京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20001号 / 工博第4245号 / 新制||工||1657(附属図書館) / 33097 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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<p dir="ltr">Antennas are used to transmit communication signals for many applications including for the navigation of aircraft. To protect the antennas from environmental conditions electromagnetic transparent structures called radomes are used. Advancements in technology have led to the development of hypersonic flight vehicles. These aircraft travel at speeds of Mach 5 and greater subjecting them to extreme environmental conditions. These aircraft require precise navigation making it important to have radome materials that can withstand the extreme conditions of high-speed flight while maintaining transparency to the incoming and outgoing signals of the antenna. Silicon nitride is a ceramic material of interest for high temperature radomes due to its mechanical properties, temperature stability, and satisfactory dielectric properties. Incorporating porosity into silicon nitride further enhances the transmission performance making porous silicon nitride a leading candidate material for high temperature radomes. In this dissertation slip casting with pressureless sintering is proposed as a route to fabricate porous silicon nitride ceramics for radomes. Modification of sintering aids and sintering temperatures are explored as a method to control the amount of porosity. Mechanical properties and dielectric properties of these materials are investigated. </p><p dir="ltr">First, an aqueous silicon nitride suspension developed for slip casting was optimized by investigating the rheological properties, zeta potential, and sedimentation behavior. It was determined that a suspension with 30 vol% solids, 0.5 wt% dispersant (PEI), and a pH of 7 was the optimized condition that resulted in uniform cast parts. This optimized suspension was used to fabricate silicon nitride samples with yttria and alumina sintering aids. An average density of 93% with an average strength of 659 MPa at room temperature and a strength of 472 MPa maintained up to 1200°C was achieved. Dielectric constant and loss tangent were measured on samples with 4-17% porosity to be 5.85-7.70 and <0.02, respectively. </p><p dir="ltr">To create samples with higher levels of porosity and therefore lower dielectric constants the yttria and alumina sintering aids were replaced with ytterbium oxide. Ytterbium oxide assists in forming porous silicon nitride due to the high melting temperature and high viscosity of the resulting glassy phase. Slip cast samples with 5% Yb₂O₃ were sintered at temperatures of 1700-1850°C resulting in porosities of 21-32% and strengths of 267-445 MPa. The dielectric constants of these materials were measured to be 4.56-5.80 with average loss tangents <0.006. The amount of ytterbium oxide was also studied to determine the effects on density, microstructure, mechanical properties, and dielectric properties. Slip-cast samples with 5-15% Yb₂O₃ were made having average porosities of 23-36% and strengths of 275-421 MPa. The dielectric constants of these materials were measured to be 4.13-4.65 with average loss tangents of <0.007. </p><p dir="ltr">Lastly, slip casting using the previously developed and evaluated suspensions was done to fabricate various radome shapes as well as layered structures. The processing method presented in this dissertation shows the potential for fabricating porous silicon nitride for high temperature radome applications with controlled porosity and relatively high strengths.</p>

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No description available.

