Les tubes amplificateurs ont été quelque peu oubliés du grand public depuis leur disparition des récepteurs de radio et d'autres équipements à la fin des années 50 et leur remplacement par les composants état solide. Toutefois, il est des régimes de fonctionnement où ils demeurent incontournables, surpassant tous les dispositifs état solide en termes de fréquence de fonctionnement, de puissance, de rendement et de fiabilité. C'est la raison pour laquelle les satellites de télécommunications embarquent à leur bord une centaine de tubes à ondes progressives pourtant lourds et volumineux. Afin de réduire leur poids et leur taille et d'atteindre des rendements encore plus élevés, différents laboratoires étudient des cathodes capables d'émettre un faisceau électronique modulable en hyperfréquence. Les! laboratoires de TRT, de l'Ecole Polytechnique (Nanocarb) et de TED, dans lesquels cette thèse a été préparée, étudient de nouvelles cathodes à émission de champ basées sur des réseaux de nanotubes de carbone. Ce travail de thèse a porté sur l'étude et le développement de méthodes pour moduler directement le faisceau électronique issu de ces cathodes. La croissance de nanotubes de carbone est ici réalisée par dépôt chimique en phase vapeur assisté par plasma. Des travaux précédents ont permis de développer et d'optimiser une technologie de croissance de nanotubes individuels orientés verticalement, et d'étudier leurs caractéristiques d'émission en continu. La première partie de cette thèse a consisté à démontrer la modulation de l'émission en utilisant des cavités résonantes qui permettent l'obtention de forts champs électriques hyperfréquence. Nous avons ainsi démontré à une fréquence de 1.5 GHz la modulation d'un courant crête de 30 mA correspondant à une densité de courant de 12 A.cm-2, puis, à 32 GHz, la modulation d'un courant crête de 3.43 mA. Ce sont les premières et les seules modulations hyperfréquence de cathodes à base de nanotubes de carbone publiées à ce jour. Cependant l'utilisation de cavités résonantes limite l'emploi de ces cathodes à des applications bande étroite. La deuxième partie de la thèse a été consacrée au développement d'un nouveau concept de photocathodes basées sur l'association de photodiodes p-i-n et de nanotubes de carbone. L'émission électronique de ces dispositifs est alors commandée par la puissance lumineuse reçue et ne requiert plus de cavité. Le contrôle de la modulation est ainsi rendu compatible large bande. Une première génération de photocathodes à nanotubes de carbone sur p-i-n silicium a permis de montrer la modulation d'un courant de 500 µA avec un taux de modulation de 97% pour une puissance optique absorbée de 12 mW.

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-03-24T21:23:22Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) monique_rocha_almeida.pdf: 4635045 bytes, checksum: 2d203824a390ae82a5006e68b621c98b (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-04-20T19:40:16Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) monique_rocha_almeida.pdf: 4635045 bytes, checksum: 2d203824a390ae82a5006e68b621c98b (MD5) / Made available in DSpace on 2017-04-20T19:40:16Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) monique_rocha_almeida.pdf: 4635045 bytes, checksum: 2d203824a390ae82a5006e68b621c98b (MD5) Previous issue date: 2016 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / A convers?o de energia solar em energia qu?mica usando c?lulas fotoeletroqu?micas ? uma estrat?gia interessante para armazenar energia. C?lulas fotoeletroqu?micas s?o dispositivos constitu?dos de fotoeletrodos semicondutores que absorvem luz com energia maior ou igual a energia de bandgap do semicondutor e geram cargas reativas (el?trons e buracos) na superf?cie dos fotoeletrodos capazes de promover a redu??o e oxida??o da ?gua em H2 e O2, respectivamente. Nesta disserta??o, quatro fotoeletrodos de g-C3N4, g-C3N4/Cu1%, g- C3N4/Cu5% e Cu2O/CuO foram preparados com o objetivo de desenvolver uma c?lula fotoeletroqu?mica para clivagem da ?gua em H2 e O2 de forma espont?nea. As medidas de difratometria de raios X confirmaram a presen?a das fases g-C3N4 e