La biopsie du ganglion sentinelle (GS) est actuellement la technique de référence pour le diagnostic des métastases ganglionnaires du cancer du sein. Cependant, les traceurs utilisés pour la cartographie du GS (colorant bleu et radiocolloïde) ne sont pas idéaux et peuvent occasionner des réactions allergiques et engendrer des coûts importants. Une alternative à l'utilisation de ces traceurs repose sur le repérage du GS par imagerie de fluorescence proche infrarouge à l'aide de nanoparticules. Deux types de nanoparticules ont été étudiés : les Quantum Dots (QDs) à base d'indium et les nanoparticules de silice (NPSi) renfermant de la cyanine 7. Dans un modèle murin de carcinome mammaire, tous les GS envahis par les métastases ont pu être visualisés grâce à la fluorescence des QDs-indium. L'étude de biodistribution a mis en évidence une capture majeure des QDs au point d'injection et dans les ganglions associée à une faible concentration dans le foie et la rate. La toxicité des QDs a été évaluée in vitro et a démontré une toxicité fortement réduite des QDs-indium par rapport aux QDs-cadmium. Les NPSi présentent les avantages suivants : biocompatibilité, amélioration de la rétention dans le ganglion et des propriétés photophysiques par rapport au fluorophore libre. Le GS est rapidement visualisable par fluorescence suite à l'injection de NPSi. Le suivi des souris, pendant 3 mois post-injection, n'a révélé aucun signe de toxicité générale ou hépatique. Ces deux types de nanoparticules fluorescentes sont particulièrement bien adaptés à la cartographie du GS et pourraient avantageusement remplacer les traceurs employés actuellement / Sentinel lymph node (SLN) biopsy is a reliable technique for the diagnosis of metastases in breast cancer. However, the tracers used (blue dye and radiocolloid) are not optimal because they can cause allergic reactions and major costs in waste processing. Our strategy was to use near-infrared emitting nanoparticles for the mapping of SLN: indium-based Quantum Dots (QDs) and cyanine 7 embedded in silica nanoparticles (SiNP). In a murine model of mammary carcinoma, all SLN containing lymphatic metastases could be visualized with fluorescent indium-based QDs. The biodistribution study concluded that the major organs of retention were the injection point and lymph nodes whereas liver and spleen accumulated fewer QDs. The cytotoxicity tests demonstrated a weak in vitro toxicity of indium- compared to cadmium-based QDs. SiNP show several advantages over free fluorophore such as biocompatibility, better retention in the SLN and greatest photophysical properties. SLN could be mapped as soon as 5 minutes after SiNP injection. The in vivo toxicity in mice was followed during 3 months after injection and did not reveal any signs of general or hepatic toxicity. Both fluorescent nanoparticles are thus well adapted for the mapping of the SLN and could be a favourable substitute to the actually tracers

Nas últimas décadas a medicina nuclear tornou-se uma grande aliada no auxílio ao diagnóstico de doenças e também para o tratamento do câncer. Parte deste sucesso está relacionada à constante pesquisa e desenvolvimento de novos radiofármacos. Uma classe de molécula que vem se mostrando promissora para o tratamento de tumores, tanto na sua forma orgânica quanto na forma de complexos organo-metálicos, é a tiossemicarbazona e seus derivados, os quais também podem formar complexos com radioisótopos metálicos dando origem a radiofármacos para diagnóstico e terapia. Neste trabalho foram preparados complexos com o ligante benzil-5-hidroxi-3-metil-5-fenil-4,5-diidro-1H-pirazol-1-carboditionato (H2bdtc) com os radioisótopos [99mTc]tecnécio, (67/68Ga)gálio e (111In)índio, e foram avaliados a pureza radioquímica, Log P e a estabilidade na presença de L-cisteína, L-histidina, soro albumina humana (SAH) e plasma de sangue humano; também foram avaliadas a taxa de captação dos radiofármacos in vitro em células de melanoma murino B16F10 e TM1M, além da avaliação da captação ex vivo e in vivo utilizando camundongos C57B/6 inoculados com as duas linhagens tumorais. Com o [99mT]tecnécio foram obtidos dois complexos diferentes, dependendo da concentração do PBS na solução, sendo que em um deles foi possível confirmar sua estrutura como [[99mTc]O(bdtc)(Hbdtc)] a partir do complexo de rênio [ReO(bdtc)(Hbdtc)], o outro complexo de [99mTc]tecnécio, bem como de (67/68Ga)gálio e (111In)índio não tiveram a estrutura caracterizada. A eficiência de marcação dos complexos foi superior a 90 %, com Log P maior que 1 para os complexos [[99mTc]O(bdtc)(Hbdtc)], [[99mTc]-bdtc] e [67/68Ga-bdtc] e 0,9 para [111In-bdtc]. Todos os complexos