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Integration, Stability, and Doping of Mono-Elemental and Binary Transition Metal Dichalcogenide Van der Waals Solids for Electronics and Sensing DevicesMehta, Ravindra K 05 1900 (has links)
In this work, we have explored 2D semiconducting transition metal dichalcogenides (TMDs), black phosphorus (BP), and graphene for various applications using liquid and mechanical exfoliation routes. The topical areas of interest that motivate our work include considering factors such as device integration, stability, doping, and the effect of gasses to modulate the electronic transport characteristics of the underlying 2D materials. In the first area, we have integrated solution-processed transparent conducting oxides (TCOs), specifically indium-doped tin oxide (ITO) with BP, which is a commonly used TCO for solar cell devices. Here we have found surface treatment of glass substrates with a plasma before spin-coating the solution-processed ITO, to be effective in improving coverage and uniformity of the ITO film by promoting wettability and film adhesion. The maximum transmittance obtained was measured to be ~75% in the visible region, while electrical measurements made on BP/ITO heterostructures showed improved transport characteristics compared to the bare ITO film. Within the integration realm, inkjet-printing of BP and MoS2 p-n hetero-junctions on standard ITO glass substrates in a vertical architecture was also demonstrated. To address the issue of stability which some 2D materials such as BP face, we experimented with ionic liquids (ILs) to passivation the hydrophilic surface of BP to minimize its oxidative degradation. The enhanced stability of BP was inferred through Raman spectroscopy and scanning probe microscopy techniques, where no observable changes in the A1g and A2g Raman vibrational modes were observed for the BP films passivated with ILs over time under ambient conditions. On the other hand, a blue-shift in these Raman modes was evident for unpassivated samples. Atomic force microscopy measurements on the unpassivated samples clearly revealed the difference in surface characteristics through localized regions of degradation that intensified with time which was absent in IL passivated BP samples. The electronic device measurements for IL coated BP devices showed a more stabilized Ids−Vds characteristic in the 5.4 K to 335 K temperature range. Prototypical demonstrations of stabilized ILs/BP devices at ambient printed on flexible polyimide substrates were also successfully made. At the same time, doping is one of the essential steps required for the modulation of carrier density and electronic transport in electronic and optoelectronic devices, which is the third topical area we have addressed in this work with semiconducting TMDs. Of the conventional approaches used to dope 3D semiconductors, ion-implantation is commonly adopted but given the ultra-thin nature of 2D materials, this approach is not feasible as it causes severe damage to the delicate crystalline lattice of ultra-thin 2D membranes. Instead, we have used plasma-based doping routes with UV-ozone treatement and solution processing using 1,2 dichloroethane, to characterize the temperature-dependent two-terminal and three-terminal electronic and optoelectronic transport of mechanically exfoliated 2D MoS2 and WSe2. A significant difference was seen in the optoelectronic properties between the two dopants, owing to differences in their respective doping mechanisms and the intrinsic structural attributes of the exfoliated flakes. A significant reduction in barrier height was evident after doping using both techniques in MoS2, while an increase in barrier height after soaking in 1,2 dichloroethane was seen in WSe2. Lastly, in the fourth topical area for sensing devices, we have studied the effect of gas-flow in inkjet-printed and spin-coated graphene and MoS2 to modulate the electronic transport for the 2D materials since their increased surface area is an ideal platform to observe interactions with external stimuli, in this case, in-coming gas species. Here, the chamber pressure and change in current with flow of gas was measured in the steady-state, as well as time-dependent dynamic transport toward nitrogen and carbon dioxide. We observed significant differences in the electrical response of mono-elemental graphene and binary MoS2, owing to differences in microstructure and joule heating response to the ambient gas. In conclusion, the findings obtained from our work will provide an important framework to help guide strategies in further improving integration schemes, stability, doping and sensing behavior driven by the unique structural attributes inherent to 2D materials for high-performance devices in the future.
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Design of passive methane oxidation biosystems considering their response to the presence of capillary barrier effect / Conception des biosystèmes d'oxydation passive du méthane considérant leur réponse à l'effet de barrière capillaireAhou Ghalandari, Bahar January 2016 (has links)
La construction des biosystèmes d’oxydation passive du méthane (BOPM) est une option économique et durable pour réduire les émissions de méthane des sites d’enfouissement de déchets et des effets subséquents du réchauffement climatique. Les BOPM sont constitués de deux couches principales: la couche d'oxydation du méthane (MOL) et la couche de distribution du gaz (GDL). L'oxydation du méthane se produit dans la MOL par les réactions biochimiques des bactéries méthanotrophes, et la GDL est construite sous la MOL pour intercepter et distribuer les émissions fugitives de biogaz à la base de la MOL. Fondamentalement, l'efficacité d'un BOPM est définie en fonction de l'efficacité d'oxydation du méthane dans la MOL. Par conséquent, il est indispensable de fournir des conditions adéquates pour les activités bactériennes des méthanotrophes. En plus des paramètres environnementaux, l'intensité et la distribution du biogaz influencent l'efficacité des BOPM, et ils peuvent rendre le matériau de la MOL - avec une grande capacité d'accueillir les activités bactériennes - inutilisables en termes d'oxydation du méthane sur place. L'effet de barrière capillaire le long de l'interface entre la GDL et la MOL peut provoquer des émissions localisées de méthane, due à la restriction ou la distribution non uniforme de l’écoulement ascendant du biogaz à la base de la MOL. L'objectif principal de cette étude est d'incorporer le comportement hydraulique non saturé des BOPM dans la conception des BOPM, afin d’assurer la facilité et la distribution adéquates de l'écoulement du biogaz à la base de la MOL. Les fonctions de perméabilité à l'air des matériaux utilisés pour construire la MOL des BOPM expérimentaux au site d’enfouissement des déchets de St Nicéphore (Québec, Canada), ainsi que celles d'autres de la littérature technique, ont été étudiés pour évaluer le comportement d'écoulement non saturé du gaz dans les matériaux et pour identifier le seuil de migration sans restriction du gaz. Ce dernier seuil a été introduit en tant que un paramètre de conception avec lequel le critère de conception recommandé ici, c’est à dire la longueur de la migration sans restriction de gaz (LMSG), a été défini. La LMSG est considérée comme la longueur le long de l'interface entre la GDL et la MOL où le biogaz peut migrer à travers la MOL sans restriction. En réalisant des simulations numériques avec SEEP/W, les effets de la pente de l'interface, des paramètres définissant la courbe de rétention d'eau, de la fonction de la conductivité hydraulique du matériau de la MOL sur la valeur de la LMSG (représentant la facilité d'écoulement du biogaz à l'interface) et de la distribution de l'humidité (et par conséquent celle du biogaz) ont été évalués. Selon les résultats des simulations, la conductivité hydraulique saturée et la distribution des tailles de pores du matériau de la MOL sont les paramètres les plus importants sur la distribution de l'humidité le long de l'interface. Ce dernier paramètre influe également sur la valeur du degré de saturation et donc la facilité du biogaz à la base de la MOL. La densité sèche du matériau de MOL est un autre paramètre qui contrôle la facilité d'écoulement ascendant du biogaz. Les limitations principales de la présente étude sont associées au nombre de matériaux de MOL testés et à l'incapacité de SEEP/W de considérer l'évapotranspiration. Toutefois, compte tenu des hypothèses raisonnables dans les simulations et en utilisant les données de la littérature, on a essayé de réduire ces limitations. En utilisant les résultats des expériences et des simulations numériques, des étapes et des considérations de conception pour la sélection du matériau de MOL et de la pente d'interface ont été proposées. En effet,le comportement hydraulique non saturé des matériaux serait intégré dans les nécessités de conception pour un BOPM efficace, de sorte que la capacité maximale possible d'oxydation du méthane du matériau de la MOL soit exploitée. / Abstract : Implementation of passive methane oxidation biosystems (PMOB) is a cost effective and sustainable solution to eliminate the methane emissions of landfills to the atmosphere and ensuing global warming effects. PMOBs consist of two main layers: methane oxidation layer (MOL) and gas distribution layer (GDL). The oxidation of methane occurs in MOL through the biochemical reactions of methanotrophic bacteria, and GDL is constructed beneath the MOL to intercept and distribute the fugitive biogas emissions at the base of MOL. Basically, the efficiency of a PMOB is defined based on the methane oxidation efficiency in MOL. Therefore, it is indispensable to provide adequate conditions for the bacterial activities of methanotrophs. In addition to the environmental parameters, the intensity and the distribution of the biogas reaching the MOL material influence the efficiency of PMOBs, and they may cause the MOL material possessing great capacity to host the bacterial activities to be unserviceable in terms of in field methane oxidation. The capillary barrier effect along the GDL MOL interface may provoke localized surface methane emissions, resulted from the restricted and/or non uniform distribution of upward flow of biogas at the base of MOL. The main focus of present study is to incorporate the unsaturated hydraulic behavior of PMOBs into the design of PMOBs, providing adequate ease and distribution of upward flow of biogas at the base of MOL. The air permeability functions of the materials used to construct the MOL of experimental PMOBs at the St Nicephore landfill (Quebec, Canada), along with other materials from the technical literature, were studied to evaluate the unsaturated gas flow behavior of the materials and to identify the threshold of unrestricted gas migration. This latter threshold was introduced as a design parameter based on which the recommended design criterion herein, i.e. the length of unrestricted gas migration (LUGM), was defined. LUGM is considered as the length along the GDL MOL interface along which biogas can migrate upwards without restriction. Performing sets of numerical simulations in SEEP/W, the effect of slope of interface and the parameters defining the water retention curve and hydraulic conductivity function of MOL material on value of LUGM (representing the ease of upward flow of biogas at the interface) and distribution of moisture (and therefore biogas) along the GDL MOL interface were assessed. The saturated hydraulic conductivity and the pore size distribution of the MOL material were the most influencing parameters in distribution of moisture along the interface. The latter parameter influences also the value of degree of saturation and therefore, the ease of biogas at the base of MOL. Dry density of MOL material is another parameter that controls the ease of upward flow of biogas. The main limitations of the present study are associated with the number of tested MOL materials and the inability of SEEP/W in considering the evapotranspiration. However, considering reasonable assumptions in simulations and using the data from the literature, it was attempted to reduce the limitations. Based on the results of experiments and numerical simulations, some design steps and considerations for selection of the MOL material and the slope of interface were suggested that incorporate the unsaturated hydraulic behavior into the design necessities for an efficient PMOB so that the maximum possible methane oxidation capacity of MOL material is exploited.
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