abstract: This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3). Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

A eletrônica molecular vem sendo investigada intensivamente por mais de vinte anos. Nesse sentido, as pesquisas científicas estão sendo focadas na busca de estruturas que possam ser utilizadas na construção de dispositivos em escalas nanométricas, que possam substituir a tecnologia tradicional do silício. O objetivo principal deste trabalho foi explorar as propriedades físicas de sistemas a base de grafano, um dos mais promissores materiais para serem usados como nanodispositivos. Para isso, foi realizada uma investigação teórica, baseada em cálculos de primeiros princípios, das propriedades estruturais e eletrônicas do grafeno numa forma pura ou com defeitos intrínsecos e extrinsecos. O primeiro grupo de estruturas investigadas foi o grafeno e grafano como nanofolhas constituídas por elementos do grupo IV da tabela periódica (C, SiC, Si, Ge e Sn). Também foram analisadas as mudanças nas propriedades eletrônicas do grafano do grupo IV com a substituição dos átomos de hidrogênio por flúor. A segunda parte do trabalho explorou as propriedades de defeitos estruturais em grafeno, tais como a monovacância, divacância, trivacância e Stone-Wales, e também o grafeno com dopantes (boro e nitrogênio) em diversas configurações. Todos os cálculos foram feitos utilizando métodos ab initio com base na teoria do funcional densidade. Foram estudadas algumas possíveis aplicações para os grupos de estruturas de grafeno investigados, através da análise de algumas de suas propriedades, tais como as densidades de estados próximas ao nível de Fermi e as estruturas de bandas eletrônicas para cada sistema. / The molecular electronics has been investigated for more than twenty years. In this sense, the scientific research has been focused on the search for structures that could be used in nanoelectronic devices that could replace the traditional silicon technology. The major goal of this work is to explore the physical properties of systems based on graphene, one of the most promising materials to be used in nanoelectronics. For that, an ab initio investigation was carried on the structural and electronic properties of graphene in its pristine form and with intrinsic and extrinsic defects. The first investigation explored the properties of group IV nanosheets (of C, SiC, Si, Ge e Sn), and the modifications on their properties as result of hydrogenation or fluorination. The second part of this work explored the physical properties of structural intrinsic defects in graphene, such as monovacancy, divacancy, trivacancy, and Stone-Wales ones. The work also explored the properties of boron and nitrogen dopants. All the calculations were performed using the ab initio methodology, based on the density functional theory.

Two dimensional (2D) systems with low carrier density is an outstanding platform for studying a wide spectrum of physics. These include both classical and quantum effects, arising from disorder, Coulomb interactions and even non-trivial topological properties of band-structure. In this thesis, we have explored the physics at low carrier number density in GaAs/AlGaAs heterostructure and bilayer graphene, by investigating in a larger phase space using a variety of electrical measurement tools. A two-dimensional electron system (2DES) formed in a GaAs/AlGaAs heterostructure offers an avenue to build a variety of mesoscopic devices, primarily because its surface gates can very effectively control its carrier density profile. In the first half of the thesis, we study the relevance of disorder in two kinds of devices made in a 2DES. A very strong negative gate voltage not only reduces the carrier density of the 2DES, but also drives it to a disordered state. In this state, we explore a new direction in parameter space by increasing in-plane electric field and investigating its magneto-resistance (MR). At sufficiently strong gate voltage and source-drain bias, we discover a remarkably linear MR. Its enormous magnitude and weak temperature dependence indicate that this is a classical effect of disorder. In another study, we examine a specially designed dual-gated device that can induce low number density in a periodic pattern. By applying appropriate gate voltages, we demonstrate the formation of an electrostatically tunable quantum dot lattice and study the impact of disorder on it. This work is important in paving way for solid state based platform for experimental simulations of artificial solids. The most striking property of bilayer graphene is the ability to open its band gap by a perpendicular electric field, giving the prospects of enabling a large set of de-vice applications. However, despite a band gap, a number of transport mechanisms are still active at very low densities that range from hopping transport through bulk to topologically protected 1D transport at the edges or along 1D crystal dislocations. In the second half of the thesis, we have used higher order statistical moment of resistance/conductance fluctuations, namely the variance of the fluctuations, to complement averaged resistance/conductance, and study and infer the dominant transport mechanism at low densities in a gapped bilayer graphene. Our results show possible evidence of percolative transport and topologically protected edge transport at different ranges of low number densities. We also explore the same phase space by studying its mesoscopic conductance fluctuations at very low temperatures. This is the first of its kind systematic experiment in a dual-gated bilayer graphene device. Its conductance fluctuations have several anomalous features suggesting non-universal behaviour which is at odds with conventional disordered systems.