Cu2O/CuO nos fotoeletrodos. As imagens de MEV mostraram que os materiais ? base de g-C3N4 possuem morfologia do tipo esponja, enquanto a heterojun??o Cu2O/CuO ? formada por nanopart?culas de forma indefinida. Medidas de reflect?ncia difusa mostraram que o acoplamento do g-C3N4 e Cu2O/CuO resulta em uma melhora significativa na absor??o ?ptica dos fotoeletrodos. Medidas de ?rea espec?fica indicaram que os nanomateriais ? base de g-C3N4 tem alta ?rea superficial (?100 m2 g?1), enquanto a ?rea espec?fica da heterojun??o Cu2O/CuO foi de 17 m2 g?1. Os resultados de redu??o ? temperatura programada evidenciaram a forma??o das heterojun??es. Os testes fotoeletroqu?micos de produ??o de O2 a partir da ?gua usando luz vis?vel indicaram que em potenciais an?dicos, apenas o fotoanodo de g-C3N4 foi est?vel apresentando uma densidade de fotocorrente de 16 ?A cm?2 que corresponde a uma efici?ncia de convers?o de luz de 0,014%. Em potenciais cat?dicos, a maior densidade de fotocorrente (60 ?A cm?2) foi obtida para o fotoeletrodo Cu2O/CuO. A efici?ncia de convers?o de luz do fotocatodo de Cu2O/CuO foi de 0,029%. Com base nos dados obtidos, uma c?lula fotoeletroqu?mica p-n foi constru?da usando a heterojun??o Cu2O/CuO como fotocatodo e g- C3N4 como fotoanodo. Esta c?lula gerou uma densidade de fotocorrente in operando de 0,62 ?A cm?2 e uma fotovoltagem de 0,62 V. A efici?ncia de convers?o solar da fotoc?lula foi de 0,004% sob irradia??o de luz vis?vel. Apesar da baixa efici?ncia obtida, espera-se que esta disserta??o possa servir de inspira??o para o desenvolvimento de novos dispositivos fotoeletroqu?micos para clivagem da ?gua em H2 e O2, usando luz vis?vel. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / The conversion of solar energy into chemical energy using photoelectrochemical cells is an interesting strategy to store energy. Photoelectrochemical cells are made up of semiconductor photoelectrodes that absorb light with energy equal or higher than the bandgap energy of the semiconductor to generate reactive charges (electrons and holes) on the surface of the photoelectrodes, which can promote the oxidation and reduction reactions of water to form H2 and O2, respectively. In this dissertation, four photoelectrodes of g-C3N4, g-C3N4/Cu1%, g- C3N4/Cu5%, and Cu2O/CuO were prepared in order to develop a photoelectrochemical cell for spontaneous water splitting into H2 and O2. The X-ray diffraction patterns confirmed the presence of g-C3N4 and Cu2O/CuO phases in the photoelectrodes. The SEM images showed that the materials based on g-C3N4 have sponge-like morphology, whereas the Cu2O/CuO heterojunction is formed by nanoparticles with undefined shapes. Diffuse reflectance measurements showed that coupling g-C3N4 and Cu2O/CuO results in a significant improvement in optical absorption of the photoelectrodes. Surface area measurements indicated that the nanomaterials based on g-C3N4 have high surface areas (?100 m2 g?1), while the specific area for the Cu2O/CuO heterojunction was 17 m2 g?1. The temperature programmed reduction results evidenced the formation of the heterojunctions. The photoelectrochemical assays of O2 production from water using visible light indicated that at anodic potentials, only the photoanode g-C3N4 was stable showing a photocurrent density of 16 ?A cm?2, which corresponds to a light conversion efficiency of 0.014%. At cathodic potentials, the higher photocurrent density (60 ?A cm?2) was obtained for the Cu2O/CuO photoelectrode. The light conversion efficiency of the Cu2O/CuO photocathode was 0.029%. Based on the obtained data, a p-n photoelectrochemical cell was constructed using the Cu2O/CuO heterojunction as the photocathode and g-C3N4 as the photoanode. This photocell generated a photocurrent density in operando of 0.62 ?A cm?2 and photovoltage of 0.62 V. The light conversion efficiency of the photocell was 0.004% under visible light irradiation. Despite the low efficiency obtained for the p-n photocell, it is expected that this dissertation may serve of inspiration for the development of new photoelectrochemical devices for water splitting into H2 and O2 using visible light.

