<p>In the realm of tunable optical devices, 3D nanostructures with metals and dielectrics have been utilized in a wide variety of practical applications ranging from optical switching to beam-steering devices. 2D materials, on the other hand, have enabled the exploration of truly new physics unattainable with 3D systems due to quantum confinement leading to unique optical properties and enhanced light-matter interactions. Transdimensional materials (TDMs) – atomically thin films of metals – can couple the robustness of 3D nanostructures with the new physics enabled by 2D features. However, the evolution of the optical properties in the transdimensional regime between 3D and 2D is still underexplored. The optical properties of metallic TDMs are expected to show unprecedented tailorability, including strong dependences on the film thickness, composition, strain, and surface termination. They also have an increased sensitivity to external optical and electrical perturbations, owing to their extraordinary light-confinement. Additionally, the small atomic thicknesses may lead to strongly confined surface plasmons and quantum and nonlocal phenomena. The strong tunability and light-confinement offered by TDMs have resulted in a search for atomically thin plasmonic material platforms that facilitate active metasurfaces with novel functionalities in the visible and near infrared (NIR) range. In this research, we explore the plasmonic properties and tailorability of atomically thin titanium nitride (TiN). We experimentally and theoretically study the thickness-dependent optical properties of epitaxial TiN films with thicknesses down to 1 nm to demonstrate confinement induced optical properties. Overall, this research demonstrates the potential of TDMs for unlocking novel optical phenomena at visible and NIR wavelengths and realizing a new generation of atomically thin tunable nanophotonic devices. </p>

Ligand-protected metal nanoclusters (NCs), which are ultra-small nanoparticles marked by their atomic precision, are distinctly importance for contemporary nanomaterials. NCs have attracted significant research attention for utilizing their novel optical and physicochemical properties in various applications, including fluorescence sensing, catalysis, and biomedical applications. This dissertation deals with ligand-protected atomically precise silver NCs and is divided into two main parts. The first part is focused on the exploration and design of well-defined silver NCs through surface co-ligand engineering. The second part is related to the development of silver NC-based frameworks (NCFs). In the first part, we designed a synthetic strategy based on engineering the structure of the phosphine co-ligands with thiols to generate the large box-shaped [Ag67(SPhMe2)32(PPh3)8]3+ (referred to as Ag67) NC. The strategy demonstrates that the combined use of judiciously chosen thiol and phosphine co-ligands can result in stable highly anisotropic box-like shapes. The optical absorption spectrum of the Ag67 NC displays highly structured multiple sharp peaks. The crystal structure shows a Ag23 core formed of a centered cuboctahedron (an unprecedented core geometry in silver clusters), which is encased by a layer with a composition of Ag44S32P8 arranged in the shape of a box. The electronic structure of this box-shaped cluster resembles a jellium box model with 32 free electrons. In the second part, a novel approach is developed for the assembly and linkage of atomically precise Ag NCs into one-dimensional (1D) and two-dimensional (2D) NC-based frameworks (NCFs) with atomic-level control over cluster size and dimensionality. With this approach three novel, but related, crystal structures (one silver NC and two NCFs) were synthesized. These structures have the same protecting ligands, and also the same organic linker. The three structures exhibit a similar square gyrobicupola geometry of the building NC unit with only a single Ag atom difference. The critical role of using a chloride template in controlling the NC’s nuclearity was demonstrated, as well as the effect of a single Ag atom difference in the NC’s size on the NCF’s dimensionality, optical properties, and thermal stability.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第21315号 / エネ博第371号 / 新制||エネ||73(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 松田 一成, 教授 佐川 尚, 教授 大垣 英明 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

This doctoral thesis is focused on the preparation of graphene layers by Chemical Vapor Deposition (CVD) and their utilization for fabrication and characterization of field effect transistors. The theoretical part of the thesis deals with different methods of graphene production and measurement of its transport properties. In the first part of the experimental section the growth of polycrystalline graphene and individual graphene crystals with sizes up to 300 m is investigated. Further, graphene layer was also grown on an atomically flat copper foils, which were fabricated in order to achieve the growth of graphene of higher quality. Subsequently, the transport properties of field effect transistors produced from the grown layers were measured. The last two chapters deal with a doping of graphene layer by gallium atoms and X-ray radiation. Whereas the deposition of gallium atoms on the graphene surface causes chemical doping of graphene layer by charge transfer, X-ray irradiation of graphene field effect transistors induces the ionization of positively charged defects in dielectrics, which electrostatically dope a graphene layer.