A eletrônica molecular vem sendo investigada intensivamente por mais de vinte anos. Nesse sentido, as pesquisas científicas estão sendo focadas na busca de estruturas que possam ser utilizadas na construção de dispositivos em escalas nanométricas, que possam substituir a tecnologia tradicional do silício. O objetivo principal deste trabalho foi explorar as propriedades físicas de sistemas a base de grafano, um dos mais promissores materiais para serem usados como nanodispositivos. Para isso, foi realizada uma investigação teórica, baseada em cálculos de primeiros princípios, das propriedades estruturais e eletrônicas do grafeno numa forma pura ou com defeitos intrínsecos e extrinsecos. O primeiro grupo de estruturas investigadas foi o grafeno e grafano como nanofolhas constituídas por elementos do grupo IV da tabela periódica (C, SiC, Si, Ge e Sn). Também foram analisadas as mudanças nas propriedades eletrônicas do grafano do grupo IV com a substituição dos átomos de hidrogênio por flúor. A segunda parte do trabalho explorou as propriedades de defeitos estruturais em grafeno, tais como a monovacância, divacância, trivacância e Stone-Wales, e também o grafeno com dopantes (boro e nitrogênio) em diversas configurações. Todos os cálculos foram feitos utilizando métodos ab initio com base na teoria do funcional densidade. Foram estudadas algumas possíveis aplicações para os grupos de estruturas de grafeno investigados, através da análise de algumas de suas propriedades, tais como as densidades de estados próximas ao nível de Fermi e as estruturas de bandas eletrônicas para cada sistema. / The molecular electronics has been investigated for more than twenty years. In this sense, the scientific research has been focused on the search for structures that could be used in nanoelectronic devices that could replace the traditional silicon technology. The major goal of this work is to explore the physical properties of systems based on graphene, one of the most promising materials to be used in nanoelectronics. For that, an ab initio investigation was carried on the structural and electronic properties of graphene in its pristine form and with intrinsic and extrinsic defects. The first investigation explored the properties of group IV nanosheets (of C, SiC, Si, Ge e Sn), and the modifications on their properties as result of hydrogenation or fluorination. The second part of this work explored the physical properties of structural intrinsic defects in graphene, such as monovacancy, divacancy, trivacancy, and Stone-Wales ones. The work also explored the properties of boron and nitrogen dopants. All the calculations were performed using the ab initio methodology, based on the density functional theory.

Oxide heterostructures are attracting huge interest in recent years due to the special functionalities of quasi two-dimensional quantum gases. In this thesis, the electronic states at the interface between perovskite oxides and pyrite compounds have been studied by first-principles calculations based on density functional theory. Optimization of the atomic positions are taken into account, which is considered very important at interfaces, as observed in the case of LaAlO3/SrTiO3. The creation of metallic states at the interfaces thus is explained in terms of charge transfer between the transition metal and oxygen atoms near the interface. It is observed that with typical thicknesses of at least 10-12 °A the gases still extend considerably in the third dimension, which essentially determines the magnitude of quantum mechanical effects. To overcome this problem, we propose incorporation of highly electronegative cations (such as Ag) in the oxides. A fundamental interest is also the thermodynamic stability of the interfaces due to the possibility of atomic intermixing in the interface region. Therefore, different cation intermixed configurations are taken into account for the interfaces aiming at the energetically stable state. The effect of O vacancies is also discussed for both polar and non-polar heterostructures. The interface metallicity is enhanced for the polar system with the creation of O vacancies, while the clean interface at the non-polar heterostructure exhibits an insulating state and becomes metallic in presence of O vacancy. The O vacancy formation energies are calculated and explained in terms of the increasing electronegativity and effective volume of A the side cation. Along with these, the electronic and magnetic properties of an interface between the ferromagnetic metal CoS2 and the non-magnetic semiconductor FeS2 is investigated. We find that this contact shows a metallic character. The CoS2 stays quasi half metallic at the interface, while the FeS2 becomes metallic. At the interface, ferromagnetic ordering is found to be energetically favorable as compared to antiferromagnetic ordering. Furthermore, tensile strain is shown to strongly enhance the spin polarization so that a virtually half-metallic interface can be achieved, for comparably moderate strain. Our detailed study is aimed at complementing experiments on various oxide interfaces and obtaining a general picture how factors like cations, anions, their atomic weights and elecronegativities, O vacancies, lattice mismatch, lattice relaxation, magnetism etc play a combined role in device design.