The future energy demand will require a change in the current energy supply. In this regard, the production of hydrogen by photoelectrochemical solar cells is a promising alternative because the fuel is obtained from water and, importantly, its combustion is free of carbon. Many metal oxides, including those having a complex stoichiometry (i.e. ternary oxides) behave as semiconductors and present good stability in aqueous environments, making them attractive candidates for water splitting devices. This thesis focuses on the preparation and study of ternary metal oxide materials as photoelectrodes for water splitting, with emphasis on photocathodes. These materials must meet the requirements for a practical device: low cost, non-toxicity, made of Earth abundant elements, environmentally friendly, etc. The thesis also aims at the study of strategies to improve their photoelectrochemical response. lt comprises the investigation of the kinetics of hydrogen generation reaction and the characteristics of the electrode solution interface by photoelectrochemical impedance spectroscopy. The main points can be summarized as: (i) the effect of an electrochemical oxidative pretreatment in CuFe2Ü4 photocathodes (ii) the investigation of water splitting mechanisms in CaFe2Ü4 photocathodes, (iii) the effect of metal doping in LaFeO3 photocathodes (iv) the study of the photoelectrochemistry of compact and nanoparticulate YFeO3 photocathodes and (v) the effect of a reductive electrochemical treatment in NiTiO3 photoanodes, and comparison with the effect of the treatment in anatase electrodes.

Les techniques de pompage optique sont habituellement bien adaptées à l'étude de la dynamique de spin des semi-conducteurs. Le silicium est un cas particulier, à cause d'un gap indirect et d'un faible couplage spin-orbite.<br />La stratégie mise en place dans nos travaux consiste à «réduire le temps de vie» des électrons de conduction, afin que leur polarisation initiale soit conservée.<br />Dans un premier temps, nous avons mené une étude de photoluminescence polarisée. La réduction du temps de vie s'opère essentiellement en faisant varier le taux de dopage en accepteurs. Nous avons mis en évidence une luminescence chaude fortement polarisée sur un échantillon très dopé. Cependant, aucun effet de dépolarisation en champ transverse n'a pu être observé.<br />Dans un deuxième temps, nous avons conduit une expérience de photo-émission résolue en spin et en énergie, pour une gamme d'énergie d'excitation variant de l'infrarouge à l'ultraviolet. L'échelle de temps pertinente est le temps d'échappement, beaucoup plus court que le temps de vie. Cela a nécessité la mise au point une procédure d'activation de photocathodes en silicium en affinité électronique négative. Une étude spectroscopique à 20 meV de résolution des distributions d'électrons photo-émis a été réalisée. L'analyse en spin de ces distributions montre une augmentation spectaculaire de la polarisation électronique lorsque l'énergie d'excitation se rapproche du gap direct. Des polarisations de l'ordre de 15% sont mesurées, proches des valeurs théoriques que nous calculons. Nous avons également observé un changement de signe de la polarisation très sensible à la température dans la partie thermalisée des distributions électroniques.

Comprehensive investigations of the electron field emission (FE) properties of annealed single crystal and polycrystalline molybdenum plugs, which are used as substrates for actual alkali-based photocathodes were performed with a FE scanning microscope. Well-polished and dry-ice cleaned Mo samples with native oxide did not show parasitic FE up to a field level of 50 MV/m required for photoinjector cavities. In situ heat treatments (HT) above 400°C, which are usual before photocathode deposition, activated field emission at lower field strength. Oxygen loading into the Mo surface, however, partially weakened these emitters. X-ray photoelectron spectroscopy of comparable Mo samples showed the dissolution of the native oxide during such heat treatments. These results reveal the suppression of field emission by native Mo oxides. Possible improvements for the photocathode preparation will be discussed.

