting across the nanowire yields a disc electrode of well-defined geometry. The probe apex geometry results in topographic information being obtained without causing damage to the electrode by contacting the substrate. Also, by placing the electrode at the apex, electric force imaging can also be realized. The probes are demonstrated to accurately identify active sites and locally generated species by combined topographic and electrochemical measurements on the sub-micron scale. The influence of the probe geometry on the diffusion of species from micrometer scale active sites will also be considered.