Broadband optical cavity absorption spectroscopy in the near-ultraviolet: applications in atmospheric chemistry

A novel spectroscopic method, incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), has been modified and extended to measure absorption spectra in the near-ultraviolet with high sensitivity. The near-ultraviolet region extends from 300 to 400 nm and is particularly important in tropospheric photochemistry; absorption of near-UV light can also be exploited for sensitive trace gas measurements of several key atmospheric constituents. In this work, several IBBCEAS instruments were developed to record reference spectra and to measure trace gas concentrations in the laboratory and field. An IBBCEAS instrument was coupled to a flow cell for measuring very weak absorption spectra between 335 and 375 nm. The instrument was validated against the literature absorption spectrum of SO2. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably owing to the extremely weak absorption. The instrument was also applied to quantifying low concentrations of the short-lived radical, BrO, in the presence of strong absorption by Br2 and O3. A different IBBCEAS system was adapted to a 4 m3 atmosphere simulation chamber to record the absorption cross-sections of several low vapour pressure compounds, which are otherwise difficult to measure. Absorption cross-sections of benzaldehyde and the more volatile alkyl nitrites agree well with previous spectra; on this basis, the cross-sections of several nitrophenols are reported for the first time. In addition, the instrument was also used to study the optical properties of secondary organic aerosol formed following the photooxidation of isoprene. An extractive IBBCEAS instrument was developed for detecting HONO and NO2 and had a sensitivity of about 10-9 cm-1. This instrument participated in a major international intercomparison of HONO and NO2 measurements held in the EUPHORE simulation chamber in Valencia, Spain, and results from that campaign are also reported here.

Development of large-scale colloidal crystallisation methods for the production of photonic crystals

Colloidal photonic crystals have potential light manipulation applications including; fabrication of efficient lasers and LEDs, improved optical sensors and interconnects, and improving photovoltaic efficiencies. One road-block of colloidal selfassembly is their inherent defects; however, they can be manufactured cost effectively into large area films compared to micro-fabrication methods. This thesis investigates production of ‘large-area’ colloidal photonic crystals by sonication, under oil co-crystallization and controlled evaporation, with a view to reducing cracking and other defects. A simple monotonic Stöber particle synthesis method was developed producing silica particles in the range of 80 to 600nm in a single step. An analytical method assesses the quality of surface particle ordering in a semiquantitative manner was developed. Using fast Fourier transform (FFT) spot intensities, a grey scale symmetry area method, has been used to quantify the FFT profiles. Adding ultrasonic vibrations during film formation demonstrated large areas could be assembled rapidly, however film ordering suffered as a result. Under oil cocrystallisation results in the particles being bound together during film formation. While having potential to form large areas, it requires further refinement to be established as a production technique. Achieving high quality photonic crystals bonded with low concentrations (<5%) of polymeric adhesives while maintaining refractive index contrast, proved difficult and degraded the film’s uniformity. A controlled evaporation method, using a mixed solvent suspension, represents the most promising method to produce high quality films over large areas, 75mm x 25mm. During this mixed solvent approach, the film is kept in the wet state longer, thus reducing cracks developing during the drying stage. These films are crack-free up to a critical thickness, and show very large domains, which are visible in low magnification SEM images as Moiré fringe patterns. Higher magnification reveals separation between alternate fringe patterns are domain boundaries between individual crystalline growth fronts.

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Beyond simple imaging with energetic beams – nanopatterning, correlative microscopy and statistical analysis of inclusions

Electron microscopy (EM) has advanced in an exponential way since the first transmission electron microscope (TEM) was built in the 1930’s. The urge to ‘see’ things is an essential part of human nature (talk of ‘seeing is believing’) and apart from scanning tunnel microscopes which give information about the surface, EM is the only imaging technology capable of really visualising atomic structures in depth down to single atoms. With the development of nanotechnology the demand to image and analyse small things has become even greater and electron microscopes have found their way from highly delicate and sophisticated research grade instruments to key-turn and even bench-top instruments for everyday use in every materials research lab on the planet. The semiconductor industry is as dependent on the use of EM as life sciences and pharmaceutical industry. With this generalisation of use for imaging, the need to deploy advanced uses of EM has become more and more apparent. The combination of several coinciding beams (electron, ion and even light) to create DualBeam or TripleBeam instruments for instance enhances the usefulness from pure imaging to manipulating on the nanoscale. And when it comes to the analytic power of EM with the many ways the highly energetic electrons and ions interact with the matter in the specimen there is a plethora of niches which evolved during the last two decades, specialising in every kind of analysis that can be thought of and combined with EM. In the course of this study the emphasis was placed on the application of these advanced analytical EM techniques in the context of multiscale and multimodal microscopy – multiscale meaning across length scales from micrometres or larger to nanometres, multimodal meaning numerous techniques applied to the same sample volume in a correlative manner. In order to demonstrate the breadth and potential of the multiscale and multimodal concept an integration of it was attempted in two areas: I) Biocompatible materials using polycrystalline stainless steel and II) Semiconductors using thin multiferroic films. I) The motivation to use stainless steel (316L medical grade) comes from the potential modulation of endothelial cell growth which can have a big impact on the improvement of cardio-vascular stents – which are mainly made of 316L – through nano-texturing of the stent surface by focused ion beam (FIB) lithography. Patterning with FIB has never been reported before in connection with stents and cell growth and in order to gain a better understanding of the beam-substrate interaction during patterning a correlative microscopy approach was used to illuminate the patterning process from many possible angles. Electron backscattering diffraction (EBSD) was used to analyse the crystallographic structure, FIB was used for the patterning and simultaneously visualising the crystal structure as part of the monitoring process, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to analyse the topography and the final step being 3D visualisation through serial FIB/SEM sectioning. II) The motivation for the use of thin multiferroic films stems from the ever-growing demand for increased data storage at lesser and lesser energy consumption. The Aurivillius phase material used in this study has a high potential in this area. Yet it is necessary to show clearly that the film is really multiferroic and no second phase inclusions are present even at very low concentrations – ~0.1vol% could already be problematic. Thus, in this study a technique was developed to analyse ultra-low density inclusions in thin multiferroic films down to concentrations of 0.01%. The goal achieved was a complete structural and compositional analysis of the films which required identification of second phase inclusions (through elemental analysis EDX(Energy Dispersive X-ray)), localise them (employing 72 hour EDX mapping in the SEM), isolate them for the TEM (using FIB) and give an upper confidence limit of 99.5% to the influence of the inclusions on the magnetic behaviour of the main phase (statistical analysis).