Photoelectrodes and photovoltaic devices have been prepared via multiple thin film deposition methods. Aerosol assisted chemical vapour deposition (AACVD), electrodeposition (ED), chemical bath deposition (CBD) and doctor blade technique (DB) have been used to deposit binary and ternary metal oxide films on FTO glass substrates. The prepared thin films were characterised by a combination of SEM (Scanning Electron Microscopy), powder X-ray diffraction, mechanical strength tests and photochemical measurements. Nickel oxide (NiO) thin films prepared by AACVD were determined to have good mechanical strength . with a photocurrent of 7.6 μA cm-2 at 0 V and an onset potential of about 0.10 V. This contrasted with the dark current density of 0.3 μA cm-2 at 0 V. These NiO samples have very high porosity with crystalline columns evidenced by SEM. In comparison with the AACVD methodology, NiO films prepared using a combination of ED and DB show good mechanical strength but a higher photocurrent of 24 μA cm-2 at 0 V and an onset potential of about 0.10 V with a significantly greater dark current density of 7 μA cm-2 at 0 V. The characteristic features shown in the SEM are smaller pores compared to the AACVD method. Copper (II) oxide (CuO) and copper (I) oxide (Cu2O) films were fabricated by AACVD by varying the annealing temperature between 100-325°C in air using a fixed annealing time of 30 min. It was shown by photocurrent density (J-V) measurements that CuO produced at 325 °C was most stable and provided the highest photocurrent of 173 μA cm-2 at 0 V with an onset potential of about 0.23 V. The alignment of zinc oxide (ZnO) nano-rods and nano-tubes fabricated by CBD have been shown to be strongly affected by the seed layer on the FTO substrate. SEM images showed that AACVD provided the best seed layer for aligning the growth of the nano-rods perpendicular to the surface. Nano-rods were successfully altered into nano-tubes using a potassium chloride bath etching method. NiO prepared by both AACVD and the combined ED/DB method were sensitized to absorb more of the solar spectrum using AACVD to deposit CuO over the NiO. A large increase in the photocurrent was observed for the p-type photoelectrode. These p-type photoelectrode showed a photocurrent density of approximately 100 μA cm-2 at 0 V and an onset potential of 0.3 V. This photocathode was then used as a base to produce a solid state p-type solar cell. For the construction of the solid state solar cells several n-type semiconductors were used, these were ZnO, WO3 and BiVO4. WO3 and BiVO4 were successfully produced with BiVO4 proving to be the optimum choice. This cell was then studied more in depth and optimised by controlling the thickness of each layer and annealing temperatures. The best solid state solar cell produced had a Jsc of 0.541 μA cm-2 (541 nA) and a Voc of 0.14 V, TX146 made up of NiO 20 min, CuFe2O4 50 min, CuO 10 min, BiVO4 27 min, using AACVD and then annealed for 30 min at 600°C.

