Doctor of Philosophy / Department of Physics / Kristan L. Corwin / Current portable near-infrared optical frequency references offer modest accuracy and instability compared to laboratory references. Low pressure reference cells are necessary to realize features narrower than the Doppler broadened overtone transitions, and most setups to date have occurred in free-space. Hollow-core photonic crystal fibers offer a potential alternative to free-space setups through their small cores (~10’s of µm) and low-loss guidance. Furthermore, HC-PCF can be made into fiber cells that could be directly integrated into existing telecommunications networks. Efforts were made to fabricate these fiber cells with a low pressure of molecules trapped inside, but this has proven to be quite challenging. Therefore, investigation of these fibers is conducted by placing the ends of the fiber inside vacuum chambers loaded with acetylene (12C2H2). The linewidths of several P branch transitions (near 1.5 µm) are investigated as a function of acetylene pressure and optical pump power in three different HC-PCFs. Frequency modulation spectroscopy is then implemented on the acetylene-filled HC-PCF to generate sub-Doppler dispersion features that are useful for frequency stabilization using standard servo electronics. Instability and accuracy of this near-IR optical reference were then determined by analysis of heterodyne experiments conducted with frequency combs referenced to a GPS-disciplined rubidium oscillator. The instability and accuracy of this HC-PCF reference are within an order of magnitude of free-space experiments, as expected based on the ratio of linewidths observed in the two experiments. Therefore, HC-PCF has been shown to be suitable for potential frequency references. Further work is necessary to fabricate gas fiber cells with high optical transmission and low molecular contamination.

Research towards the development of a gas-discharge fibre laser using noble gases, with target emission wavelengths in the mid-IR. Additional and separate work on gas treatment methods for managing the formation of photo-induced defects in silica glass.

This thesis focuses on the investigation and development of an integrated optical biosensor based on enhanced Raman techniques that will provide label-free detection of biomolecules. This is achieved by using hollow core photonic crystal fibers (HC-PCF), nanoparticles, or both. HC-PCF is a unique type of optical fiber, with continuous ‘channels’ of air (typically) running the entire length. The channels serve to confine electromagnetic waves in the core of the fiber, and tailor its transmission properties. Using HC-PCF as a biosensor requires development of a robust technique to fill hollow-core photonic crystal fibers. Though several groups have reported selective filling of HC-PCF’s core, the processes are cumbersome and limit the choice of liquid to avoid multimode behavior. In my Master’s thesis, I presented a simple technique to non-selectively fill all the HC-PCF channels with samples. The non-selective filling preserves the photonic bandgap property of the fiber, and yields an extremely strong interaction of light and the sample that produces considerable enhancement of the Raman signal from the analyte. Up to now, non-selective filling was accomplished through capillary action and it delivered a Raman signal enhancement of approximately 30-fold, which is not sensitive enough to detect biomolecules at the clinical level. Moreover, there were issues of reliability and reproducibility, due to evaporation, filling and coupling light into the fiber. The objective of this PhD research was to overcome these problems by developing a robust optical fiber platform based on Raman spectroscopy that can be used in a clinical setting. I initially focused on heparin, an important blood anti-coagulant that requires precise monitoring and control in patients undergoing cardiac surgery or dialysis. Since the Raman spectra of heparin-serum mixtures exhibits Raman peaks of heparin with poor signal-to-noise ratios, I concentrated on enhancing the heparin Raman signal and filtering out the spectral background of the serum to improve detection sensitivity. Reaching maximum enhancement of the Raman signal required a strong interaction of light and analyte, which can be achieved by using hollow core photonic crystal fiber as I had used in my Master’s research. Using a small piece of HC-PCF I was able to reach an enhancement in the heparin Raman signal of greater than 90-fold. With this degree of enhancement, I was able to successfully detect and monitor heparin in serum at clinical levels, something that had never been accomplished previously. After developing HC-PCF as a Raman signal enhancer, I focused on making the HC-PCF sensor robust, reliable and reusable. This was achieved by integrating the HC-PCF with a differential pressure system that allowed effective filling, draining and refilling of the samples in an HC-PCF, under identical optical conditions. To demonstrate the device’s detection capabilities, various concentrations of aqueous ethanol and isopropanol, followed by different concentrations of heparin and adenosine in serum, were successfully monitored. To further improve the sensitivity of the HC-PCF based Raman sensor, I incorporated surface enhanced Raman scattering (SERS), by introducing nanoparticles into the HC-PCF fibers. The research focused on determining the optimal volume and size of silver nanoparticles to achieve maximum enhancement of the Raman signal in the HC-PCF. The HC-PCF enhanced the Raman signal of Rhodamine 6G (R6G) approximately 90-fold. In addition, the optimal size and volume of AgNP enhanced the Raman signal of R6G approximately 40-fold, leading to a total enhancement of approximately 4,000 in HC-PCF. This was then used to demonstrate the application of a SERS based HC-PCF sensing platform in monitoring adenosine (a clinically important molecule), as well as malignant cells such as leukemia. Finally, I used hollow core crystal fibers to significantly enhance the efficiency of two-photon photochemistry. Although two-photon photochemical reactions are difficult to achieve with a small volume, I accomplished it by using a novel platform of HC-PCF to efficiently execute the two-photon induced photodecarbonylation reaction of cyclopropenone 1, and its conversion to the corresponding acetylene. The simple optical design configuration involved coupling an 800-nm tsunami laser to a short piece of HC-PCF filled with the sample. This allowed me to increase the efficiency of two-photon induced photochemistry by 80-fold, compared to a conventional spectrophotometer cuvette. Thus, this work leads to the use of HC-PCFs to more effectively study two-photon induced photochemistry processes, which was limited due to the difficulty of detecting photochemical events with a small excitation volume.

Depuis leur avènement, les fibres à cristal photonique à cœur creux ont prouvé leur capacité à convertir des fréquences avec une haute efficacité, notamment en jouant sur le phénomène de diffusion Raman stimulée. Dans le cadre d’un contrat CIFRE entre la société GLOphotonics et l’institut de recherche Xlim, ce projet de thèse a consisté à développer ces fibres afin d’améliorer leurs performances optiques pour cibler deux voies d’applications: une industrielle pour proposer un laser compact multi-ligne dans le visible et dans l’UV et une seconde plus fondamentale pour réaliser un synthétiseur d’onde optique. L’amélioration de ces performances repose sur l’exacerbation de l’inhibition du couplage entre le mode du coeur d’air et les modes de silice de la gaine. Pour cela deux types de micro-structures ont été explorées à savoir une maille Kagomé et une maille tubulaire. Plusieurs fibres ont été alors fabriquées démontrant des performances records sur toute une gamme de longueurs d’onde (8,5 dB/km à 1 µm, 7,7 dB/km à 750 nm, 13,8 dB/ km à 549 nm, et autour de 70 dB/km à 355 nm). Concernant la fonctionnalisation de ces fibres, des micro-capsules photoniques ont été conçues et réalisées permettant à la fois de palier au problème de la perméabilité de la silice au gaz (stabilité de la conversion dépassant 12 mois) et de démontrer une conversion de 26 lignes dans le visible. Un produit industriel nommé CombLas a alors été produit puis appliqué à une étude de cytométrie en flux pour étudier l’influence du taux de répétition du laser de pompe. Ce produit a également été étendu à la gamme spectrale de l’UV avec la génération de 24 lignes entre 225-400 nm. Enfin, des travaux plus fondamentaux ont été réalisés consistant à développer un synthétiseur d’onde optique à base de génération Raman dans ces fibres creuses. Une nouvelle dynamique a été observée démontrant le piégeage de molécules d’hydrogène par un réseau optique auto-assemblé de puits de potentiel ultra-profonds et nanométriques. Cela permis de générer un régime Lamb-Dicke de la diffusion Raman stimulée. Des signatures sub-Doppler usuellement vues dans les atomes froids ont été mesurées avec des largeurs de bandes plus étroites de plus de 5 ordres de grandeurs par rapport à ce qui est prédit dans la littérature. Finalement, cette largeur de bande a été optimisée d’un ordre de grandeur en jouant sur la longueur de la fibre et la pression de l’hydrogène. / Since their advent, hollow-core photonic crystal fibers have proved to be highly efficient for frequency conversion, especially via by playing with stimulated Raman scattering. Within the frame work of a CIFRE contract between the firm GLOphotonics and the Xlim research institute, this thesis project has consisted in developing these fibers to enhance their optical performances, in order to target two different field of applications: an industrial one to offer a a compact multi-line laser in the visible and UV and a second more fundamental one to realize a optical wave synthesizer. The amelioration of these performances relies on the exacerbation of the inhibition of the coupling between the air core mode and the silica cladding modes. Two types of micro-structures have been explored, a Kagomé and a tubular lattice. Several fibers have been fabricated demonstrating record performances on all a wavelength range (8.5 dB/km at 1 µm, 7.7 dB/km at 750 nm, 13.8 dB/km at 549 nm, and around 70 dB/km at 355 nm). Concerning the functionalization of the fibers, photonic micro-cells have been designed and realized enabling to overcome the problem the permeability of silica to gas (conversion stability over 12 months) and demonstrate a conversion to 26 lines in the visible. An industrial product coined CombLas has been made and used for flow cytometry in order to study the influence of the repetition rate of the pump laser. This product has also been extended to the UV range with 24 lines generated between 225-400 nm. Also, more fundamental research has been realized consisting in developing an optical wave synthesizer based on Raman generation in hollow core fibres where a new dynamic has been observed demonstrating the trapping of hydrogen molecules by an auto-assembled optical lattice of ultra-deep and nano-metric potential wells. This configuration has enabled to generate a Lamb-Dicke regime of stimulated Raman scattering. Sub-Doppler signatures usually found in cold atoms have been measured with linewidths narrower than 5 orders of magnitude than what is predicted in the literature. Finally, this linewidth has been optmised of an order of magnitude by plaing on the length of the fiber and the pressure of hydrogen.