se mostraram com boa estabilidade na presença de L-cisteína e L-histidina, principalmente na primeira hora de incubação, mas não o foram na presença de SAH e plasma. A captação in vitro dos complexos em células B16F10 e TM1M variou entre 0,6 % e 1,8 %, e nos estudos de biodistribuição ex vivo foi obesrvada intensa e persistente captação hepática e no baço, superando 90 %, e captação no tumor variando de 0,2 % a 3 %, enquanto que nas imagens in vivo não foi possível observar de forma uma adequada captação nos tumores a ponto de permitir o uso como agente de diagnóstico. Os resultados permitem concluir que os complexos de derivados tiossemicarbazonas podem formar complexos com diferentes metais, mas novos derivados devem ser preparados para tentar melhorar o desempenho nos sistemas biológicos. Os experimentos com animais foram aprovados pela Comissão de Ética em Pesquisa da Faculdade de Medicina - USP, processo 372/12 / In recent decades, nuclear medicine has been used as diagnostic agent for disease and for the treatment of cancer. Part of this success is related to the constant research and development of new radiopharmaceuticals. Thiosemicarbazone and their derivatives have proven to be promising agent for the treatment of tumors, both in its organic form or as organo-metallic complexes. Also, they can to form complexes with metal radioisotopes giving radiopharmaceuticals for diagnosis and therapy. In this work we prepared complex of benzyl-5-hydroxy-3-methyl-5-phenyl-4,5-dihydro-1H-pyrazol-1-carboditionato (H2bdtc) with radioisotopes [99mTc]technetium (67/68Ga)gallium and (111In)indium and the radiochemical purity, Log P and stability in the presence of L-cysteine, L-histidine, human serum albumin (HSA) and human blood plasma were assessed; also were assessed the in vitro uptake rate of radiopharmaceuticals in murine melanoma cells B16F10 and TM1M, besides the evaluation of ex vivo uptake and in vivo using C57Bl/6 mice inoculated with both tumor lines. With [99mT] technetium two different complexes were obtained, depending on the concentration of the PBS in the solution, and one of them was had its structure to confirm as [[99mTc]O(bdtc)(Hbdtc)] from the standard rhenium complex [ReO(bdtc)(Hbdtc)], the other [99mTc] echnetium complex as well as (67/68Ga)gallium and (111In)indium not have characterized the structure. The labeling efficiency of compleos was higher than 90%, with log P higher than 1 for the complexes [[99mTc]O(bdtc)(Hbdtc)], [[99mTc]-bdtc] and [(67/68Ga)-bdtc] and 0.9 to [111In-bdtc]. All the complexes showed good stability in the presence of L-cysteine and L-histidine, especially in the first hour of incubation, but not in the presence of HSA and plasma. The uptake in vitro complexes in B16F10 and TM1M cells varied between 0.6% and 1.8%, and in ex vivo biodistribution studies was obesrvada intense and persistent liver uptake and spleen, exceeding 90%, and tumor uptake in changing from 0.2% to 3%, while in vivo imaging was not possible to observe a properly uptake in tumors, not allowing to use these molecules as a diagnostic agent. The results indicate that the thiosemicarbazone derivative complex can give complexes with different metals, but new derivatives should be prepared to try to improve performance in biological systems. The animal experimentation was approved by Comissão de Ética em Pesquisa da Faculdade de Medicina - USP, proccess 372/12

Ce travail de thèse porte sur la synthèse organo-métallique de nanoparticules (NPs) semi-conductrices colloïdales de phosphures d’indium (InP), de zinc (Zn3P2) et de structures cœur/coquille obtenues par la croissance d’une couche de sulfure de zinc (ZnS) à la surface des NPs. Les objectifs consistent à comprendre et maîtriser la synthèse dans le but de décaler les longueurs d’onde d’absorption et d’émission vers le proche infra-rouge, domaine spectral intéressant pour l’imagerie biomédicale.Le premier chapitre présente l’état de l’art sur les nanocristaux (NCx) d’InP et d’InP/ZnS. Un bref rappel sur les propriétés physico-chimiques des NCx semi-conducteurs est présenté et différentes synthèses sont décrites. Une attention toute particulière a été portée sur la taille des NCx, le décalage de l’émission de fluorescence vers les plus grandes longueurs d’onde et l’optimisation des rendements quantiques. Les potentialités offertes par ces objets soit pour les diodes électroluminescentes (LED) blanches soit pour l’imagerie biomédicale montrent l’intérêt d’utiliser les NCx de type InP/ZnS plutôt que d’autres matériaux à base d’éléments toxiques (Cd, Pb, …).Le deuxième chapitre porte sur une synthèse à partir des carboxylates d’indium connue de la