L'électronique basée sur le graphène fait face à un verrou technologique, qui est l'absence d'une bande interdite (gap) permettant une commutation entre les états logiques allumé et éteint. Les nano-rubans de graphène rendent possible l'obtention de ce gap mais il est difficile de produire de tels rubans avec une largeur précise à l'échelle atomique et des bords bien ordonnés. Le confinement électronique est une façon élégante d'ouvrir un gap et peut en principe être réglé en ajustant la largeur des nano-rubans. Cette thèse est consacrée à la compréhension de l'ouverture du gap par nano-structuration. Nous avons suivi deux approches: l'introduction d'un potentiel super-périodique sur le graphène par des substrats vicinaux de métaux nobles et le confinement électronique dans des nano-rubans sur des facettes artificielles du SiC. Des potentiels super-périodiques ont été introduits avec deux substrats nano-structurés: l'Ir(332) et un cristal courbé de Pt(111) multi-vicinale. Le graphène modifie les marches initiales des substrats et les transforme en une succession de terrasses (111) et de régions d'accumulation de marches, observés par STM. La nano-structuration du substrat induit alors un potentiel super-périodique dans le graphène entraînant l'ouverture de gaps sur la bande π du graphène observée par ARPES, ce qui est cohérent avec la périodicité structurale observé par STM et LEED. Les gaps peuvent être convenablement expliqués par un modèle de type hamiltonien de Dirac; ce dernier nous permet de retrouver la force du potentiel à la jonction entre les terrasses (111) et la région d'accumulation des marches. La force du potentiel dépend du substrat, de la périodicité associée à la surface et du type de bord des marches (soit type A ou B). Nous avons aussi changé le potentiel de surface en intercalant du Cu sur l'Ir(332), qui reste préférentiellement au niveau de l'accumulation des marches. La surface présente des régions dopées n alors que les régions non-intercalées restent dopées p, conduisant à une succession de rubans dopés n et p pour une même couche de graphène continue. La seconde approche pour contrôler le gap est par confinement électronique dans des nanorubans de graphène synthétisés sur du SiC. Ces rubans sont obtenus sur des facettes du SiC ordonnées périodiquement. Comme l'ouverture d'un gap d'origine inconnue avait été observée par ARPES, nous avons réalisé les premières études atomiquement résolues par STM. Nous démontrons la régularité et la chiralité des bords, nous localisons précisément les nanorubans de graphène sur les facettes et nous identifions des mini-facettes sur du SiC. Afin de comprendre le couplage entre le graphène et le substrat, nous avons étudié une coupe transversale par STEM/EELS, en complément des études par ARPES et STM/STS. Nous observons que la facette (1-107) où le graphène se trouve présente un sub-facettage sur les extrémités haute et basse. Le sub-facettage comprend des mini-terrasses (0001) et des mini-facettes (1-105). Le graphène s'étend tout au long du la région sub-facettée, et est couplé au substrat dans les mini-terrasses (0001), ce qui le rend semi-conducteur. En revanche, le graphène au-dessus des mini-facettes (1-105) est découplé du substrat mais présente un gap observé par EELS, et compatible avec les observations faites par ARPES. L'origine du gap est expliquée par le confinement électronique sur des nano-rubans de graphène de 1 - 2 nm de largeur localisés sur ces mini-facettes (1-105). / The major challenge for graphene-based electronic applications is the absence of the band-gap necessary to switch between on and off logic states. Graphene nanoribbons provide a route to open a band-gap, though it is challenging to produce atomically precise nanoribbon widths and well-ordered edges. A particularly elegant method to open a band-gap is by electronic confinement, which can in principle be tuned by adjusting the nanoribbon width. This thesis is dedicated to understanding the ways of opening band-gaps by nanostructuration. We have used two approaches: the introduction of a superperiodic potential in graphene on vicinal noble metal substrates and the electronic confinement in artificially patterned nanoribbons on SiC. Superperiodic potentials on graphene have been introduced by two nanostructured substrates, Ir(332) and a multivicinal curved Pt(111) substrate. The growth of graphene modifies the original steps of the pristine substrates and transforms them into an array of (111) terraces and step bunching areas, as observed by STM. This nanostructuration of the underlying substrate induces the superperiodic potential on graphene that opens mini-gaps on the π band as observed by ARPES and consistent with the structural periodicity observed in STM and LEED. The mini-gaps are satisfactorily explained by a Dirac-hamiltonian model, that allows to retrieve the potential strength at the junctions between the (111) terraces and the step bunching. The potential strength depends on the substrate, the surface periodicity and the type of step-edge (A or B type). The surface potential has also been modified by intercalating Cu on Ir(332), that remains preferentially on the step bunching areas, producing there n-doped ribbons, while the non-intercalated areas remain p-doped, giving rise to an array of n- and p- doped nanoribbons on a single continuous layer. In the second approach to control the gap, we have studied the gap opening by electronic confinement in graphene nanoribbons grown on SiC. These ribbons are grown on an array of stabilized sidewalls on SiC. As a band-gap opening with unclear atomic origin had been observed by ARPES, we carried-out a correlated study of the atomic and electronic structure to identify the band gap origin. We performed the first atomically resolved study by STM, demonstrating the smoothness and chirality of the edges, finding the precise location of the metallic graphene nanoribbon on the sidewalls and identifying an unexpected mini-faceting on the substrate. To understand the coupling of graphene to the substrate, we performed a cross-sectional study by STEM/EELS, complementary of our ARPES and STM/STS studies. We observe that the (1-107) SiC sidewall facet is sub-faceted both at its top and bottom edges. The subfacetting consists of a series of (0001) miniterraces and (1-105) minifacets. Graphene is continuous on the whole subfacetting region, but it is coupled to the substrate on top of the (0001) miniterraces, rendering it there semiconducting. On the contrary, graphene is decoupled on top of the (1-105) minifacets but exhibits a bandgap, observed by EELS and compatible with ARPES observations. Such bandgap is originated by electronic confinement in the 1 - 2 nm width graphene nanoribbons that are formed over the (1-105) minifacets.

