Attilio A. Cafolla

Optimisation and characterisation of biosensors based on polyaniline

With lower limits of detection and increased stability constantly being demanded of biosensor devices, characterisation of the constituent layers that make up the sensor has become unavoidable, since this is inextricably linked with its performance. This work describe the optimisation and characterisation of two aspects of sensor performance: a conductive polymer layer (polyaniline) and the immobilised protein layer. The influence of the thickness of polyaniline films deposited electrochemically onto screen-printed electrode surfaces is described in this work in terms of its influence on a variety of amperometric sensor performance characteristics: time to reach steady state, charging current, catalytic current, background current and signal/background ratios. The influence of polymer film thickness on the conductivity and morphology of finished films is also presented. An electrostatic method of protein immobilisation is used in this work and scanning electron microscopy in conjunction with gold-labelled antibodies and back-scattered electron detection has enabled the direct visualisation of individual groups of proteins on the sensor surface. Such information can provide an insight into the performance of sensors under influence of increasing protein concentrations.

Correlation of Raman and X-ray diffraction measurements of annealed pulsed laser deposited ZnO thin films

Abstract Raman spectroscopy, X-ray diffractometry and atomic force microscopy have been used to characterise ZnO thin films grown by pulsed laser deposition as a function of the post-growth annealing temperature. The results show substantial enhancement and broadening of certain Raman features which correlate excellently with the change in width of the X-ray diffraction peaks. The 570 cm−1 Raman feature showed pronounced asymmetry and enhanced intensity in the unannealed sample. An increase in grain size observed after subsequent annealing produced a substantial reduction in both the asymmetry and intensity of this peak. Our experimental data suggest that electric fields, due to charge trapping at grain boundaries, in conjunction with localised and surface phonon modes are the cause of the intensity enhancement and asymmetry of this feature.

Evidence for the formation of an intermediate complex in the direct metalation of tetra(4-bromophenyl)-porphyrin on the Cu(111) surface

A strong molecule-surface interaction between free-base-tetra(4-bromophenyl)-porphyrin and Cu(111) results in a distortion of both the molecule and the underlying copper surface in the vicinity of the molecule. This in turn leads to the formation of an intermediate complex due to bonding between the iminic nitrogens and surface copper atoms.

Reactive amine surfaces for biosensor applications, prepared by plasma-enhanced chemical vapour modification of polyolefin materials

Here we have demonstrated a solventless plasma-based process that integrates low-cost, high throughput, high reproducibility and ecofriendly process for the functionalization of the next-generation point-of-care device platforms. Amine functionalities were deposited by plasma-enhanced chemical vapour deposition (PECVD) using a new precursor. The influence of the plasma RF power and the deposition time on surfacial properties, as well as their effect on the reactivity and content of amino groups was investigated. The key process determinants were to have a sufficient power in the plasma to activate and partially fragment the monomer but not too much as to lose the reactive amine functionality, and sufficient deposition time to develop a reactive layer but not to consume or erode the amine reactivity. An immunoassay performed using human immunoglobulin (IgG) as a model analyte showed an improvement of the detection limit by two orders of magnitude beyond that obtained using devices activated by liquid-phase reaction.

Plasma Surface Modification of Cyclo-olefin Polymers and Its Application to Lateral Flow Bioassays

The modification of cyclo-olefin polymer Zeonor by plasma-enhanced chemical vapor deposition to form a silica-like surface and evaluation of its application for lateral flow bioassays applications are discussed in this study. The SiOx layer was extensively characterized using contact angle measurements, atomic force microscopy, and Fourier transform infrared spectroscopy in attenuated total internal reflectance mode where the presence of a uniform SiOx film was clearly identified. The SiOx modification resulted in a surface with enhanced wettability and excellent fluidic properties when combined with a hot-embossed micropillar capillary fill-based substrate. The SiOx surface also had the ability to accelerate the clotting of human plasma, which may have application in certain types of blood coagulation assays.