littérature. Le but est alors de caractériser la structure des NPs pour comprendre le déroulement de la synthèse et de l’enrobage. Des mesures par résonance magnétique nucléaire (RMN) en phase solide et spectroscopie photo-électronique par rayons X (XPS) révèlent l’oxydation des NPs d’InP. La couche d’oxyde qui se forme durant la synthèse des NPs d’InP s’épaissit lors de l’enrobage. Cette oxydation provient d’un couplage décarboxylant des acides carboxyliques à haute température en présence des NPs. Elle serait à l’origine de l’inhibition de croissance des objets, ce qui limiterait les gammes de longueurs d’onde atteignables.Le troisième chapitre concerne une nouvelle synthèse à partir d’amidinate d’indium au lieu des carboxylates d’indium. L’intérêt de cette approche est la possibilité d’abaisser considérablement la température de réaction (150°C au lieu de 280°C) et ainsi d’éviter la réaction secondaire de décarboxylation. Un enrobage à basse température (150°C) est aussi mis en place. La synthèse induit également une oxydation de la surface des NPs d’InP. Un nouveau couplage a lieu entre les ligands, l’acide palmitique et l’hexadécylamine, et donne de nouvelles conditions oxydantes. Le jeu sur les ratios des ligands montre qu’en bouleversant le milieu réactionnel, les NPs d’InP ne présentent pas de réponse en luminescence concluante. La synthèse et l’enrobage sont alors réalisés sous atmosphère de dihydrogène (H2) en réacteur Fisher-Porter dans le but de contrer ces conditions oxydantes. La synthèse et l’enrobage donnent des tailles de NPs de l’ordre de 3,4 nm (condition nécessaire pour s’approcher d’une émission dans l'infra-rouge) et un rendement quantique de 18-20 %, résultats encore jamais atteints lors de cette thèse.Le dernier chapitre est consacré à une étude exploratoire sur les NPs de Zn3P2. Le phosphure de zinc est un matériau prometteur du fait de l’abondance de ses constituants non toxiques et des longueurs d’onde potentiellement accessibles. Différents paramètres de synthèse sont étudiés et les propriétés structurales et optiques sont caractérisées. Des résultats préliminaires sur l’enrobage montrent des difficultés liées à la stabilité des NPs de Zn3P2. L’utilisation de l’oxyde de trioctylphosphine (TOPO) semble permettre la passivation de ces NPs à l’air et en travaillant sous H2 une meilleure stabilité est envisageable / Résumé de la thèse en anglais : This PhD investigation focuses on organometallic synthesis of indium phosphide (InP), zinc phosphide (Zn3P2) colloidal semiconductor nanoparticles (NPs) and core/shell structures which were obtained by the growth of a layer of zinc sulfide (ZnS) on the surface. The objectives are to understand and control the synthesis in order to shift the absorption and emission wavelengths to the near infra-red range, interesting for biomedical imaging.The first chapter presents the state of the art on the InP and InP/ZnS nanocrystals (NCx). A brief recall on the physical and chemical properties of semiconductor NCx is presented and various syntheses are described. Particular attention was paid to the size of NCx, the shift of the fluorescence emission to higher wavelengths and the optimization of quantum yields. The potential of these objects for white light emitting diodes (LED) or biomedical imaging shows the value added of using InP/ZnS NCx rather than other materials based on toxic elements such as cadmium, lead elements…The second chapter focuses on a synthesis from indium carboxylates known in the literature. The goal is to characterize the structure of NPs to understand the procedure of the synthesis and the coating. Measurements by Nuclear Magnetic Resonance (NMR) in solid state and Photoelectronic X-ray spectroscopy (XPS) revealed the oxidation of InP of the NPs. This oxide layer increases during the coating. This originates from a decarboxylating coupling of carboxylic acids at high temperature in the presence of NPs. This oxidation is believed to inhibit the growth of the object, which restricts the attainable range of wavelengths.The third chapter provides a novel synthesis from indium amidinate instead of indium carboxylate. The advantage of this approach is the potential to lower significantly the reaction temperature (150°C instead of 280°C) and to avoid secondary decarboxylation reaction. A coating with ZnS at low temperature (150°C) is also developed. The synthesis of InP NPs also causes an oxidation of the surface. A coupling takes place again between the ligands, palmitic acid and hexadecylamine providing new oxidizing conditions. The study of different ratios of ligands shows that when the reaction medium is modified, the InP NPs do not exhibit a conclusive luminescence response. Synthesis and coating are carried out under an atmosphere of hydrogen (H2) in Fisher-Porter reactor in order to counter these oxidizing conditions. NPs with diameters of the order of 3,4 nm (a necessary condition to approach the infra-red emission) and a quantum yield of 18-20% are thus obtained. These had never been observed before during this thesis.The last chapter is devoted to an exploratory study on Zn3P2 NPs. Zinc phosphide is a promising material because of non-toxic and abundant constituents, and potential access to near infra-red wavelengths. Different synthesis parameters are studied and the structural and optical properties are characterized. Preliminary results on the coating show instabilities of the Zn3P2 NPs. The use of trioctylphoshine oxide (TOPO) appears to allow the passivation of the NPs in the air and a better stability is possible under an atmosphere of H2

L'optomécanique est la science des interactions entre la lumière et les mouvements mécaniques. Ce rapport de thèse décrit des expériences réalisées avec des microdisques fabriqué dans différents résonateurs semi-conducteurs III-V: l'Arséniure de Gallium (GaAs), l'Arséniure d'Aluminium Gallium (AlGaAs) et l'Arséniure d'Indium Phosphide (InGaP). Ces matériaux sont compatibles avec les fonctionnalités de l’optoélectronique et procurent un couplage optomécanique géant. Pour améliorer les performances des résonateurs en GaAs, nous avons développé des méthodes de traitement de surface permettant de réduire la dissipation optique par un facteur dix et ainsi d'atteindre un facteur de qualité de six millions. En plus de ces études sur le GaAs, nous avons réalisés une étude comparative des interactions optomecaniques dans des microdisques d'InGaP et d'AlGaAs, et nous avons mis en évidences leurs résonances optomécaniques. Finalement, nous avons réalisé des mesures de force avec des résonateurs en GaAs, démontrant un nouveau principe de détection basé sur notre étude de leur la trajectoire dans l'espace de phase et leur bruit de phase / Optomechanics studies the interaction between light and mechanical motion. This PhD thesis reports on optomechanical experiments carried with miniature disk resonators fabricated out of distinct III-V semiconductors: Gallium Arsenide (GaAs), Aluminium Gallium Arsenide (AlGaAs) and Indium Gallium Phosphide (InGaP). These materials are compliant with optoelectronics functionalities and provide giant optomechanical coupling. In order to boost performances of GaAs resonators, we implemented surface control techniques and obtained a ten-fold reduction of optical dissipation, attaining a Q of six million. On top of GaAs, we performed a comparative investigation of optomechanical interactions in InGaP and AlGaAs disk resonators, and demonstrated their operation as optomechanical oscillators. Finally, we carried out optomechanical force sensing experiments with GaAs resonators, analyzing a new sensing principle in light of the phase space trajectory and phase noise of the corresponding oscillators

Previous research in InGaN/GaN light emitting diodes (LEDs) employing semi-classical drift-diffusion models has used reduced polarization constants without much physical explanantion. This paper investigates possible physical explanations for this effective polarization reduction in InGaN LEDs through the use of the simulation software SiLENSe. One major problem of current LED simulations is the assumption of perfectly discrete transitions between the quantum well (QW) and blocking layers when experiments have shown this to not be the case. The In concentration profile within InGaN multiple quantum well (MQW) devices shows much smoother and delayed transitions indicative of indium diffusion and drift during common atomic deposition techniques (e.g. molecular beam epitaxy, chemical vapor deposition). In this case the InGaN square QW approximation may not be valid in modeling the devices' true electronic behavior. A simulation of a 3QW InGaN/GaN LED heterostructure with an AlGaN electron blocking layer is discussed in this paper. Polarization coefficients were reduced to 70% and 40% empirical values to simulate polarization shielding effects. QW shapes of square (3 nm), trapezoidal, and triangular profiles were used to simulate realistic QW shapes. The J-V characteristic and electron-hole wavefunctions of each device were monitored. Polarization reduction decreased the onset voltage from 4.0 V to 3.0 V while QW size reduction decreased the onset voltage from 4.0 V to 3.5 V. The increased current density in both cases can be attributed to increased wavefunction overlap in the QWs.

Photonic crystals (PhCs) are structures periodic in thedielectric constant. They exhibit a photonic bandgap, i.e., arange of wavelengths for which light propagation is forbidden.Engineering of defects in the PhC lattice offers new ways toconfine and guide light. PhCs have been manufactured usingsemiconductors and other material technologies. This thesisfocuses on two-dimensional PhCs etched in InP-based materials.Only recently, such structures were identified as promisingcandidates for the realization of novel and advanced functionsfor optical communication applications. The primary focus was on fabrication and characterization ofPhC structures in the InP/GaInAsP/InP material system. Thedemands on fabrication are very high: holes as small as100-300nm in diameter have to be etched at least as deep as 2µm. Thus, different etch processes had to be explored andspecifically developed for InP. We have implemented an etchingprocess based on Ar/Cl2chemically assisted ion beam etching (CAIBE), thatrepresents the state of the art PhC etching in InP. Different building blocks were manufactured using thisprocess. A transmission loss of 10dB/mm for a PhC waveguide, areflection of 96.5% for a 4-row mirror and a record qualityfactor of 310 for a 1D cavity were achieved for this materialsystem. With an etch depth of 4.5 µm, optical loss wasfound to be close to the intrinsic limit. PhC-based opticalfilters were demonstrated using (a) a Fabry-Pérot cavityinserted in a PhC waveguide and (b) a contra-directionalcoupler. Lag effect in CAIBE was utilized positively to realizehigh quality PhC taper sections. Using a PhC taper, a couplingefficiency of 70% was demonstrated from a standard ridgewaveguide to a single line defect PhC waveguide. During the course of this work, InP membrane technology wasdeveloped and a Fabry-Pérot cavity with a quality factorof 3200 was demonstrated. Keywords:photonic crystals, photonic bandgap materials,indium phosphide, dry etching, chemically assisted ion beametching, reactive ion etching, electron beam lithography,photonic integrated circuits, optical waveguides, resonantcavities, optical filtering, finite difference time domain,plane wave expansion.

Core- and Valence Photoelectron Spectroscopy (PES), X-ray- and Ultraviolet-Visible Absorption Spectroscopy (XAS and UV-Vis), Scanning Tunneling Microscopy (STM) and Density Functional Theory (DFT) calculations are used to study the electronic and geometrical structure of a class of macro-cyclic molecules, Phthalocyanines (Pc), on surfaces. These molecules are widely studied due to their application in many different fields. Multilayer and monolayer coverages of Iron Phthalocyanine (FePc) and metal-free Phthalocyanine (H2Pc) deposited on different surfaces are investigated in order to get insight in the electronic and geometrical structure of the obtained overlayers, of crucial importance for the understanding of the film functionality. Sublimation of molecular thick films on Si(100) and on conducting glass results in films with molecules mainly oriented with their molecular plane orthogonal to the surface. Ex-situ deposited H2Pc films on conductive glass show different molecular orientation and morphology with respect to the vacuum sublimated films. We study the monolayer adsorption structure of FePc and H2Pc and compare our results with other Pc’s adsorbed on graphite. We find that the molecular unit cell and the superstructure is characteristic for each Pc adsorbed on graphite, even if the geometrical size of the compared molecules is the same. The PE- and XA- spectra of FePc on graphite are essentially identical for the mono- and multilayer preparations, evidencing weak intermolecular and molecular-substrate interactions of van der Waals nature. Furthermore, we characterize Pc’s on InSb (001)-c(8x2). The substrate In rows are observed to be the adsorption site for Pc’s. We find that the growth of the two-dimensional islands of FePc is prolonged in the [-110] direction, in contrast to ZnPc adsorbed on the same substrate at room temperature. We interpret this result as an indication that the adsorption is controlled by the substrate corrugation observed at 70 K.

Photonic crystals (PhCs) are periodic dielectric structures that exhibit a photonic bandgap, i.e., a range of wavelength for which light propagation is forbidden. The special band structure related dispersion properties offer a realm of novel functionalities and interesting physical phenomena. PhCs have been manufactured using semiconductors and other material technologies. However, InP-based materials are the main choice for active devices at optical communication wavelengths. This thesis focuses on two-dimensional PhCs in the InP/GaInAsP/InP material system and addresses their fabrication technology and their physical properties covering both material issues and light propagation aspects. Ar/Cl2 chemically assisted ion beam etching was used to etch the photonic crystals. The etching characteristics including feature size dependent etching phenomena were experimentally determined and the underlying etching mechanisms are explained. For the etched PhC holes, aspect ratios around 20 were achieved, with a maximum etch depth of 5 microns for a hole diameter of 300 nm. Optical losses in photonic crystal devices were addressed both in terms of vertical confinement and hole shape and depth. The work also demonstrated that dry etching has a major impact on the properties of the photonic crystal material. The surface Fermi level at the etched hole sidewalls was found to be pinned at 0.12 eV below the conduction band minimum. This is shown to have important consequences on carrier transport. It is also found that, for an InGaAsP quantum well, the surface recombination velocity increases (non-linearly) by more than one order of magnitude as the etch duration is increased, providing evidence for accumulation of sidewall damage. A model based on sputtering theory is developed to qualitatively explain the development of damage. The physics of dispersive phenomena in PhC structures is investigated experimentally and theoretically. Negative refraction was experimentally demonstrated at optical wavelengths, and applied for light focusing. Fourier optics was used to experimentally explore the issue of coupling to Bloch modes inside the PhC slab and to experimentally determine the curvature of the band structure. Finally, dispersive phenomena were used in coupled-cavity waveguides to achieve a slow light regime with a group index of more than 180 and a group velocity dispersion up to 10^7 times that of a conventional fiber. / QC 20100712

In order to meet the requests of the application as pixel switch and current driver in next generation active-matrix liquid crystal displays (AMLCD) and active-matrix organic light-emitting diodes (AMOLED). The materials of low temperature poly-silicon (LTPS) and metal-oxide are supposed to be the most potential material for active layer of thin-film transistors (TFTs) due to their high mobility compared to the traditional amorphous silicon TFTs. Therefore, in order to make the LTPS TFTs and metal-oxide TFTs affordable for the practical applications, the understanding of instability and reliability is critically important. In the first part, we studied the nonvolatile memory characteristics of polycrystalline-silicon thin-film-transistors (poly-Si TFTs) with a silicon-oxide-nitride-oxide-silicon (SONOS) structure. As the device was programmed, significant gate induced drain leakage current was observed due to the extra programmed electrons trapped in the nitride layer which. In order to suppress the leakage current and thereby avoid signal misidentification, we utilized band-to-band hot hole injection method to counteract programmed electrons and this method can exhibit good sustainability because the injected hot holes can remain in the nitride layer after repeated operations. On the other hand, we also investigated the degradation behavior of SONOS-TFT under off-state stress. After the electrical stress, the significant on-state degradation indicates that the interface states accompanied with hot-hole injection. Moreover, the ISE-TCAD simulation tool was utilized to model the degradation mechanism and analyze trap states distribution. Furthermore, we also performed the identical off-state stress for the device with different memory states. The different degradation behavior under different memory states is attributed to the different overlap region of injected holes and trap states. In the second part, the degradation mechanism of indium-gallium-zinc oxide (IGZO) thin film transistors (TFTs) caused by gate-bias stress performed in the dark and light illumination was investigated. The parallel threshold voltage indicates that charge trapping model dominates the degradation behavior under positive gate-bias stress. However, the degradation of negative gate bias stress is much slighter than the positive gate bias stress since the IGZO material is hard to induced hole inversion layer. In addition, the hole mobility is much lower than electron resulting in ignorable hole trapping effect. On the other hand, the identical positive and negative gate bias stress performed under light illumination exhibit opposite degradation behavior compared with dark stress. This degradation variation under dark and light illumination can be attributed to the effectively energy barrier variation of electron and hole trapping. Furthermore, to further investigate the light induced instability for IGZO TFTs, the device with and without a SiOx passivation were investigated under light illumination. The experiment results indicate that oxygen adsorption and desorption dominate the light induced instability for unpassivated device and the trap states caused during the passivation layer deposition process will induce apparent subthreshold photo-leakage current under light illumination. In the third part, we investigated the degradation mechanism of IGZO TFTs under hot-carrier and self-heating stress. Under hot-carrier stress, except the electron trapping induced positive Vt shift, an apparent on-current degradation behavior indicates that trap states creation. On the other hand, the identical hot-carrier stress performed in the asymmetric source/drain structure exhibits different degradation behavior compared with symmetric source/drain structure. For asymmetric structure, the strong electrical field in the I-shaped drain electrode will induce channel hot electron injection near the drain side and cause asymmetric threshold voltage degradation. In this part we also investigated the degradation behavior under self-heating stress. The apparent positive threshold voltage (Vt) shift and on-current degradation indicate that the combination of trap states generation and electron trapping effect occur during stress. The trap states generation is caused by the combination of Joule heating and the large vertical field. Moreover, the Joule heating generated by self-heating operation can enhance electron trapping effect and cause larger Vt shift in comparison with the gate-bias stress. Finally, the electrical properties and photo sensitivity of dual gate IGZO TFTs were investigated. The asymmetric electrical properties and photo sensitivity under top gate and bottom gate operation is attributed to the variation of gate control region. Furthermore, the obvious asymmetric photo sensitivity can be utilized to the In-cell touch panel technology and lower the process cost compared with the traditional a-Si TFTs due to the elimination of black matrix.

Porous metal oxides formed by supercritical carbon dioxide (SCCO2) treatments at low temperature were used for displays, solar cells, and light emitting diodes (LEDs) applications. The SCCO2 fluid, also known as green solvents, exhibits low viscosity, low surface tension and high diffusivity as gases, and high density and solubility same with liquids. In this thesis, we successfully fabricated porous antimony-doped tin oxide (ATO) and porous indium tin oxide (ITO) by the SCCO2 treatments. In addition, the treatment can also be used to improve the work function and surface energy of ITO anode of an organic LED (OLED). The performance of the OLEDs was drastically enhanced in comparison with that of the devices without any ITO surface treatments. First, the porous ATO films were formed by the SCCO2 treatment for absorption of silver molecules in silver electro deposition devices. The porosity, resistivity and average optical transmittance of the porous ATO film in visible wavelength were 43.1%, 3 £[-cm and 90.4%, respectively. For the silver electro deposition devices with the porous ATO film, the transmittance contrast ratio of larger than 12 in visible spectrum was obtained at an operating voltage of 1.5 V. Furthermore, for the 0.25 cm2 device, the switching time of 4.5 seconds was achieved by applying a square-wave voltage ranging from 1.5 to -0.2 V between the electrodes. On the other hand, the porous ITO with low refractive index was prepared by SCCO2/IPA treatment on gel-coated ITO thin films. The high refractive index of the ITO film was achieved by long-throw radio-frequency magnetron sputtering technique at room temperature. The index contrast (£Gn) was higher than 0.6 between porous ITO and sputtered ITO films. The large £Gn is useful for fabricating conductive anti-reflection (AR) and high reflection (HR) structures using the porous ITO on sputtered ITO bilayers. The weighted average reflectance and transmittance of 4.3% and 83.1% were achieved for the double-layer ITO AR electrode with a sheet resistance of 1.1 K£[/¡E. For HR structures, the reflectance and sheet resistance were 87.9% and 35 £[/¡E with 4 periods ITO bilayers. Finally, the SCCO2 treatments with strong oxidizer H2O2 were proposed to modify surface property of ITO anode of a fluorescent OLED. The highest work function and surface energy of 5.5 eV and 74.8 mJ/m2 was achieved by the SCCO2/H2O2 treatment. For the OLED with 15 min SCCO2 treatment at 4000 psi, the turn-on voltage and maximum power efficiency of 6.5 V and 1.94 lm/W were obtained. The power efficiency was 19.3% and 33.8% higher than those of the OLEDs with oxygen plasma treated and as-cleaned ITO anodes.