Hamburg, Univ., Diss., 2003. / Computerdatei im Fernzugriff.

Hamburg, University, Diss., 2003.

Univ., Diss., 2010--Kassel. / Parallelt.: Patent DE 10 2004 037 519 B4 "Sensor-Vorrichtung und Verfahren zur Ermittlung einer physikalischen Größe"

Universiẗat, Diss., 2000--Hamburg.

La réalisation d'une transformation chimique dans un espace confiné constitue pour les chimistes molécularistes un véritable défi. Des recherches récentes ont montré que des réactions se déroulant dans une poche ou une cavité moléculaire étaient de nature à engendrer des sélectivités nouvelles et faciliter des réactions thermodynamiquement défavorables. L'association métal-cavité permet également le déroulement de processus catalytiques en milieu aqueux, dès lors que la cavité a été rendue hydrosoluble.L’objectif de cette thèse était de préparer des ligands originaux intégrant une ou plusieurs cavités moléculaires de type calix[4]arène et d’en étudier les propriétés complexantes. L’ensemble des calixarènes synthétisés sont porteurs d’un ou plusieurs groupes PPh2 directement liés au bord supérieur du macrocycle. Plusieurs types de molécules ont été préparées : (i) des bis-calixarènes formant, après complexation, des métallo-capsules; (ii) des calixar!ène-diphosphines adaptées à la formation de complexes bimétalliques dans lesquels les centres métalliques sont placés entre deux coquilles se faisant face. L’activité catalytique de certains de ces métallo-capsules est jusqu’à 40 fois supérieurs à celle observé pour un catalyseur classique.La dernière partie de cette thèse a pour objectif de mettre à la disposition des spécialistes de la chimie des surfaces des phosphacalixarènes originaux destinés à la confection de supports solides P(III)-fonctionnalisés et donc de nouveaux catalyseurs supportés. / The realization of a chemical transformation in a confined space is for molecularist chemists a challenge. Recent research has shown that reactions occurring in a pocket or a molecular cavity were such as to generate selectivities and facilitate new thermodynamically unfavorable reactions.The metal-cavity association allows also the course of catalytic processes in aqueous medium, when the cavity has been made water soluble.The objective of this thesis was to prepare original ligands incorporating one or more cavities of molecular type calix[4]arene and to study their complexing properties. All the synthesized calixarenes are carriers of one or more groups PPh2 directly related to the upper rim of the macrocycle.Several types of molecules were prepared: (i) bis-calixarenes forming, after complexation, metallocapsules, (ii) calixarene-diphosphines suitable for the formation of bimetallic complexes in which the metal centers between two shells are placed facing each other. The catalytic activity of some of these metallo-capsules is 40 times higher than that observed for a conventional catalyst.The last part of this thesis aims to make available experts in surface chemistry of the original phosphacalixarenes for making solid supports P (III)-functionalized and thus new supported catalysts

The extraction of high power with high beam quality from semiconductor lasers has long been a goal of semiconductor laser research. Optically pumped vertical-external-cavity surface-emitting lasers (VECSELs) have already shown the potential for their high power high brightness operation. In addition, the macroscopic nature of the external cavity in these lasers makes intracavity nonlinear frequency conversion quite convenient. High-power high-brightness VECSELs with wavelength flexibility enlarge their applica-tions. The drawbacks of the VECSELs are their poor spectral characteristics, thermal-induced wavelength shift and a few-nm-wide linewidth.The objective of this dissertation is to investigate tunable high-power high-brightness VECSELs with spectral and polarization control. The low gain and microcavity reson-ance of the VECSEL are the major challenges for developing tunable high-power VECSELs with large tunability. To overcome these challenges, the V-shaped cavity, where the anti-reflection coated VECSEL chip serves as a folding mirror, and an extremely low-loss (at tuned wavelength) intracavity birefringent filter at Brewster's angle are employed to achieved the high gain, low-loss wavelength selectivity and the elimination of microcavity. This cavity results in multi-watt TEM00 VECSELs with a wavelength tuning range of 20~30 nm about 975 nm. Also the longitudinal mode discrimination introduced by birefringent filter makes the linewidth narrow down to 0.5 nm. After the tunable linearly polarized fundamental beam is achieved, the tunable blue-green VECSELs are demonstrated by using type I intracavity second-harmonic generation. The spectral control of VECSELs makes it possible to apply them as an efficient pump source for Er/Yb codoped single-mode fiber laser and to realize the spectral beam combining for multi-wavelength high- brightness power scaling.In this dissertation, theory, design, fabrication and characterization are presented. Rigorous microscopic many-body theory of the quantum well gain, based on semiconductor Bloch equations and k.p theory, is introduced. The closed loop design tool based on this theory is not only used to design the VECSEL structure, but also used as a precise on-wafer diagnostics tool by the experiment/theory comparison of the photo-luminescence. The characterization of the wafer shows that the modeling is in good agreement with the measured results.The VECSEL high power high brightness performance relies on the fabrication of the chip. The fabrication method of the VECSEL chip, which provides the optically smooth surface and good heat dissipation, is presented. The anti-reflection coating on the chip surface can significantly improve the slope efficiency of VECSEL when high reflectivity output coupler is used. Over 12-W VECSEL cw output power with 43 % slope efficiency is demonstrated at 0 oC. A beam quality factor (M^2 factor) of 1.75 is obtained at 11 W output power.