Ni(II) porphine nanolines grown on a Ag(111) surface at room temperature

The room temperature growth and ordering of (porphyrinato)nickel (II) (or nickel (II) porphine, NiP) molecules on a Ag(111) surface have been investigated using scanning tunnelling microscopy and low-energy electron diffraction (LEED). At a coverage of one monolayer, NiP molecules form a well-ordered molecular layer, having a hexagonal structure, on the Ag(111) surface. Porphyrin molecules have a flat orientation in this overlayer with the molecular plane lying parallel to the substrate. LEED data obtained from one monolayer of the NiP on the Ag(111) surface show the formation of two mirror domains each rotated either clockwise or anticlockwise by 6 degrees with respect to the substrate. NiP molecules forming a second layer self-assemble into well-ordered and uniformly separated nanolines at room temperature. These nanolines consist of hexagonally ordered NiP molecules and are found to be 1-4 molecules wide, depending on the molecular coverage. The completed second monolayer preserves the same planarity and hexagonal ordering as the first molecular layer but with a 4% lateral relaxation which produces a periodic modulation of approximately 5 nm.

A re-interpretation of the Cu{100}/Sn surface phase diagram

The coverage dependent structural phase transitions of Sn on Cu{100} have been re-examined by low energy electron diffraction (LEED). Double scattering LEED pattern simulations have been applied both to a range of possible new models and to previously suggested structures with the aim of identifying the most likely surface geometries throughout the sub-monolayer coverage regime. A model consistent with both the Sn surface coverage and the complex split beam LEED pattern observed has been suggested for the low coverage (θ Sn = 0.21 ML) ordered phase based on a p(2 x 2) structure with light antiphase domain walls. We also demonstrate that higher coverage p(2 x 6) (θ Sn = 0.37 ML) and p(3√2 x √2)R45° (θ Sn = 0.50 ML) structures based on c(2 x 2) local periodicity yield a consistent explanation of the LEED data. While the simulations identify likely structures, the limitations of this approach mitigate against definitive structural assignments. However simulations for models based on c(2 x 2) structures incorporating defects in the form of periodic density modulations combined with substrate reconstruction lead to an enhanced agreement with observed LEED data compared to overlayer models previously suggested.

Extreme-ultraviolet studies with laser-produced plasmas

A new multilaser multichannel spectrometer system has been developed that allows a wide range of investigations of the interaction of extreme-ultraviolet (EUV) photons with matter in the form of free atoms or ions, e.g., in gases or plasmas or bound as in solids. The EUV photons are generated by a laser-produced plasma. Applications to the study of photoabsorption by thin foils, gases, and ground- and excited-state atoms and ions are described. The design and performance of a collimated, quasi-monochromatic, intense source of EUV radiation based on the combination of a laser-produced plasma with a EUV multilayer mirror is also reported.

Air sensitivity of MoS2, MoSe2, MoTe2, HfS2, and HfSe2

A surface sensitivity study was performed on different transition-metal dichalcogenides (TMDs) under ambient conditions in order to understand which material is the most suitable for future device applications. Initially, Atomic Force Microscopy and Scanning Electron Microscopy studies were carried out over a period of 27 days on mechanically exfoliated flakes of 5 different TMDs, namely, MoS2, MoSe2, MoTe2, HfS2, and HfSe2. The most reactive were MoTe2 and HfSe2. HfSe2, in particular, showed surface protrusions after ambient exposure, reaching a height and width of approximately 60 nm after a single day. This study was later supplemented by Transmission Electron Microscopy (TEM) cross-sectional analysis, which showed hemispherical-shaped surface blisters that are amorphous in nature, approximately 180–240 nm tall and 420–540 nm wide, after 5 months of air exposure, as well as surface deformation in regions between these structures, related to surface oxidation. An X-ray photoelectron spectroscopy study o...

Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene.

The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.