Semiconducting aromatic-boron carbide composite/alloyed films formed by plasma enhanced chemical vapor deposition from carborane and aromatic precursors have been demonstrated to be excellent detectors for thermal neutrons because of the large 10B cross section. The electronic properties of these films derived from XPS show that the properties of boron carbide can be tuned by co-deposition of aromatic compounds and carborane. Aromatic doping results in narrower indirect band gaps (1.1 - 1.7 eV vs ~3 eV for orthocarborane-derived boron carbide without aromatics) and average charge transport lifetimes (as long as 2.5 ms for benzene-orthocarborane and 1.5 - 2.5 ms for indole-orthocarborane) that are superior to those of boron carbide (35 µs). The films also show enhanced electron-hole separation that is also superior to those of boron carbide where the states at the top of the valence band is made of aromatic components while states at the bottom of the conduction band is a combination of aromatic and carborane moeities. These properties result in greatly enhanced (~850%) charge collection, relative to films without aromatic content, in thermal neutron exposures at zero-bias, and are gamma-blind. Such films are therefore excellent candidates for zero-bias neutron detector applications. These properties also show little variation with increasing aromatic content beyond a critical concentration, indicating that at some point, excess aromatic results in the formation of regions of polymerized aromatic within the film, rather than in additional carborane/aromatic linkages. While previous studies on these aromatic-boron carbide materials indicate the potential for neutron detection due to the narrowed band gap, enhanced electron-hole separation and charge transport lifetimes compared to the boron carbide counterpart, the mechanisms of charge transport and photoconductivity (important for photovoltaic applications) of these materials have remained unexplored. Properties such as narrowed band gap, efficient electron-hole separation and long charge transport lifetimes, are also desirable in photovoltaic applications. This, plus ease of fabrication and environmental robustness makes aromatic-boron carbide films promising candidates for photovoltaic applications. Plasma enhanced chemical vapor deposition (PECVD) has been used to synthesize these aromatic-boron carbide composite films by co-deposition of pyridine, aniline or indole with orthocarborane/metacarborane. Film chemical composition and bonding were characterized by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), variable angle spectroscopic ellipsometry (VASE) and (in collaboration with Dowben Group at UNL) charge transport and photoconductivity measurements. Results show narrowed band gaps (indirect) where the top of the valence band is made up of the aromatic moiety and the conduction band minimum us made of aromatic and carborane moeities, improved charge carrier mobilities that is stoichiometry and frequency dependent (aniline-orthocarborane films). Photoconductivity measurement results obtained from ~2.6:1 indole-orthocarborane film show fourth quadrant conductivity. I(V) curves indicate a photocurrent of 2.36 µA at zero bias, with an appreciable open-circuit voltage of 1V. The ability for these aromatic-boron carbide films to operate at zero bias for both neutron detection and photovoltaic applications is an excellent advantage that indicates low cost of operation of these materials.

