Hydrogen exposure of insulating d0-titanates, such as SrTiO3 (STO), has displayed the formation of intriguing conducting states. These conducting states form through the use of forming gas (N2/H2) annealing or hydrogen plasma exposure, where hydrogen gas is exposed to high energy microwaves. The exposure of STO to hydrogen causes metallic conductivity due to the introduction of hydrogen cations on some of the oxygen sites. However, the optical properties of this hydrogen-exposed STO have not been well-studied. Further, Ba0.5Sr0.5TiO3 (BST), an insulating dielectric, also shows changes in its conductivity upon hydrogen exposure. Unlike STO where the conductivity of the hydrogen-exposed material has been characterized, the optical, electronic, and transport properties of hydrogen exposed BST have not been studied. Thus, by studying hydrogen-exposed BST and STO, our understanding of the effects of hydrogen on insulators can be enhanced. In the first study, the effects of the exposure of insulating dielectric BST thin films to a hydrogen plasma is presented. These BST thin films are deposited on GdScO3 (GSO) substrates via Pulsed Laser Deposition (PLD). After deposition, the thin films are exposed to a hydrogen plasma. Just five minutes of hydrogen plasma exposure is enough to induce conductivity in the BST thin film. This conducting state is dominated by the interplay of disorder and strong electron correlations introduced during hydrogen exposure. Further, the optical properties indicate the formation of a transparent conductor, as the introduction of disorder and strong correlations has not changed the optical properties of the BST thin film in the visible spectrum. BST demonstrates an example of a new type of transparent conductor that utilizes large effective mass carriers to generate conductivity. In the second study, the effects of hydrogen doping on the surface of STO is explored. The conducting heterointerface that forms between PLD-deposited thin films of LaAlO3 (LAO) on STO is used as the standard to explore this hydrogen surface doping. The optical, electronic, and transport properties of water-leached and buffered hydrofluoric acid (BHF) etched heterointerfaces are characterized and compared. The recently developed water-leaching method is compared with the well-known BHF etching method, which has been shown to unintentionally dope the STO surface with fluorine and hydrogen. Both methods generate single-terminated atomically flat STO substrate surfaces that are ideal for heterointerface formation. After deposition, the optical, electronic, and transport properties of both the water-leached and BHF-etched heterointerfaces show no meaningful difference, demonstrating that water-leaching may also unintentionally dope the STO substrate surface with hydrogen. However, these results confirm that water-leaching generates a high-quality conducting heterointerface without the safety concerns of BHF.

abstract: The origins of carrier mobility (μe) were thoroughly investigated in hydrogenated indium oxide (IO:H) and zinc-tin oxide (ZTO) transparent conducting oxide (TCO) thin films. A carrier transport model was developed for IO:H which studied the effects of ionized impurity scattering, polar optical phonon scattering, and grain boundary scattering. Ionized impurity scattering dominated at temperatures below ~240 K. A reduction in scattering charge Z from +2 to +1 as atomic %H increased from ~3 atomic %H to ~5 atomic %H allowed μe to attain >100 cm^2/Vs at ~5 atomic %H. In highly hydrogenated IO:H, ne significantly decreased as temperature increased from 5 K to 140 K. To probe this unusual behavior, samples were illuminated, then ne, surface work function (WF), and spatially resolved microscopic current mapping were measured and tracked. Large increases in ne and corresponding decreases in WF were observed---these both exhibited slow reversions toward pre-illumination values over 6-12 days. A hydrogen-related defect was proposed as source of the photoexcitation, while a lattice defect diffusion mechanism causes the extended decay. Both arise from an under-coordination of the In. An enhancement of μe was observed with increasing amorphous fraction in IO:H. An increase in population of corner- and edge-sharing polyhedra consisting of metal cations and oxygen anions is thought to be the origin. This indicates some measure of medium-range order in the amorphous structure, and gives rise to a general principle dictating μe in TCOs---even amorphous TCOs. Testing this principle resulted in observing an enhancement of μe up to 35 cm^2/Vs in amorphous ZTO (a-ZTO), one of the highest reported a-ZTO μe values (at ne > 10^19 cm^-3) to date. These results highlight the role of local distortions and cation coordination in determining the microscopic origins of carrier generation and transport. In addition, the strong likelihood of under-coordination of one cation species leading to high carrier concentrations is proposed. This diverges from the historical indictment of oxygen vacancies controlling carrier population in crystalline oxides, which by definition cannot occur in amorphous systems, and provides a framework to discuss key structural descriptors in these disordered phase materials. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