Le développement de capteurs pour la détection de molécules présentes en très faible concentration est un enjeu sociétal et économique. Il permet de répondre à des besoins de mesure d’analytes dans les secteurs de la santé, de la défense ou encore de l’environnement. Les capteurs optiques intégrés possèdent plusieurs avantages permettant de répondre à ces problématiques. Dans cette thèse, des capteurs optiques intégrés à base de deux micro-résonateurs sont développés. Ils fonctionnent dans le domaine du proche infrarouge et permettent de détecter des molécules d’intérêt présentes en très faible quantité dans un échantillon biologique. Dans un premier temps, les critères de performances comme la sensibilité ou la limite de détection de micro-résonateurs seuls sont définis et optimisés. Puis, l’intérêt de transducteurs à base de deux micro-résonateurs cascadés ou insérés dans une structure interférométrique de type Mach-Zehnder permettant d’utiliser l’effet Vernier est mis en avant. Un algorigramme permettant d’optimiser la conception des transducteurs à effet Vernier est mis en place. Son efficacité est démontrée par la fabrication d’un transducteur à effet Vernier en matériaux polymères qui possède des performances dans l’état de l’art. Ensuite, des transducteurs en matériau silicium poreux sont étudiés. Ce matériau poreux permet d’augmenter la sensibilité du capteur en facilitant le greffage des analytes dans la structure. Les guides en silicium poreux pour la réalisation de micro-résonateurs simples sont optimisés théoriquement. L’avantage de l’utilisation conjointe de guides en polymères et en silicium poreux couplés sur la même puce intégrée, qui permet à la fois de réduire les pertes de propagation optique et d’augmenter la sensibilité du transducteur, ainsi qualifié d’hybride, est détaillé dans ce manuscrit. Les performances en sensibilité et limite de détection de transducteurs à effet Vernier hybride fabriqués à l’aide de guides en silicium poreux et en polymères sont étudiées théoriquement afin de prédire les performances de ces dispositifs. Enfin la mise en œuvre et les premiers essais de fabrication de transducteurs hybrides avec des guides en polymères et en silicium poreux sont détaillés. / The development of biosensors for the detection of extremely low concentration analytes is an economic and societal challenge. It ensures the needs to detect analytes in the economic fields of healthcare, defense and environment. Integrated optical sensors have several advantages to address these challenges. In this thesis, near infrared integrated biosensors for detection of low concentration molecules in biological samples are developed. They are based on two integrated micro-resonators transducers. Firstly, performances criterions such as sensitivity and limit of detection are defined and optimized for single micro-resonator biosensors. The advantage of micro-resonator transducers based on the Vernier effect are presented. To do so, a flowchart is developed in order to optimize the design of Vernier effect integrated transducers based on cascaded micro-resonators or micro-resonators positioned in a Mach-Zehnder interferometric structure. The efficiency of the design procedure is tested by the fabrication of a polymer transducer based on the Vernier effect with state of the art performances. Then, transducers based on porous silicon material are studied. This porous material eases the penetration and the grafting of the analytes in the sensor. Porous silicon waveguides are theoretically optimized for the fabrication of single micro-resonators. The interest of the implementation of polymer and porous silicon waveguides coupled on the same integrated chip, in order to reduce optical propagation losses and to increase sensor sensitivity, is demonstrated. The performances in sensitivity and limit of detection of hybrid porous silicon and polymer waveguides Vernier effect transducers are theoretically studied in order to estimate the performances of these integrated biosensors. Eventually, the design and the first fabrication trials of hybrid porous silicon and polymer waveguides transducers are presented.

Dans le traitement du cancer, l'utilisation de nanoparticules comme vecteurs de molécules thérapeutiques est de plus en plus étudiée dans le but de limiter les effets secondaires toxiques dus à l'administration systémique de molécules thérapeutiques libres. En effet, de par leur taille, les nanoparticules sont capables de s'accumuler de façon plus importante dans les tumeurs que dans les tissus sains. Fonctionnalisées avec des agents de ciblage spécifiques des cellules cancéreuses, leur accumulation dans les tumeurs peut être optimisée. Les nanoparticules de silicium poreux sont particulièrement intéressantes pour des applications biomédicales car elles sont biocompatibles et biodégradables in vivo. Elles possèdent également des propriétés physico-chimiques et photophysiques intéressantes, telles que leurs propriétés texturales, leur photoluminescence intrinsèque et leur capacité à produire de 1O2. L'objectif de cette thèse a été d'étudier le potentiel de nanoparticules de silicium poreux fonctionnalisées pour la thérapie photodynamique, et comme vecteur d'agent de chimiothérapie. Dans un premier temps, la préparation et la caractérisation physico-chimique des nanoparticules de silicium poreux a été réalisée. Les nanoparticules ont ensuite été fonctionnalisées avec un agent de ciblage, le mannose, et des molécules photosensibilisatrices, des porphyrines. Leur utilisation en imagerie et en thérapie photodynamique du cancer avec une excitation mono- ou biphotonique a été montrée in vitro sur des cellules de cancer du sein. Une autre étude a porté sur la vectorisation d'un agent anti-cancéreux hydrophobe, la camptothécine, par des nanoparticules de silicium poreux fonctionnalisées avec des anticorps pour le ciblage de cellules de glioblastome, de neuroblatome et de lymphocytes. Enfin, une étude plus fondamentale de caractérisation de la texture interne du silicium poreux combinant expérience et modélisation moléculaire est présentée. / In cancer therapy, the use of nanoparticles as drug nanovectors is intensively studied in order to overcome the toxic side effects due to the systemic administration of the anti-cancer molecules. Indeed, because of their size, nanoparticles tend to accumulate in tumor cells more importantly than in healthy cells. When functionalized with targeting agents specific to cancer cells, their accumulation in tumors can be optimized. Porous silicon nanoparticles are particularly interesting for biomedical applications because they are biocompatible and biodegradable in vivo. They also have interesting physico-chemical and photochemical properties, such as their textural properties, their intrinsic photoluminescence and their ability to produce 1O2. The goal of this thesis was to study the potential of functionalized porous silicon nanoparticles for photodynamic therapy, and as nanovectors for chemotherapeutic agents. In this purpose, we first studied the preparation and the physico-chemical characterization of the porous silicon nanoparticles. Then, the nanoparticles were functionalized with a targeting agent, mannose, and porphyrin photosensitizers. Their use in imaging and in photodynamic therapy of cancer under 1-photon or 2-photon excitation was shown in vitro on breast cancer cell lines. An other study consisted in the vectorization of a hydrophobic anti-cancer drug, camptothecin, by porous silicon nanoparticles functionalized with antibodies to specifically target glioblastoma, neuroblastoma and lymphocyte cells. Finally, a study of the internal texture of porous silicon combining experiments and molecular modelization is presented.

O objetivo do presente trabalho foi o estudo e análise da resposta óptica de dispositivos de cristal fotônico uni-dimensional (1D) fabricados através do uso da tecnologia de silício poroso. Os resultados obtidos neste trabalho apresentam contribuições significativas no desenvolvimento de uma tecnologia para a fabricação de dispositivos ópticos em silício. As principais contribuições deste trabalho estão direcionadas ao aprimoramento dos processos de fabricação de cristais fotônicos 1D e processos de tratamento térmico. Os resultados da análise estrutural através de microscopia óptica de varredura (MEV) e da resposta óptica (refletância ou absorbância) mostraram que dispositivos de cristal fotônico fabricados em soluções altamente diluídas de HF apresentam melhor desempenho, tendo sido otimizado o processo de fabricação utilizando-se uma célula de duplo compartimento (célula dupla). A otimização da resposta óptica dos dispositivos foi atribuída ao efeito de minimização das rugosidades de interface e minimização de efeitos de anisotropia na taxa de corrosão durante o processo de anodização eletroquímica. O processo eletroquímico utilizado para a fabricação de cristais fotônicos 1D apresentou limitação quanto ao número máximo de camadas, sendo observado que dispositivos com número de camadas acima de 60 apresentavam degradação das suas camadas superficiais, comprometendo a resposta óptica do dispositivo. Este resultado foi atribuído a efeitos de diluição química das camadas expostas à solução por longos períodos de processo. Os dispositivos fotônicos 1D mostraram-se sensíveis a processos de recozimento térmico, deslocando suas bandas fotônicas proibidas para regiões de menor comprimento de onda devido à mudança do índice de refração das camadas e aos efeitos de expansão e compressão das camadas constitutivas do dispositivo. Os dispositivos de micocavidade Fabry-Perot mostraram-se mais sensíveis aos processos de recozimento térmico. Os resultados obtidos no presente trabalho vislumbram grandes possibilidades de aplicação dos cristais fotônicos de PS na fabricação de dispositivos ópticos na tecnologia de silício como filtros, lentes, cavidades ressonantes, guias de ondas, grades de difração e dispositivos sensores. / The aim of the present work was to study and analyze the optical response of one- dimensional (1D) photonic crystal devices obtained by using the porous silicon technology. The experimental results obtained from this work showed the significant contribution to the development of a technological process for optical device fabrication in the silicon substrate. The most important contributions of the work are pointed out to improve the electrochemical process for device fabrication and thermal annealing process in order to improve the optical response of the devices. The results obtained from Scanning electronic microscopy (SEM) and from the optical response of the devices, showed that devices fabricated in the double cell and diluted HF solution improved their optical response due to minimization of the anisotropy of corrosion rate and decreasing of the surface roughness between layers. The electrochemical process used for device fabrication showed the existence of limitation on the numbers of layers because of the existence of chemical dissolution effect that became important for long time process. The 1D photonic crystal devices in PS technology showed high sensibility to thermal annealing process, due to the refraction index change after thermal annealing the photonic band gap position shift down to low wavelength region. The Fabry-Perot devices showed higher sensibility to thermal annealing process improving their optical response after annealing process. The results obtained from the present work showed that the PS 1D photonic device could be applied to optical devices fabrication in silicon technology such as optical filters, lenses, resonant cavities, wave-guide devices, diffraction grade and optical sensor device.

Durante os últimos cinco anos, a nanotecnologia tem atingido avanços significativos em diversas áreas da ciência e tecnologia. Um dos assuntos que está sendo intensamente estudado pela comunidade científica é a intensificação de campo próximo (hot spot) que pode ser aplicada em dispositivos sensores com capacidade de detecção de apenas uma molécula e em nano-antenas ópticas aplicadas na fabricação de dispositivos plasmônicos. Neste sentido, as principais contribuições da presente tese são processos de fabricação de nanoestruturas metálicas e de silício e o estudo da intensificação de campo próximo denominada de pontos quentes (hot spots) nestas estruturas. As nanoestruturas metálicas de Au (ouro) foram obtidas a partir do processo de auto-organização de esferas de poliestireno. As esferas de poliestireno serviram como camada sacrificial (molde) para a obtenção de nanoestruturas metálicas organizadas. Sobre as estruturas de Au organizadas foram depositadas moléculas de cristal violeta para serem utilizadas como moléculas de prova (sondas) no monitoramento da existência dos pontos quentes com o auxílio do espalhamento Raman das moléculas. As nanoestruturas de Au possibilitaram uma intensificação do espalhamento Raman devido à intensificação do campo próximo na superfície metálica periódica de Au. As nanoestruturas e microestruturas de silício foram obtidas a partir da tecnologia de silício poroso. As propriedades do silício poroso foram moduladas através da implantação de íons de hidrogênio (H +) que possibilitou a formação de silício microporoso com forte emissão fotoluminescente (PL) e intensificação do espalhamento Raman superficial devido ao fenômeno de Raman ressonante. Sobre as estruturas macroporosas de silício foram adsorvidas moléculas de azul de metileno para serem utilizadas como moléculas de prova para monitoramento da intensificação do campo próximo e do efeito SERS no silício. A obtenção da intensificação de campo próximo em silício é uma contribuição completamente inédita, pois este fenômeno devia-se, até o momento, somente a materiais metálicos (nanoestruturas metálicas), mostrando sua existência também no silício. / During the last five years, nanotechnology has achieved significant progress in several areas of science and technology. One of the issues that are being intensively studied by the scientific community is the intensification of near-field (hot spot) that can be applied to devices with sensors capable of detecting a single molecule and nano-optical antennas used in the fabrication of plasmonic devices. In this sense, the main contributions of this thesis are processes for manufacture of metal and silicon nanostructures and the study of near-field intensification called hot spots in these structures. The metal nanostructures of Au (gold) were obtained from the process of self-assembling of polystyrene beads. The polystyrene beads were used as sacrificial layer (mold) for obtaining organized metallic nanostructures. On the structures of organized Au were deposited molecules of violet crystal to be used as proof of molecules (probes) to monitor the existence of hot spots with the help of Raman scattering of molecules. The Au nanostructures allowed an intensification of the Raman scattering due to the intensification of the near-field in the periodic Au surface. The microstructures and nanostructures of silicon were obtained using the porous silicon technology. The properties of porous silicon were modulated by the implantation of hydrogen ions (H +) that allowed the formation of microporous silicon which showed high photoluminescence emission (PL) and Raman scattering intensification of the surface due to the phenomenon of resonant Raman. Methylene blue molecules were adsorbed on the macroporous silicon structures to be used as probe molecule for the monitoring of near-field intensification and the SERS effect in silicon. The obtaining of near-field intensification in silicon is an entirely unprecedented contribution, because this phenomenon had been observed, so far, only on the metallic materials (metal nanostructures), showing its existence in the silicon too.