Wide band-gap semiconductor materials such as silicon carbide (SiC) and gallium nitride (GaN) have been widely investigated these years for their preferred operation at higher switching frequency, higher blocking voltage, higher temperature, with a compacter volume, in comparison with the traditional silicon (Si) devices. SiC MOSFETs have been utilized in photovoltaic systems, wind turbine converters, electric vehicles, solid-state transformers, more electric ships, and airplanes. GaN based transistors have also been adopted in the DC-to-DC converters in data centers, personal computers, AC-to-DC power factor correction converters for the consumer electronic adaptors, and DC-to-AC photovoltaic micro-inverters. The first part of this dissertation is regarding the lifetime modeling and condition monitoring for the SiC MOSFETs. Since SiC-based devices have different failure modes and mechanisms compared with Si counterparts, a comprehensive review will be conducted to develop accurate lifetime prediction, condition monitoring, and lifetime extension strategies. First, a novel comprehensive online updated system-level lifetime modeling approach will be presented. Second, to monitor the SiC MOSFET ageing, the typical degradation indicators of SiC MOSFET gate oxide will be investigated. Third, to measure the junction temperature, the dynamic temperature-sensitive electrical parameters for the medium-voltage SiC devices will be studied. The other part is the topology investigation of these emerging wide band-gap devices. A generalized topology that would leverage the advantages of the wide band-gap devices will be introduced and analyzed in detail. Following it is a new evaluation index for comparing different topologies with the consideration of the semiconductor die information. The topology and its derivatives will be utilized in the subsequent chapters for three applications. First, a 100 kW switched tank converter (STC) will be designed using SiC MOSFETs for transportation power electronic systems. Second, an updated STC topology integrating with the partial-power voltage regulation will be introduced for electric vehicle applications. Third, two novel single-phase resonant multilevel modular boost inverters will be designed based on the voltage-regulated STC. These topologies will be validated through designed prototypes. As a result, the high power density and high efficiency will be realized by combining the well-suited topologies and the advantages of the WBG devices.

Philosophiae Doctor - PhD / The main aim of this study was to prepare band gap-engineered graphene quantum dot (GQD) structures which match the different energies of the visible region in the solar spectrum. These band gap-engineered graphene quantum dot structures were used as donor materials in rainbow Schottky junction solar cells, targeting all the energies in the visible region of the solar spectrum for improved solar-to-electricity power conversion efficiency. Structural characterisation of the prepared nanomaterials under solid-state nuclear magnetic resonance spectroscopy (SS-NMR) showed appearance of bands at 40 ppm due to the presence of sp3 hybridised carbon atoms from the peripheral region of the GQD structures. Other bands were observed at 130 ppm due to the presence of polycyclic aromatic carbon atoms from the benzene rings of the GQD backbone, and around 180 ppm due to the presence of carboxylic acid carbons from oxidation due to moisture. Fourier-transform infrared resonance (FTIR) spectroscopy further confirmed the presence of aromatic carbon atoms and oxidised carbons due to the presence of C=O, C=C and -OH functional groups, concurrent with SS-NMR results. / 2023-12-01

