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Elaboration et caractérisation de nouvelles couches sensibles pour la réalisation de capteurs de CO2 / Elaboration and characterization of new thin films for CO2 gas sensorsEl Younsi, Imane 24 November 2015 (has links)
La mesure du taux de CO2 est un besoin relativement récent. Les travaux sur l'utilisation de nouveaux matériaux pour la réalisation de capteurs de gaz, efficaces et peu chers, suscitent des intérêts scientifique et technologique croissants. L'objectif de ces travaux de thèse est l'élaboration et la caractérisation de nouvelles couches sensibles obtenues par pulvérisation cathodique radiofréquence pour la réalisation de capteurs de CO2. Les films minces ont été déposés à partir d'une cible céramique de CuO, dans diverses conditions de dépôt, en variant la pression d'argon dans l'enceinte et la puissance RF appliquée. Dans un premier temps, nous avons caractérisé la structure et la microstructure des films bruts et recuits sous air par DRX, MEB, AFM et spectroscopie Raman. Nous avons également étudié les propriétés physiques des films minces ainsi que leur surface accessible par adsorption de gaz krypton (méthode de Brunauer, Emmett et Teller). Le traitement thermique à 450°C n'affecte pas la structure cristalline des couches, en revanche il tend à faire chuter fortement la surface accessible entre les colonnes. Après l'optimisation des paramètres de fonctionnement de la cellule de mesure, nous avons caractérisé les performances des films de CuO pour la détection du CO2. La meilleure réponse (?R/R=51 %) a été obtenue pour une couche élaborée à 2 Pa avec une puissance RF de 30W. De plus, la température optimale de mesure est relativement basse (T= 250°C). Le contrôle de la microstructure et plus particulièrement de la taille des grains s'est avéré être le paramètre principal qui impacte la réponse sous CO2. Les meilleurs résultats ont été obtenus avec des tailles de grains proches d'une vingtaine de nanomètres de diamètre. Une bonne modélisation de la réponse électrique en fonction de la taille des grains a pu être réalisée en prenant en compte un circuit électrique équivalent comportant une zone enrichie en porteur de type trous à la surface des grains et dont l'épaisseur est de l'ordre de la longueur de Debye. / The measure of the rate of CO2 is a recent need. The works on the use of new materials for the conception of gas sensors based semiconductor oxides, effective and not expensive; arouse a huge interest in our society. The objective of this thesis is the elaboration and the characterization of new sensitive layers obtained by RF sputtering for the realization of the sensors of CO2. Thin films were deposited using two targets: CuFeO2 and CuO, under three conditions by varying argon pressure and RF power. First of all, the structure and the microstructure were studied for the as-deposited samples. Surface investigations carried out by Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), Raman spectroscopy, BET measurements and MEB-FEG images have shown a strong influence of deposition technique parameters on film surface topography and morphology. In a second step, the thin films were annealed in air in order to oxidize the phase. For the composite CuO/CuFe2O4, Glow discharge optical emission spectrometry technique showed a structure in two layers stacked on top of each other for the thinner films. For the cupric films, no changes on both structure and microstructure have been revealed. Our films have then been evaluated for CO2 detection. The sensitive layers with different thicknesses were sensitive to 5000 ppm of CO2. The deposition parameters are optimized to obtain microstructure features which can enhance the sensitivity of the thin films as gas sensors. Best response was obtained for a cupric sample deposited in P2 30W conditions and was close to 50% at T = 250°C. We have demonstrates that cupric oxide alone can detect the CO2 gas and that the growth conditions determine the film surface characteristics. The gas sensing characteristics of these films are strongly influenced by both surface morphology and microstructure.
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Studies of p-type semiconductor photoelectrodes for tandem solar cellsSmith, Thomas January 2014 (has links)
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.
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