Interface effects in two-dimensional (2D) materials play a critical role for the electronic properties and device characteristics. Here we use first-principles calculations to investigate interface effects in 2D materials enabling new applications. We first show that graphene in contact with monolayer and bilayer PtSe2 experiences weak van der Waals interaction. Analysis of the work functions and band bending at the interface reveals that graphene forms an n-type Schottky contact with monolayer PtSe2 and a p-type Schottky contact with bilayer PtSe2, whereas a small biaxial tensile strain makes the contact Ohmic in the latter case as required for transistor operation. For silicene, which is a 2D Dirac relative of graphene, structural buckling complicates the experimental synthesis and strong interaction with the substrate perturbs the characteristic linear dispersion. To remove this obstacle, we propose solid argon as a possible substrate for realizing quasi-freestanding silicene and argue that a weak van der Waals interaction and small binding energy indicate the possibility to separate silicene from the substrate. For the silicene-PtSe2 interface, we demonstrate much stronger interlayer interaction than previously reported for silicene on other semiconducting substrates. Due to the inversion symmetry breaking and proximity to PtSe2, a band gap opening and spin splittings in the valence and conduction bands of silicene are observed. It is also shown that the strong interlayer interaction can be effectively reduced by intercalating NH3 molecules between silicene and PtSe2, and a small NH3 discussion barrier makes intercalation a viable experimental approach. Silicene/germanene are categorized as key materials for the field of valleytronics due to stronger spin-orbit coupling as compared to graphene. However, no viable route exists so far to experimental realization. We propose F-doped WS2 as substrate that avoids detrimental effects and at the same time induces the required valley polarization. The behavior is explained by proximity effects on silicene/germanene due to the underlying substrate. Broken inversion symmetry in the presence of WS2 opens a substantial band gap in silicene/germanene. F doping of WS2 results in spin polarization, which, in conjunction with proximity-enhanced spin orbit coupling, creates sizable spin-valley polarization. For heterostructures of silicene and hexagonal boron nitride, we show that the stacking is fundamental for the details of the dispersion relation in the vicinity of the Fermi energy (gapped, non-gapped, linear, parabolic) despite small differences in the total energy. We also demonstrate that the tightbinding model of bilayer graphene is able to capture most of these features and we identify the limitations of the model.

Sodium-ion batteries (SIBs) are rechargeable batteries analogous to lithium-ion batteries but use sodium ions (Na+) as the charge carriers. They are considered a promising alternative for lithium-ion batteries (LIBs) in renewable large-scale energy storage applications due to their similar electrochemical mechanisms and abundant sodium resources. Two-dimensional (2D) materials, with atomic or molecular thickness and large lateral lengths, have emerged as important functional materials due to their unique structures and excellent properties. These 2D nanosheets have been highly studied as sodium-ion battery anodes. They have large interlayer spacing, which can effectively buffer the big volume expansion and prevent electrode collapse during the charge-discharge process. Different strategies such as preparing composites, heterostructures, expanded structures, and chemical functionalization can greatly improve cycling stability and lead to high reversible capacity. In this dissertation, state-of-the-art SIB based on 2D material electrodes will be presented. In particular, Tin-based 2D materials and laser-scribed graphene anodes are discussed. Different strategies involving engineering both synthesis methods, intrinsic properties of materials, and device architecture are used to optimize the battery performance.

The effects of fin-leading-edge radius and sweep angle on peak heating rates due to shock-shock interactions were investigated in the NASA Langley Research Center 20-inch Mach 6 Air Tunnel.  The fin model leading edges, which represent cylindrical leading edges or struts on hypersonic vehicles, were varied from 0.25 inches to 0.75 inches in radius.  A 9° wedge generated a planar oblique shock at 16.7° to the flow that intersected the fin bow shock, producing a shock-shock interaction that impinged on the fin leading edge.  The fin angle of attack was varied from 0° (normal to the free-stream) to 15° and 25° swept forward.  Global temperature data was obtained from the surface of the fused silica fins through phosphor thermography.  Metal oil flow models with the same geometries as the fused silica models were used to visualize the streamline patterns for each angle of attack.  High-speed zoom-schlieren videos were recorded to show the features and temporal unsteadiness of the shock-shock interactions.  The temperature data were analyzed using one-dimensional semi-infinite as well as one- and two-dimensional finite-volume methods to determine the proper heat transfer analysis approach to minimize errors from lateral heat conduction due to the presence of strong surface temperature gradients induced by the shock interactions.  The general trends in the leading-edge heat transfer behavior were similar for the three shock-shock interactions, respectively, between the test articles with varying leading-edge radius.  The dimensional peak heat transfer coefficient augmentation increased with decreasing leading-edge radius.  The dimensional peak heat transfer output from the two-dimensional code was about 20% higher than the value from a standard, semi-infinite one-dimensional method. / Master of Science

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18275号 / 工博第3867号 / 新制||工||1593(附属図書館) / 31133 / 京都大学大学院工学研究科原子核工学専攻 / (主査)教授 福山 淳, 教授 功刀 資彰, 准教授 村上 定義 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21109号 / 工博第4473号 / 新制||工||1695(附属図書館) / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 白石 誠司, 教授 木本 恒暢, 教授 山田 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM