Giant defect emission enhancement from ZnO nanowires through desulfurization process.

Zinc oxide (ZnO) is a stable, direct bandgap semiconductor emitting in the UV with a multitude of technical applications. It is well known that ZnO emission can be shifted into the green for visible light applications through the introduction of defects. However, generating consistent and efficient green emission through this process is challenging, particularly given that the chemical or atomic origin of the green emission in ZnO is still under debate. In this work we present a new method, for which we coin term desulfurization, for creating green emitting ZnO with significantly enhanced quantum efficiency. Solution grown ZnO nanowires are partially converted to ZnS, then desulfurized back to ZnO, resulting in a highly controlled concentration of oxygen defects as determined by X-ray photoelectron spectroscopy and electron paramagnetic resonance. Using this controlled placement of oxygen vacancies we observe a greater than 40-fold enhancement of integrated emission intensity and explore the nature of this enhancement through low temperature photoluminescence experiments

Élaboration et caractérisation de capteurs de gaz à base de nanofils de ZnO

Les capteurs de gaz à base d'oxydes métalliques connaissent un engouement croissant pour des applications industrielles, militaires et environnementales. Néanmoins, ces capteurs se montrent peu sélectifs et nécessitent des températures de travail élevées pour obtenir une bonne sensibilité. La nanostructuration des matériaux permet d'augmenter la surface de réaction entre le gaz et le matériau hôte, améliorant ainsi la performance du capteur. ZnO est un semi-conducteur à large gap direct (3,37 eV) possédant de nombreuses propriétés physico-chimiques intéressantes, et aussi un matériau très prometteur pour les capteurs de gaz de type oxyde métallique. L'Elaboration de nanostructures de ZnO a conduit à un grand nombre d'études pour divers domaines d'applications. Dans ce contexte, cette thèse a pour objectif la synthèse des réseaux de nanofils de ZnO par voie hydrothermale et l'étude de leurs propriétés de détection. La première partie de ce travail porte sur l'étude systématique des différents paramètres influençant la synthèse des nanofils de ZnO. Les résultats montrent que la température de croissance, le pH de la solution et le temps de croissance influent sur la morphologie des nanofils de ZnO. Des nanofils avec un facteur d'aspect proche de 30 ont été obtenus sous conditions d'élaboration optimisées. La seconde partie de ce travail consiste en l'étude des propriétés de détection de nanofils de ZnO, par des méthodes électrique et optique. Les mesures électriques montrent une variation de résistance des nanofils, tandis que l'absorption UV révèle un déplacement du bandgap en présence du gaz. Une diminution de la résistance et un blue-shift de bandgap ont été observés lors de la présence d'un gaz réducteur tel que l'éthanolMetal oxides based gas sensors are widely used in industrial, military and environmental applications. But the main fault of these sensors remains on their lack of selectivity and requiring high working temperature to obtain a good sensitivity. Nanostructuration of the materials presents an efficient way to enhance the reaction surface between gas and the host material, thus improving the sensor performance. ZnO is an n-type semiconductor with large bandgap energy of 3.37 eV at room temperature owning many interesting physical and chemical properties, and is also very sensitive for reducing gases. In recent years, many studies develop and improve the ZnO related nanostructures for various applications. The goal of this thesis consists in the synthesis of the ZnO nanowire arrays via hydrothermal method and the study of their sensing properties. The first part of this work shows a systematic study of the various influencing parameters during the ZnO nanowire synthesis. The results show that the growth temperature, the solution pH value and the growth time influence the nanowire morphology. Nanowires with an aspect ratio about 30 have been obtained under optimized growth conditions. The second part of this work consists of the study of the ZnO nanowire sensing properties, using both electrical and optical methods. The electrical measurements show a resistivity variation of the nanowires, while the UV absorption spectra reveal a bandgap shift under injected gas. A resistivity reduction and a blue-shift of a bandgap of the ZnO nanowires were observed under injected reducing gas such as ethanolPARIS-EST-Université (770839901) / SudocSudocFranceF

Gold metallization of hybrid organic-inorganic polymer microstructures 3D printed by two-photon polymerization

International audienceTwo-photon polymerization is a femtosecond laser-based technique enabling printing of three-dimensional structures down to submicron resolution within photocurable polymers. Rendering the dielectric 3D printed structures conductive can be of great benefit for various applications in domains such as energy, photonics, or multifunctional devices. In this work, the microstructures of interest are made of a silicon-zirconium hybrid organic-inorganic polymer exhibiting low shrinkage during development. A simple and efficient metallization method by electroless plating is investigated to deposit a gold layer on the surface of the printed microstructures. The influence of the method parameters on the quality and properties of the deposited layer is studied. Among these parameters, the surface modification agent concentration and step duration, as well as the seeding solution concentration, must be adapted to the specific case of the considered hybrid microstructures. The concentration of metal ions in the plating bath is the most influential parameter on the morphology of the deposited gold layers. In particular, higher concentrations lead to smooth and continuous layers with electrical conductivities higher than half that of bulk gold. Finally, the deposited layers are shown to coat 3D printed microstructures of arbitrary shapes, thus confirming the conformality of the method at the micrometric scale

Giant defect emission enhancement from ZnO nanowires through desulfurization process

International audienceZinc oxide (ZnO) is a stable, direct bandgap semiconductor emitting in the UV with a multitude of technical applications. It is well known that ZnO emission can be shifted into the green for visible light applications through the introduction of defects. However, generating consistent and efficient green emission through this process is challenging, particularly given that the chemical or atomic origin of the green emission in ZnO is still under debate. In this work we present a new method, for which we coin term desulfurization, for creating green emitting ZnO with significantly enhanced quantum efficiency. Solution grown ZnO nanowires are partially converted to ZnS, then desulfurized back to ZnO, resulting in a highly controlled concentration of oxygen defects as determined by X-ray photoelectron spectroscopy and electron paramagnetic resonance. Using this controlled placement of oxygen vacancies we observe a greater than 40-fold enhancement of integrated emission intensity and explore the nature of this enhancement through low temperature photoluminescence experiments