Το αντικείμενο της παρούσας Διδακτορικής Διατριβής είναι η αλληλεπίδραση της ηλεκτρομαγνητικής ακτινοβολίας με νανοδομημένους ημιαγωγούς. Για το σκοπό αυτό σχεδιάστηκε και κατασκευάστηκε μια διάταξη καταγραφής φασμάτων φωτοφωταύγειας, συναρτήσει της θερμοκρασίας. Τα δείγματα που εξετάστηκαν περιέχουν νανοκρυστάλλους του πυριτίου. Ερευνήθηκαν δυο διαφορετικές προσεγγίσεις για την παρασκευή τέτοιων δειγμάτων. Η πρώτη αφορά την θερμική αποσύνθεση του SiO σε θερμοκρασίες άνω των 850 ºC και οδηγεί στην παρασκευή δειγμάτων με νανοκρυστάλλους πυριτίου σε μια μήτρα από οξείδιο του πυριτίου. Η δεύτερη είναι ο σχηματισμός πορώδους πυριτίου μέσω ανοδικής ηλεκτροδιάβρωσης, τόσο σε συνθήκες ανοδικής πόλωσης, όσο και σε συνθήκες ανοιχτού κυκλώματος. Τα δείγματα που προήλθαν από θερμική αποσύνθεση του SiO επιδεικνύουν έντονη φωτοφωταύγεια, σε θερμοκρασία περιβάλλοντος, στο εγγύς υπέρυθρο και σε ενέργειες μεγαλύτερες του ενεργειακού χάσματος του πυριτίου (1.12 eV), ως αποτέλεσμα της εξιτονικής επανασύνδεσης υπό συνθήκες κβαντικού εντοπισμού. Τα φάσματα φωτοφωταύγειας και ο δομικός χαρακτηρισμός, έδωσαν χρήσιμες πληροφορίες σχετικά με την αλληλεπίδραση και προέλευση της εκπεμπόμενης ακτινοβολίας, της δομής και κινητικής του SiO που υπόκειται σε θερμική αποσύνθεση. Με την παρασκευή πορώδους πυριτίου, αναπτύχθηκε μια νέα μεθοδολογία για την ανάπτυξη μικροδομών πορώδους πυριτίου σε συνθήκες ανοιχτού κυκλώματος, με απολύτως ελεγχόμενη γεωμετρία και ιδιότητες φωτοφωταύγειας. Η μεθοδολογία αυτή είναι ενδιαφέρουσα για την ανάπτυξη μιας πληθώρας μικρο-ηλεκτρομηχανικών συστημάτων βασισμένα στο πορώδες πυρίτιο, όπως οπτοηλεκτρονικές διατάξεις και αισθητήρες. / The objective of this Thesis is the study of the interaction of electromagnetic radiation with nanostructured semiconductors. For this purpose we have designed and constructed a photoluminescence setup for the recording of spectra at various temperatures. The samples that have been investigated contain nanocrystals of silicon. We investigated two different approaches for the synthesis of such samples. The first one involves the thermal decomposition of SiO at temperatures above 850 ºC and results in silicon nanocrystals embedded in silicon oxide matrix. The second is the formation of porous silicon using the anodic dissolution of silicon under external anodic bias, as well as under open circuit potential conditions. Samples prepared by thermal decomposition of SiO exhibit strong photoluminescence, at room temperature, in the near infrared and at energies higher than the band gap of bulk silicon (1.12 eV), as a result of excitonic recombination under quantum confinement conditions. The recorded spectra and the structural characterization, gave us valuable information about the interaction, the origin of the emitted radiation, the structure and the kinetics of SiO undergoing thermal decomposition. The investigations concerning the formation of porous silicon, resulted in the development of a novel technique for the formation of porous silicon microstructures under open circuit potential conditions. The microstructure geometry and photoluminescence characteristics can be tuned. This technique is interesting for the fabrication of a variety of micro-electromechanical systems, based on porous silicon, such as optoelectronic devices and sensors.