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No description available.

No description available.

Cavity enhanced absorption spectroscopies have earned themselves a place as one of the methods of choice for sensitive absorption measurements on gas-phase samples, but their application to liquid samples has so far been more limited. Sensitive short pathlength analysis of liquid samples is required for online analysis of microfluidic samples, which are processed in channels with dimensions of tens to hundreds of micrometres. Microfluidics is important for a range of applications including drug discovery and environmental sensing. This thesis explores the application of cavity enhanced absorption spectroscopies to short pathlength (0.010 mm to 2 mm) analysis of sub-microlitre volumes of liquids. Three experimental set-ups have been been examined. Firstly, a single-wavelength cavity ringdown (CRD) spectrometer operating at 532 nm was assembled using two 99.8% reflectivity mirrors. High optical quality flow cells with short pathlengths ranging from 0.1 mm to 2 mm were inserted into this cavity at Brewster’s angle. The detection limit of the set-up with each inserted flow cell was established using a concentration series of aqueous potassium permanganate (KMnO₄) solutions. For the 1 mm flow cell, a detection limit of 29 nM KMnO₄ or 1.4 x 10⁻⁴ cm⁻¹ was established. Several different types of microfluidic devices were also inserted into the cavity, and it was found that the losses arising from the inserted chip were highly dependent on the method of chip manufacture. The CRD set-up with inserted 1 mm flow cell was applied to the detection of two important species, nitrite and iron(II), via analyte-specific colourimetric reactions. Detection limits of 1.9 nM nitrite and 3.8 nM iron(II) were established. The second experimental set-up utilised broadband, supercontinuum light generated in a 20 m length of nonlinear photonic crystal fibre. Broadband mirrors with around 99% reflectivity over the wavelength range from 400 to 800 nm were used to form the cavity, and a miniature spectrometer was used to wavelength-resolve the time-integrated cavity output. Flow cells and microfluidic chips were inserted into the cavity either at normal incidence or at Brewster’s angle. This set-up was employed for reaction analysis of an iron complexation reaction with bathophenanthroline, and for a model organic reaction, the Diels-Alder reaction between anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione. The same broadband set-up was also used for pH measurements using bromocresol green indicator solution. Using dual-wavelength CRD spectroscopy, the pH sensitivity was established to be around a few milli pH units. Finally, an alternative type of cavity, formed from a loop of optical fibre has been investigated. A novel light-coupler was designed and fabricated in 365 μm core diameter multimode optical fibre. Sample designs employing both direct and evanescent wave absorption were investigated in small-core and large-core optical fibres, and the lowest detection limit of 0.11 cm⁻¹ was determined in direct absorption measurements, with a pathlength of 180 μm, using our novel light coupler in 365 μm core diameter optical fibre.

La qualité des interfaces dans les multicouches périodiques est essentielle au développement de miroirs réfléchissant efficacement dans les domaines des rayons X et extrême ultraviolet (X-EUV). De manière générale, la structure des interfaces dépend des possibles interdiffusion et processus chimiques aux interfaces entre couches. L'idée principale de cette thèse est d'appliquer la technique des ondes stationnaires dans le domaine X à la caractérisation de matériaux, principalement mais non exclusivement aux multicouches périodiques. Cette méthode est basée sur l'interférence de deux faisceaux de rayons X cohérents. L'interférence constructive sur un plan anti-nodal amplifie le champ électrique tandis que l'interférence destructive minimise ce dernier sur un plan nodal. Cette technique des ondes stationnaires dans le domaine X permet l'excitation (photoémission, fluorescence, ...) d'endroits spécifiques dans un empilement périodique de matériaux. De cette manière, les spectres expérimentaux ainsi obtenus sont principalement les spectres caractéristiques des atomes situés sur un plan anti-nodal. Combinée avec d'autres techniques expérimentales telles que la spectroscopie d'émission X (XES) ou la spectroscopie de photoélectrons dans le domaine X (XPS), une information sélective en profondeur, avec une sensibilité sub-nanométrique, peut être obtenue. / The interfacial information of periodic multilayers can be crucial for the development of reflecting mirrors which operate in the X-ray and extreme ultraviolet (X-EUV) ranges. Such information may contain the interdiffusion and chemical process at the interfaces of the layers. The idea of this thesis is to apply the X-ray standing wave technique to the characterization of materials, mainly but not limited to the periodic multilayers. X-ray standing wave technique enables to enhance the excitation (photoemission, fluorescence etc.) of specific locations within a periodic stack. The nature of such advantage is the interference of two coherent X-ray beams. One may compare the X-ray standing waves with the mechanical standing waves. The constructive interference at the anti-nodal plane amplifies the electric field; while the destructive interference at the nodal plane minimizes the electric field. In this way, the experimental spectra obtained under standing wave field will be mostly the material located on the anti-nodal plane. Combined with other techniques such as X-ray emission spectroscopy and X-ray photoelectron spectroscopy, a depth-selective information with a sub-nanoscale sensitivity can be obtained.