The landscape of consumer electronics has drastically changed over the last decade. Technological advances have led to the development of portable media devices, such as the iPod, smart phones and laptops. This has been achieved primarily through miniaturisation and using materials such as Lithium and Indium Tin Oxide (ITO) to increase energy density in batteries and as transparent electrodes for light emitting displays respectively. However, ten years on there are now new consumer demands, which are dictating the direction of research and new products are under constant development. Graphene is a promising next-generation material that was discovered in 2004. It is composed of a two-dimensional lattice made only from carbon. The atoms are arranged in a two atom basis hexagonal crystal structure which forms a fundamental building block of all sp2 hybrid forms of carbon. The production of large area graphene has a high cost, due to the long growth times and the high temperatures required. This is relevant as graphene is not viable compared to other transparent conductors which are produced on industrial scales for a fraction of the cost of graphene growth. Furthermore, graphene has a high intrinsic resistivity (2KW/_) which is three orders of magnitude greater than the current industry standard ITO. This limits the size of the electrodes as there is dissipation of energy across the electrode leading to inefficiency. Furthermore a potential drop occurs across the electrode leading to a non-uniform light emission when the electrode is used in a light emitting display. I investigate alternative methods of large area graphene growth with the aim of reducing the manufacturing costs, while maintaining the quality required for graphene human interface devices. Building on this I develop new fabrication methods for the production of large-area graphene devices which are flexible and transparent and show the first all graphene touch sensor. Focusing on the reducing the high resistivity of graphene using FeCl3 intercalation, while maintaining high optical transmission, I show low resistivity achieved using this process for microscopic graphene flakes, large-area graphene grown on silicon carbide and large-area graphene grown by CVD. Furthermore, I explore the stability of FeCl3 intercalated graphene and a process to transfer a material to arbitrary flexible substrates.

Dans cette thèse, des films à base de graphène ont été étudiés comme alternatives viables dans la fabrication d'électrodes transparentes (TCE). Elle met l'accent sur des couches fines de graphène (FLG), sur l'oxyde de graphène réduit (RGO) et leurs hybrides avec des nanotubes de carbone (NTCs) pour être utilisé comme TCE dans les cellule solaires organiques (OSC). Les FLGs et RGO ont été préparés par des méthodes d'exfoliation mécanique ou en phase liquide assistée par micro-ondes. Ces nanomatériaux dilués dans un solvant liquide ont été déposé en couche mince par aérographe. Des caractérisations de transport de charge ont été obtenues grâce à la méthode des 4 pointes. Ces échantillons ont été caractérisés: leur transparence(UV-Visible), leur morphologie et leur topographique (MEB, MET, AFM) ainsi que le travail de sortie (UPS). Pour obtenir des informations sur la qualité structurelle des échantillons, nous avons utilisés les méthodes de spectroscopie XPS, Raman et la photoluminescence. / Graphene mate rials have been researched as viable alternatives of transparent conductors electrodes (TCEs) in this thesis. Current study focuses on few layer graphene (FLG), reduced graphene oxide (rGO) and their hybrids with carbon nanotubes (CNTs) for TCE applications inorganic solar cells (OSCs). FLGs and rGOs have been prepared by mechanical and microwave-assisted exfoliation methods. This films of these materials have been produced by hot-spray method. Results of charge transport characterizations by four-point probes, transparency (UV-Vis), measurements, along with morphological (SEM, TEM) and topgraphic (AFM) studies of films have been presented. UPS studies were performed to determine for a work-function. XPS,Raman and Photoluminescence studies have been employed to obtain the information about the structural quality of the samples.