Accelerator mass spectrometry (AMS) is by far the predominant technology deployed for radiocarbon tracer studies. Applications are widespread from archaeology to biological, environmental, and pharmaceutical sciences. In spite of its excellent performance, AMS is expensive and complicated to operate. Consequently, alternative detection techniques for 14C are of great interest, with the vision of a compact, user-friendly, and inexpensive analytical method. Here, we report on the use of intracavity optogalvanic spectroscopy (ICOGS) for measurements of the 14C/12C ratio. This new detection technique was developed by Murnick et al. (2008). In the infrared (IR) region, CO2 molecules have strong absorption coefficients. The IR-absorption lines are narrow in line width and shifted for different carbon isotopes. These properties can potentially be exploited to detect 14CO2, 13CO2, or 12CO2 molecules unambiguously. In ICOGS, the sample is in the form of CO2 gas, eliminating the graphitization step that h is required in most AMS labs. The status of the ICOGS setup in Uppsala is presented. The system is operational but not yet fully developed. Data are presented for initial results that illustrate the dependence of the optogalvanic signal on various parameters, such as background and plasma-induced changes in the sample gas composition.

Extreme ultraviolet (XUV) frequency combs exhibit promise for enabling high-precision spectroscopic measurements of myriad chemical species for the first time. Coherent XUV radiation can be generated through high harmonic generation (HHG) in femtosecond enhancement cavities. HHG efficiency is limited by nonlinear phase shifts induced by residual intracavity plasma. The goal of this work is to gain insight regarding plasma dynamics in order to allay the detrimental effects of plasma interactions. Our approach is to conduct simulations of cavity pump-probe experiments by probing with higher-order transverse modes. We propose methods for estimating spatial plasma profiles, gas jet velocities, and the plasma recombination coefficient based on measurements of plasma-induced phase shifts. Beam distortion due to plasma interaction is analyzed and used as another reference for plasma dynamics.

Universiẗat, Diss., 2004--Heidelberg.

La détection de gaz est un domaine d’intérêt pour de nombreuses applications telles que la surveillance de la pollution atmosphérique, la détection d’explosifs, l’analyse des émissions respiratoire de patients, etc... La spectrométrie par lasers accordables permet la réalisation d’instruments compacts et bénéficiant de performances élevées (sélectivité, résolvance et résolution temporelle). Par ailleurs, l’utilisation de lasers à cascade quantique (QCL) permet d’accéder au moyen infrarouge (Mid-IR), où les raies d’absorption des molécules d’intérêt sont plus intenses, ce qui améliore la sensibilité des dispositifs. Les travaux de cette thèse ont porté sur le développement de dispositifs basés sur des QCL pour la détection de gaz. La première partie des travaux porte sur l’exploitation de nouvelles sources Mid-IR telles que les barrettes de QCL multiplexées et les barrettes de QCL cohérents. La seconde partie concerne le développement d’un dispositif intracavité sur lequel une technique de détection par mesure de la tension du laser a été validée. Cette technique possède l’avantage de ne pas nécessiter de détecteur optique et de fonctionner quelle que soit la longueur d’onde du laser. / The field of gas detection is interesting for many applications such as monitoring of air pollution, explosives detection, breath analysis, etc. Tunable laser spectrometry allows to create compact instruments with high performances (selectivity, spectral and temporal resolution). Mid-Infrared (Mid-IR) region can be accessed with the use of Quantum Cascade Laser (QCL). In this region, absorption lines of the molecules of interest are more intense, which improves the devices sensitivity. The work presented in this thesis is focused on the development of QCL-based gas detection devices. First part presents the use of new Mid-IR sources such as multiplexed QCL array and coherent QCL array. Second part is focused on the development of an intracavity setup and a detection technique based on the QCL voltage measurement. This technique does not need the use of an optical detector and can be performed whatever the laser wavelength.