A titanium dioxide powder co-doped with boron and zirconium was prepared by mechanical ball milling. Photocatalytic performance of the powder was evaluated by degradation of methylene blue (MB) solution under UV illumination. XRD patterns were refined by Rietveld analysis method to obtain accurate lattice parameters and position of the atoms in the crystal structure of TiO2. XRD analysis indicated that the B and/or Zr doped TiO2 powders composed of anatase and did not exhibit any additional phase. Rietveld analysis suggested that dopant B and Zr elements were successfully weaved into crystal structure and distorted the lattice of TiO2. The highest distortion was obtained by co-doping. SEM investigations confirmed that mechanical ball milling technique led to a decrease in particle size of TiO2 powder. XPS analysis revealed that dopant B and Zr atoms did not appear in any form of compound including Ti and O elements. Results of photocatalytic activity test suggested that boron and zirconium co-doped TiO2 particles exhibited a better visible light response and photocatalytic activity than that of mono element doped TiO2 (i.e. B-TiO2 and Zr-TiO2) and undoped TiO2 particles. A 20% improvement in photocatalytic activity of reference TiO2 powder (powder ball milled without dopant addition) was achieved by B and Zr co-doping. The enhanced photocatalytic activity is attributed to synergistic effects of B-Zr co-doping the lattice of TiO2 as well as particle size reduction.

Lutetium oxide doped with europium (Lu2O3:Eu3+) has been established as a promising scintillator material with properties that are advantageous when compared to other scintillators such as cesium iodide doped with thallium (CsI:Tl). Due to high X-ray attenuation characteristics, Lu2O3:Eu3+ is an attractive material for use in high resolution digital X-ray imaging systems. However, challenges still remain especially in the area of light output for Lu2O3:Eu3+. Processing by physical vapor deposition (PVD) and manipulation of oxygen defect structure was explored in order to better understand the effect on the scintillation phenomena. PVD results were obtained using high temperature radio frequency sputtering (RF) and pulsed laser deposition (PLD) systems. Characterization of light output by radial noise power spectrum density measurements revealed that high temperature RF films were superior to those obtained using PLD. Optimization of sputtered films based on light output over a range of process parameters, namely temperature, power, pressure, and substrate orientation was investigated. Parameterization of deposition conditions revealed that: 75 watts, 10.00 mtorr, and 800°C were optimum conditions for Lu2O3:Eu3+ films. Manipulation of anionic defect structure in similar material systems has been shown to improve scintillation response. Similar methods for Lu2O3:Eu3+ were explored for hot pressed samples of Lu2O3:Eu3+; via controlled atmosphere annealing, and use of extrinsic co-doping with calcium. The controlled atmosphere experiments established the importance of oxygen defect structure within Lu2O3:Eu3+ and showed that fully oxidized samples were preferred for light output. The second method utilized co-doping by the addition of calcium which induced oxygen vacancies and by Frenkel equilibrium changed the oxygen interstitial population within the Lu2O3:Eu3+ structure. The addition of calcium was investigated and revealed that scintillation was improved with a maximum response occurring at 340ppm of calcium. PVD optimization and co-doping experimental results provided a template for the use of calcium co-doped Lu2O3:Eu3+ targets for deposition of films. Preliminary deposition results were promising and revealed that small additions (around 550 ppm) of calcium resulted in better activator efficiency. Calcium co-doped films have a predicted increase in the light yield greater than 14% when compared to analogous un-doped Lu2O3:Eu3+ films at 60keV.

No description available.

Les fibres optiques dont on façonne la réponse spectrale incorporent des ions luminescents, des ions de terres rares (TR), dans des nanoparticules (NP) formées in situ dans un verre de silice par séparation de phase. Cette ingénierie nécessite de comprendre le lien entre la composition des NP et l’environnement des TR.En Dynamique Moléculaire, les potentiels interatomiques existants pèchent à reproduire la séparation de phase observée expérimentalement. Le mélange xMgO-(1-x)SiO2 présente un domaine où coexistent deux phases mixtes, riche en Mg ou en Si. Une telle séparation de phase ne se modélise qu’avec un potentiel interatomique prenant en compte la ionicité des liaisons, réalisé ici par l’ajustement des charges des Oxygène selon l’environnement local. Ce modèle adaptatif, transférable, permet de suivre pour la 1ère fois la formation de NP amorphes de quelques nm. Mixtes et riches en Mg, elles se séparent d’une matrice riche en Si.Le dopage TR (Er3+ ou Eu3+) montre que leur voisinage dépend de la taille des NP les contenant : plus les NP sont grosses, plus les fractions de TR et de Mg augmentent. Ce voisinage riche en Mg permet à ces TR d’augmenter leur coordinence en Oxygène et elles n’ont plus besoin de s’agréger entre elles pour satisfaire cette tendance naturelle.Une simulation de l’étirage à chaud d’un verre de silice confirme l’existence d’une anisotropie dans la fibre optique, venant de l’orientation persistante des petits anneaux de silice, et se manifeste par une anisotropie élastique. Les effets que ces conditions extrêmes induisent sur les NP seront étudiés ultérieurement.La mise en œuvre d'un modèle de champ cristallin corrélera les modifications de l'environnement des TR avec leur réponse spectrale. / Optical fibers with tailored spectral response are doped with luminescent ions, rare-earth ions (re), embedded in nanoparticles (np) formed in situ in silica glass through a phase separation process. This engineering requires to understand the relation between the np composition and the re environment. In molecular dynamics, the existing interatomic potentials fail to reproduce the phase separation as experimentally observed. The system xmgo-(1-x)sio2 exhibits a domain inside of which two mixed phases coexist, mg-rich either si-rich. Such a phase separation can only be modeled by an interatomic potential that takes into account bond ionicity, and the transferability isEnabled here by the adaptation of oxygen charges according to the local environment. This adaptive model allows for the 1st time to track the formation of amorphous np of few nanometers. Mixed and mg-rich, they separate from a si-rich matrix. The re doping (er3+ or eu3+) shows that re environment depends on the size of the containing np: the bigger it is, the more the proportions of embedded re and mg increase. Thus, this mg-rich environment enables re ions to increase their oxygen coordination and to no more aggregate to each other to satisfy this natural trend. A simulation of the high-temperature drawing of silica-glass confirms the existence of an anisotropy in optical fiber, explained by the persistent orientation that small silica rings acquire in this fiber, and manifests itself by an elastic anisotropy. The nontrivial effects induced on np by these extreme conditions of temperature and stress can be studied later. The crystal-field model can be used to correlate the changes of the re environment with their spectral response.

M-type barium hexaferrite powders doped with titanium and/or cobalt have been synthesized according to the stochiometric formulations BaFe(12 &amp / #8211 / (4/3)x)TixO19, BaFe12-xCoxO19 , BaFe12-2xTixCoxO19 (x varying from 0 to 1.5 with an increment of 0.5) by the mixed oxide approach. The powders were used to manufacture small ceramic tiles by sintering each composition at 1250 &deg / C with soaking times ranging from 1 to 16 hours. XRD work revealed formation of the magnetoplumbite crystal structure in all ceramics. The variations in processing parameters led to differences in microstructure and various dielectric and magnetic properties of the ceramic tiles. The interaction of the ceramics with electromagnetic waves was characterized by using a vector network analyzer in the X and Ku bands. The results revealed that, undoped barium hexaferrite ceramics and those doped with low titanium exhibited good microwave absorption properties.

Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2016-10-25T10:51:21Z No. of bitstreams: 1 TeseRHP.pdf: 8778601 bytes, checksum: eb4553a13387041c0fd36d153b524c3c (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T19:10:09Z (GMT) No. of bitstreams: 1 TeseRHP.pdf: 8778601 bytes, checksum: eb4553a13387041c0fd36d153b524c3c (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T19:10:15Z (GMT) No. of bitstreams: 1 TeseRHP.pdf: 8778601 bytes, checksum: eb4553a13387041c0fd36d153b524c3c (MD5) / Made available in DSpace on 2016-11-08T19:10:21Z (GMT). No. of bitstreams: 1 TeseRHP.pdf: 8778601 bytes, checksum: eb4553a13387041c0fd36d153b524c3c (MD5) Previous issue date: 2016-09-30 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / InO1.5-stabilized zirconia (InSZ) is a potential hot corrosion resistant thermal barrier coating (TBC). However, the thermal instability prevents real applications of InSZ-based TBC. This thesis investigates the hypothesis of co-doping using the charge compensation to improve the phase stability of InSZ. Four co-doping systems were synthesized by coprecipitation and studied: (ZrO2)1-(x+y)(InO1.5)x(MOz)y with MOz = TaO2.5, NbO2.5, MoO3, or WO3. After synthesis, 9 mol% of InO1.5 plus the charge-compensating oxides was sufficient to stabilize the tetragonal phase. Specific surface area up to 106.1 m2.g-1 and crystallite size ~11 nm were achieved using ethanol washing followed by azeotropic distillation as dehydration technique in the precipitates. In these powders, initial thermal stability analysis indicated instability of the tetragonal phase, with extension of the t→m transformation less detrimental in the InMoSZ system. Further increase in the concentration of InO1.5:MoO3 results in monophasic samples with retention of cubic phase in the InMoSZ. Cubic InMoSZ exhibited hardness and thermal expansion coefficient of 13.5% and 9% higher than those of InSZ, respectively. However, thermal treatments at T ≥ 1200 °C showed that the InMoSZ is also passive to destabilization of the high temperature cubic polymorph. Although the cubic InMoSZ was the most promising system found in this thesis, the stability results do not support its application as TBC for temperatures ≥ 1000 ºC. A deep evaluation of the phase transformations between 1000 to 1200 °C indicated that the instability of the proposed systems is due to a progressive c→t→m destabilization of the polymorphs. This c→t→m transformation is directly associated with the reduction of the InO1.5 stabilizer in solid solution by volatilization as In2O during heat treatment. At temperatures ≤ 800 ºC, the c→t phase transformation do not occurs, then, InSZ-based TBC is stable in these conditions. / A zircônia estabilizada com InO1,5 (InSZ) é um material com potencial aplicação como revestimentos para barreira térmica (TBC) resistentes à corrosão. Contudo, a instabilidade de fases impede aplicações industriais da InSZ. Esta tese investiga a ação da co-dopagem por compensação de cargas como uma estratégia para aumentar a estabilidade de fases da InSZ. Quatro sistemas de co-dopagem foram sintetizados por co-precipitação e estudados: (ZrO2)1-(x+y)(InO1,5)x(MOz)y com MOz = TaO2,5, NbO2,5, MoO3 ou WO3. Após a síntese, 9 %mol de InO1,5 somado a concentração de óxidos compensadores de carga foi suficiente para estabilização da fase tetragonal. Área superficial específica de até 106,1 m2.g‒1 e tamanho de cristalitos de ~11 nm foram obtidos utilizando a lavagem com etanol seguida por destilação azeotrópica como técnica de desidratação dos precipitados. Para estes pós, testes de estabilidade térmica indicaram instabilidade da fase tetragonal, com extensão de transformação t→m menos detrimental no sistema InMoSZ. Aumentando gradativamente a concentração de InO1,5-MoO3 na InMoSZ resulta em amostras monofásicas com retenção da fase cúbica. A InMoSZ cúbica exibiu dureza e coeficiente de expansão térmica até 13,5% e 9% superiores aos valores da InSZ, respectivamente. No entanto, tratamentos em temperaturas ≥ 1200 ºC indicaram que a InMoSZ é também suscetível a desestabilização da fase cúbica. Embora a InMoSZ cúbica tenha sido o sistema mais promissor obtido nesta tese, os resultados de estabilidade indicam que sua aplicação como TBC não é possível em temperaturas ≥ 1000 ºC. Uma avaliação detalhada das fases formadas após os tratamentos entre 1000 a 1200 ºC demonstrou que a instabilidade dos sistemas estudados é decorrente de uma transformação progressiva tipo c→t→m. A origem da transformação c→t→m é associada a redução da concentração do estabilizador InO1,5 em solução sólida por volatilização como In2O durante os testes de estabilidade térmica. Em temperaturas ≤ 800 ºC, a transformação c→m não ocorre, neste caso, TBCs baseadas em InSZ são estáveis termicamente para aplicações industriais.

Le silicium (Si) et le germanium (Ge) sont les matériaux de base utilisés dans les circuits intégrés. Cependant, à cause de leur gap indirect, ces matériaux ne sont pas adaptés à la fabrication de dispositifs d'émission de lumière, comme les lasers ou diodes électroluminescentes. Comparé au Si, le Ge pur possède des propriétés optiques uniques, à température ambiante son gap direct est de seulement 140 meV au-delà du gap indirect tandis qu'il est supérieur à 2 eV dans le cas du Si. Compte tenu du coefficient de dilatation thermique du Ge, deux fois plus grand que celui du Si, une croissance de Ge sur Si à hautes températures suivie d'un refroidissement à température ambiante permet de générer une contrainte en tension dans le Ge. Cependant, l'existence d'un désaccord de maille de 4,2% entre deux matériaux conduit à une croissance Stranski-Krastanov avec la formation des films rugueux et contenant de forte densité des dislocations. Nous avons mis en évidence l'existence d'une fenêtre de température de croissance, permettant de supprimer la croissance tridimensionnelle de Ge/Si. En combinant la croissance à haute température à des recuits thermiques par cycles, une contrainte de 0,30% a pu être obtenue. Le dopage de type n a été effectué en utilisant la décomposition de GaP, ce qui produit des molécules P2 ayant un coefficient de collage plus grand par rapport à celui des molécules P4. En particulier, en mettant en oeuvre la technique du co-dopage en utilisant le phosphore et l'antimoine, nous avons mis en évidence une augmentation de l'émission du gap direct du Ge à environ 150 fois, ce qui constitue l'un des meilleurs résultats obtenus jusqu'à présent. / Silicon (Si) and germanium (Ge) are the main materials used as active layers in microelectronic devices. However, due to their indirect band gap, they are not suitable for the fabrication of light emitting devices, such as lasers or electroluminescent diodes. Compared to Si, pure Ge displays unique optical properties, its direct bandgap is only 140 meV above the indirect one. As Ge has a thermal expansion coefficient twice larger than that of Si, tensile strain can be induced in the Ge layers when growing Ge on Si at high temperatures and subsequent cooling down to room temperature. However, due to the existence of a misfit as high as 4.2 % between two materials, the Ge growth on Si proceeds via the Stranski-Krastanov mode and the epitaxial Ge films exhibits a rough surface and a high density of dislocations. We have evidenced the existence of a narrow substrate temperature window, allowing suppressing the three-dimensional growth of Ge on Si. By combining high-temperature growth with cyclic annealing, we obtained a tensile strain up to 0.30 %. The n-doping in Ge was carried out using the decomposition of GaP to produce the P2 molecules, which have a higher sticking coefficient than the P4 molecules. In particular, by implementing a co-doping technique using phosphorus and antimony, we have evidenced an intensity enhancement of about 150 times of the Ge direct band gap emission. This result represents as one of the best results obtained up to now.

This thesis focuses on the effects of dopant compensation on the electrical properties of crystalline silicon relevant to the operation of solar cells. We show that the control of the net dopant density, which is essential to the fabrication of high-efficiency solar cells, is very challenging in ingots crystallized with silicon feedstock containing both boron and phosphorus such as upgraded metallurgical-grade silicon. This is because of the strong segregation of phosphorus which induces large net dopant density variations along directionally solidified silicon crystals. To overcome this issue, we propose to use gallium co-doping during crystallization, and demonstrate its potential to control the net dopant density along p-type and n-type silicon ingots grown with silicon containing boron and phosphorus. The characteristics of the resulting highly-compensated material are identified to be: a strong impact of incomplete ionization of dopants on the majority carrier density, an important reduction of the mobility compared to theoretical models and a recombination lifetime which is determined by the net dopant density and dominated after long-term illumination by the boron-oxygen recombination centre. To allow accurate modelling of upgraded-metallurgical silicon solar cells, we propose a parameterization of these fundamental properties of compensated silicon. We study the light-induced lifetime degradation in p-type and n-type Si with a wide range of dopant concentrations and compensation levels and show that the boron-oxygen defect is a grown-in complex involving substitutional boron and is rendered electrically active upon injection of carriers through a charge-driven reconfiguration of the defect. Finally, we apply gallium co-doping to the crystallization of upgraded-metallurgical silicon and demonstrate that it allows to significantly increase the tolerance to phosphorus without compromising neither the ingot yield nor the solar cells performance before light-induced degradation.

Made available in DSpace on 2014-12-17T14:07:19Z (GMT). No. of bitstreams: 1 WilsonJO_TESE.pdf: 5377189 bytes, checksum: 886cb0d3eb97075a3db2f3b7c1a15af0 (MD5) Previous issue date: 2013-10-21 / Fuel cells are considered one of the most promising ways of converting electrical energy due to its high yield and by using hydrogen (as fuel) which is considered one of the most important source of clean energy for the future. Rare earths doped ceria has been widely investigated as an alternative material for the electrolyte of solid oxide fuel cells (SOFCs) due to its high ionic conductivity at low operating temperatures compared with the traditional electrolytes based on stabilized zirconia. This work investigates the effect of gallium oxide (Gallia) as a sintering aid in Eu doped ceria ceramic electrolytes since this effect has already been investigated for Gd, Sm and Y doped ceria electrolytes. The desired goal with the use of a sintering aid is to reduce the sintering temperature aiming to produce dense ceramics. In this study we investigated the effects on densification, microstructure and ionic conduction caused by different molar fraction of the dopants europium (10, 15 and 20%) and gallium oxide (0.3, 0.6 and 0.9%) in samples sintered at 1300, 1350 and 1450 0 C. Samaria (10 and 20%) doped ceria samples sintered between 1350 and 1450 ?C were used as reference. Samples were synthesized using the cation complexation method. The ceramics powders were characterized by XRF, XRD and SEM, while the sintered samples were investigated by its relative density, SEM and impedance spectroscopy. It was showed that gallia contents up to 0.6% act as excellent sintering aids in Eu doped ceria. Above this aid content, gallia addition does not promote significant increase in density of the ceramics. In Ga free samples the larger densification were accomplished with Eu 15% molar, effect expressed in the microstructure with higher grain growth although reduced and surrounded by many open pores. Relative densities greater than 95 % were obtained by sintering between 1300 and 1350 ?C against the usual range 1500 - 1600 0 C. Samples containing 10% of Sm and 0.9% of Ga reached 96% of theoretical density by sintering at 1350 0 C for 3h, a gain compared to 97% achieved with 20% of Sm and 1% of Ga co-doped cerias sintered at 1450 0 C for 24 h as described in the literature. It is found that the addition of gallia in the Eu doped ceria has a positive effect on the grain conductivity and a negative one in the grain boundary conductivity resulting in a small decrease in the total conductivity which will not compromise its application as sintering aids in ceria based electrolytes. Typical total conductivity values at 600 and 700 ?C, around 10 and 30 mS.cm -1 respectively were reached in this study. Samples with 15% of Eu and 0.9 % of Ga sintered at 1300 and 1350 ?C showed relative densities greater than 96% and total conductivity (measured at 700 ?C) between 20 and 33 mS.cm -1 . The simultaneous sintering of the electrolyte with the anode is one of the goals of research in materials for SOFCs. The results obtained in this study suggest that dense Eu and Ga co-doped ceria electrolytes with good ionic conductivity can be sintered simultaneously with the anode at temperatures below 1350 ?C, the usual temperature for firing porous anode materials / As c?lulas a combust?vel s?o tidas como uma das mais promissoras formas de convers?o de energia el?trica devido ao seu alto rendimento e por utilizar o hidrog?nio como combust?vel, considerado por muitos a principal fonte limpa de energia para o futuro. C?ria dopada com terras raras tem sido amplamente investiga como material alternativo para eletr?lito de c?lulas a combust?vel de ?xido s?lido (SOFC) devido sua alta condutividade i?nica em baixas temperaturas de opera??o quando comparado com os tradicionais eletr?litos ? base de zirc?nia estabilizada. Neste seguimento de pesquisa, este trabalho investiga o efeito do ?xido de g?lio (G?lia) como aditivo de sinteriza??o em eletr?litos cer?micos a base de c?ria dopada com eur?pio, uma vez que este efeito j? foi investigado por outros em eletr?litos ? base de c?ria dopada com Gd, Sm e Y. A meta almejada com a utiliza??o do aditivo de sinteriza??o ? reduzir a temperatura de sinteriza??o para a produ??o de cer?micas densas. Neste trabalho investigou-se o efeito na densifica??o, na microestrutura e na condu??o i?nica causado por diferentes fra??es molares do dopante eur?pio (10, 15 e 20%) e do aditivo de sinteriza??o ?xido de g?lio (0,3; 0,6 e 0,9%), em amostras sinterizadas a 1300, 1350 e 1450 0 C. A c?ria co-dopada com 10 e 20% de Sm e com os mesmos teores do aditivo de sinteriza??o g?lia, sinterizadas a 1350, 1450 e 1500 0 C, tamb?m foi investigada, por sua vez, como par?metro de refer?ncia experimental, haja visto que, nesta pesquisa, adotou-se s?nteses pelo m?todo de complexa??o de c?tions enquanto que os trabalhos encontrados na literatura utilizaram o m?todo convencional. Os p?s cer?micos sintetizados foram caracterizados por FRX, DRX e MEV e as amostras cer?micas sinterizadas por sua densidade relativa, MEV e espectroscopia de imped?ncia. Verifica-se que a G?lia com teores at? 0,6% atua como um excelente aditivo de sinteriza??o na c?ria dopada com Eu. Acima deste teor e at? 0,9% a adi??o da g?lia n?o promove significativos aumentos na densidade da cer?mica. Nas amostras livres do Ga, as maiores densifica??es foram alcan?adas com 15% de Eu, efeito manifestado na micro-estrutura com os maiores crescimentos de gr?os, embora ainda reduzidos e circundados por muitos poros abertos. Densidades relativas superiores a 95% da densidade te?rica podem ser obtidas com sinteriza??es entre 1300 e 1350 0 C, contra as usuais 1500 a 1600 0 C. Com a c?ria co-dopada com 10% de Sm e 0,9% de Ga alcan?ou-se neste trabalho 96% da densidade te?rica com sinteriza??o a 1350 0 C por 3h, um ganho em rela??o aos 97% alcan?ados com a c?ria co-dopada com 20% de Sm e 1% de Ga sinterizada a 1450 0 C por 24h conforme encontrado na literatura. Verifica-se que a adi??o da G?lia em eletr?litos ? base de c?ria dopada com Eu apresenta efeito positivo na condutividade do gr?o e negativo na do contorno de gr?o resultando em uma pequena redu??o na condutividade total, a qual n?o compromete sua promissora aplica??o como aditivo de sinteriza??o. Valores t?picos da condutividade total a 600 e 700 0 C, em torno de 10 e 30 mS.cm -1 respectivamente, foram alcan?ados neste trabalho. As amostras de eletr?litos ? base de c?ria co-dopada com 15% de Eu e 0,9% de Ga, sinterizados a 1300 e 1350 0 C, alcan?aram densidades relativas superiores a 96% e condutividade a 700 0 C entre 20 e 33 mS.cm -1 . A sinteriza??o simult?nea do eletr?lito com o anodo ? uma das metas da pesquisa em materiais para SOFCs. Os resultados alcan?ados neste trabalho sugerem que eletr?litos densos ? base de c?ria co-dopada com Eu e Ga podem ser sinterizados simultaneamente com o anodo ? temperatura de sinteriza??o entre 1300 e 1350 0 C, a faixa de temperatura usual de sinteriza??o do anodo poroso

Ce travail de thèse traite de la production d’hydrogène par le procédé de photoélectrocatalyse en utilisant une photoanode à base de nanotubes de TiO2 verticalement alignés. L’utilisation du TiO2 étant limité pour des applications solaires en raison de son large gap, il est nécessaire de le modifier. Deux approches sont proposées pour modifier les nanotubes de TiO2 et leur permettre d’absorber la lumière visible. La première est une modification chimique du TiO2 par co-dopage cationique-anionique (Ta-N) ou (Nb-N). Les cations sont insérés durant la croissance des nanotubes grâce à une approche inédite, et l’azote est inséré durant le traitement thermique. Ceci a pour effet la formation d’orbitales hybrides qui entraîne une réduction du gap et une activité sous lumière visible, tout en permettant une stabilité de la structure. La seconde approche consiste à déposer des nanoparticules d’Ag sur la surface des nanotubes de TiO2. Grâce au contrôle de la morphologie des nanoparticules d’Ag, leur résonnance plasmonique permet de stimuler l’absorption du TiO2 et ainsi d’augmenter son rendement à la fois sous lumière UV et sous lumière visible. / This work is about the production of hydrogen by photoelectrocatalysis using a vertically aligned TiO2 nanotubes based photoanode. Utilization of TiO2 for solar applications is limited due to its large band gap, it has to be modified. Two approaches are proposed for the modification of the TiO2 nanotubes to make them absorb visible light. The first one is the chemical modification of the TiO2 by (Ta-N) or (Nb-N) cationic-anionic co-doping. Cations are inserted during the growth of the nanotubes by a novel approach, and nitrogen is inserted during heat treatment. This leads to the formation of hybrid orbitals resulting in a band gap reduction and of activity under visible light. The second approach consists of the deposition of Ag nanoparticles on the surface of the TiO2 nanotubes. Thanks to the control of the morphology of the Ag nanoparticles, their plasmonic resonance can enhance the absorption of TiO2 and thus increase its activity both under UV and visible light.