Radiations can be classified as either ionizing or non-ionizing according to whether it ionizes or does not ionize the medium through which they propagate. X-rays photons and gamma rays are the typical examples of ionizing radiations whereas radiowave, heat or visible light are examples of non ionizing radiations. UV photons have some features of both ionizing and non-ionizing radiation. Both ionizing and non-ionizing radiation can be harmful to living organisms and to the natural environment. Hence the detection and measurement of radiation is very important for the well being of living organisms as well as the natural environment. Not only for safety reasons, have radiation detectors found their applications in various fields including medical physics, nuclear and particle physics, astronomy and homeland security. Industrial sectors that use radiation detection include medical imaging, security and baggage scanning, the nuclear power industry and defense. Gas electron multiplier (GEM) is one of the most successful representatives of gaseous detectors used for UV photon and X-ray photon detection. Recently there is a growing demand for large area photon detectors with sensitivity reaching to the level of single photon. They are used in spectroscopy and imaging in astronomy high energy physics experiments etc. Thick GEM (THGEM) is a mechanical expansion of standard GEM. It has all the necessary requirements needed for large area detector and offers a multiplication factor that permits efficient detection of light. Hence, the development and performance study of THGEM based radiation detector is chosen as the topic of study in the present thesis. The initial part of the thesis contains simulation studies carried out for the understanding the working of the detector and the effect of various design parameters of THGEM for the above said applications. Different steps for the fabrication of THGEM and the technical challenges faced during the process are discussed. In the view of application of the fabricated THGEM for UV photon detection, cesium iodide photocathode is prepared using thin film technology and characterized. The performance of the photocathode under various operating conditions is studied in terms of its photoemission property. The effect of vacuum treatment on the photoemission property of the photocathode exposed to moist air is studied in detail. A major portion of this thesis focuses on maximizing the detection efficiency of the UV photon detector realized using the fabricated THGEM coupled with the cesium iodide photocathode. Simulations are used at different stages to interpret the experimental observations. The electron spectrum obtained from the detector under study was analyzed. The dependence of secondary effect like photon feedback on the operating parameters is also discussed. The last portion of the thesis deals with the application of THGEM as an X-ray detector. The performance is evaluated in terms of the gain and energy resolution achieved. The thesis is organized as follows: Chapter 1 is divided into two sections. Section A gives a general introduction to different types of radiation detectors found in the present day and their working principles. This is followed by discussion about gas ionization based detector and its working principle in detail. A brief literature survey of the different types of micropattern gas detectors is also given in this section. In Section B of this chapter GEM and THGEM are introduced with discussion about their working principle and areas of application. Chapter 2 deals with the simulation study of THGEM undertaken to have a clear understanding of the detector’s working. Section A of this chapter gives an overview of the simulation tools used for the present thesis in particular ANSYS and GARFIELD. Section B presents the results of the simulation study highlighting the effects of different geometrical and operating parameters on the electric field distribution in and around the THGEM aperture. The relevance of the study to the detectors performance is discussed vividly for all the cases. In Chapter 3, the details of the different steps involved in THGEM fabrication are given. Design aspects involved, fabrication of the THGEM using standard PCB technology coupled with photolithography technique are discussed in this chapter. This is followed by an elaborate description of the test setup used for all the performance study. Preface In the view of application of THGEM as a UV photon detector, cesium iodide photocathode was prepared and characterized. Chapter 4 discusses about the CsI photocathode preparation and its characterization for the above said application. Photoemission property of the photocathode was analyzed under various operating parameters. The effect of vacuum treatment on the photocathode performance is a new aspect of this thesis. Its correlation with the microstructure of the film is reported for the first time. Chapter 5 deals with the application of THGEM as a UV photon detector. The study mainly focuses on the improvement of the detection efficiency of the detector. The effect of drift parameters on the electron transfer efficiency and hence on the detection efficiency of the detector is a major contribution of this thesis. There are no literature available which discusses this aspect of a UV photon detector. The experimental study has been supported with simulation results. In addition to the study on detection efficiency, electron spectrum has also been acquired from the UV photon detector. The spectrum has been analyzed under various operating conditions. Discussions about secondary effects like photon feedback prevailing in the detector output are also present in this chapter. Chapter 6 presents the results of THGEM as an X-ray detector. The performance of the detector has been evaluated in terms of the effective gain and energy resolution achieved under different operating conditions. The gain instability with time and its uniformity across the THGEM area are also studied. The effect of drift field on the energy resolution and its correlation with ETE is a new aspect of this work. Chapter 7 summarizes the salient features of the work presented in this thesis. Also the scope of future work based on this thesis is discussed at the end of the chapter.