Monolayer molybdenum disulfide (MoS2) is a three-atom-thick direct band gap semiconductor, which has received considerable attention for use as a channel material in atomically thin transistors, photodetectors, excitonic LED’s, and many other potential applications. It is also a mechanically exceptional material with a large stiffness and flexibility, and can withstand very large strains (11%) before rupture. In this dissertation we investigated the mechanics of the stiffness and adhesion forces in atomically thin MoS2 membranes, and how biaxial strains can be used to induce large modulations in the band structure of the material. First, we used chemical vapor deposition (CVD) to grow MoS2 crystals that are highly impermeable to gas, and used a pressure difference across suspended membranes to induce large biaxial strains. We demonstrated the continuous and reversible tuning of the optical band gap of suspended monolayer membranes by as much as 500 meV, and induced strains of as much as 5.6% before rupture. We observed the effect of strain on the energy and intensity of the peaks in the photoluminescence (PL) and Raman spectra and found their linear strain tuning rates, then report evidence for the strain tuning of higher level optical transitions. Second, we determined the Young’s modulus and works of separation and adhesion of MoS2 membranes, and found that adhesion hysteresis is an important effect in determining the behavior of our systems. Finally, we investigated the use of atomically thin materials as nanofiltration membranes, by perforating the material with nanopores which selectively permit the transport of smaller molecules while rejecting larger ones. We studied ion transport through nanopores in graphene membranes and demonstrate that in-situ atomic force microscope measurements in liquid are a powerful way to reveal occlusions and contaminants around the pores - work which will aid future researchers in further unveiling the properties of these fascinating systems.

The design of a dc generation system is posed as a multi-objective optimization problem which simultaneously designs the generator and the power converter. The proposed design methodology captures the interaction between various system component models and utilizes the system steady state analysis, stability analysis, and disturbance rejection analysis. System mass and power loss are considered as the optimization metrics and minimized. The methodology is demonstrated through the design of a notional dc generation system which contains a Permanent Magnet Synchronous Machine (PMSM), passive rectifier, and a dc-dc converter. To this end, a high fidelity PMSM model, passive rectifier model, semiconductor model and passive component model are developed. The output of optimization is a set of designs forming a Pareto-optimal front. Based on the requirements and the application, a design can be chosen from this set of designs. The methodology is applied to SiC based dc generation system and Si based dc generation system to quantify the advantage of Wide Bandgap (WBG) devices. A prototype SiC based dc generation system is constructed and tested at steady state. Finally a thermal equivalent circuit (TEC) based PMSM thermal model is included in the design paradigm to quantify the impact of the PMSM’s thermal performance to the system design.

We present the dielectric function of a bcc-In2O3 thin film in the wide spectral range from nearinfrared to vacuum-ultraviolet and for temperatures 10 K–300K, determined by spectroscopic ellipsometry. From the temperature dependence of electronic transition energies, we derive electron-phonon coupling properties and found hints that the direct parabolic band-band transitions involve In-d states. Further we discuss possible excitonic contributions to the dielectric function.

We determined the dielectric function of the alloy system (AlxGa1−x)2O3 by spectroscopic ellipsometry in the wide spectral range from 0.5 eV to 8.5 eV and for Al contents ranging from x = 0.11 to x = 0.55. For the composition range x<0.4, we observe single phase material in the b-modification and for larger Al content also the occurrence of γ-(Al,Ga)2O3. We derived spectra of the refractive index and the absorption coefficient as well as energy parameters of electronic bandband transitions by model analysis of the dielectric function. The dependence of the dielectric functions lineshape and the energy parameters on x is highly continuous, reflecting theoretical expectations. The data presented here provide a basis for a deeper understanding of the electronic properties of this material system and may be useful for device engineering.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18295号 / 工博第3887号 / 新制||工||1596(附属図書館) / 31153 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 赤木 和夫, 教授 辻 康之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第20460号 / 人博第810号 / 新制||人||194(附属図書館) / 28||人博||810(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 田部 勢津久, 教授 加藤 立久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM