The development of metals that can overcome the strength-ductility-weight trade-off has been an ongoing challenge in engineering for many decades. A promising option for making such materials are Metal matrix composites (MMCs). MMCs contain dispersions of reinforcement in the form of fibers, particles, or platelets that significantly improve their thermal, electrical, or mechanical performance. This dissertation focuses on reinforcement with two-dimensional (2D) materials due to their unprecedented mechanical properties. For instance, compared to steel, the most well-studied 2D material, graphene, is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa). Examples of reinforcement by graphene have achieved increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. However, the superior mechanical properties of graphene are not fully transferred to the matrix in conventional MMCs, a phenomenon known as the "valley of death." In an effort to develop key insight into how the relationships between composite design, processing, structure, properties, and mechanics can be used to more effectively transfer the intrinsic mechanical properties of reinforcements to bulk composite materials, nanolayered composite systems made of Ni, Cu, and NiTi reinforced with graphene or 2D hexagonal boron nitride h-BN is studied using experimental techniques and molecular dynamics (MD) simulations. / Doctor of Philosophy / The design of new metals with concurrently improved strength and ductility has been an enduring goal in engineering for many decades. The utilization of components made with these new materials would reduce the weight of structures without sacrificing their performance. Such materials have the potential to revolutionize many industries, from electronics to aerospace. Traditional methods of improving the properties of metals by thermomechanical processing have approached a point where only minor performance improvements can be achieved. The development of Metal matrix composites (MMCs) is among the best approaches to achieving the strength-ductility goal. Metal matrix composites are a class of materials containing reinforcements of dissimilar materials that significantly improve their thermal conductivity, electrical conductivity, or mechanical performance. Reinforcements are typically in the form of dispersed fibers, particles, or platelets. The ideal reinforcement materials have superior mechanical properties compared to the metal matrix, a high surface area, and a strong interfacial bond with the matrix. Two-dimensional (2D) materials (materials made up of a single to a few layers of ordered atoms) are attractive for reinforcement in composite materials because they possess unprecedented intrinsic properties. The most well-studied 2D material, graphene, is made of a single layer of carbon atoms arranged in a hexagonal honeycomb pattern. It is nearly forty times stronger (130 GPa) and five times stiffer (1 TPa) than steel. Examples of graphene reinforcing have shown increases in strength of 60% due to load transfer at the metal/graphene interface and dislocation blocking by the graphene. Despite their exceptional mechanical properties, the superior mechanical properties of graphene are not fully transferred to the matrix when incorporated into conventional metal matrix composites. This phenomenon, known as the "valley of death," refers to the loss of mechanical performance at different length scales. One cause of this phenomenon is the difficulty of evenly dispersing the reinforcements in the matrix using traditional fabrication techniques. Another is the presence of dislocations in the metal matrix, which cause very large local lattice strains in the graphene. This atomistic-scale deformation at the interface between the metal and the graphene can significantly weaken it, leading to failure at low strains before reaching its intrinsic failure stress and strain. This dissertation aims to provide insight into how the relationships between composites' design, processing, structure, properties, and mechanics can be used to transfer intrinsic mechanical properties of reinforcements to bulk composite materials more effectively. For this, nanolayered composite systems of Ni and Cu reinforced with graphene or 2D h-BN were studied using experimental techniques and molecular dynamics (MD) simulations to elucidate the underlying mechanisms behind the composites' material structure and mechanical behavior. Additionally, we explore the incorporation of graphene in a metallic matrix that does not deform through dislocations (or shear bands), such as the shape memory alloy nickel-titanium ( Nitinol or NiTi), to avoid low strain failure of the metal/graphene interface. This theoretical strengthening mechanism is investigated by designing and fabricating NiTi/graphene composites.

Electrical transport in materials is typically diffusive, due to dominant momentum-relaxing scattering of carriers with the phonons or defects. In ultraclean material systems such as GaAs/AlGaAs or graphene/hBN heterostructures, momentum-relaxing can be suppressed, leading to the onset of non-diffusive transport regimes, where Ohm's law is no longer valid. Within these non-diffusive regimes, the hydrodynamic regime occurs when momentum-conserving electron-electron scattering length scale is smaller than the device length scale (usually at intermediate temperatures). On the other hand, weak electron-electron scattering (at low temperatures) results in ballistic transport, commonly understood using the familiar single-particle framework of injected carriers travelling in straight line trajectories with intermittent reflections off device boundaries. Both the ballistic and hydrodynamic regimes can exhibit a emph{negative} nonlocal resistance, and collective behaviour such as the formation of current vortices. In this work, we study nonlocal current-voltage characteristics in mesoscopic devices fabricated from a GaAs/AlGaAs heterostructure that hosts a two-dimensional electron system in a GaAs quantum well. First, we report a quadratic non-linearity in the nonlocal current-voltage characteristics that manifests in any device where a nonlocal voltage measurement is possible. Using measurements at low temperatures ($sim$ 4 K) across multiple devices and considering various contact configurations for each device, we show that the non-linearity is universal. We apply the non-linearity to rectification and frequency multiplication. We also report on a periodic peaks in the nonlocal voltage vs. magnetic field, in an enclosed mesoscopic geometry in which transverse magnetic focusing (TMF) is typically studied. These peaks occur at weak magnetic fields, are independent of the source-detector separation and are distinct from TMF. Our experimental findings are backed by an extensive set of simulations using in both the semiclassical as well as quantum-coherent transport models. / Master of Science / Current is made up of charged particles such as electrons moving through a material. Typically, current is proportional to the applied voltage and flows from higher to lower potential within the device with the potential decreasing monotonically as we move from the source contact to the drain contact irrespective of the path taken through the device. This is commonly known as Ohm's law, and is followed in most materials we come across. The motion of electrons carrying this current is akin to the motion of balls inside a pinball machine, their momentum randomized by intermittent collisions due to lattice vibrations, defects and impurities present in the material. In ultraclean two-dimensional materials at low-intermediate temperatures (where lattice vibration is weak), these collisions become sparse. Collisions of electrons with other electrons now become important. When electron-electron collisions are frequent, the electrons collectively behave like a fluid, giving rise to so called hydrodynamic transport. On the other hand, when electron-electron collisions are sparse as well, electrons move unhindered in ballistic straight line trajectories until they reflect off the device boundaries. This is known as ballistic transport. Under both these transport regimes, Ohm's law breaks down, leading to interesting physical phenomena such as the formation of current whirlpools. In this work, we study the voltage measured at a point in the device which is distinct from the point where current is injected or extracted. This is commonly known as the nonlocal voltage. We explore the relationship between the nonlocal voltage and the injected current and find it to be significantly different from predictions made by Ohm's law. We use this novel current-voltage relationship to build a rectifier and frequency multiplier - two devices commonly used in high-frequency detection, radar systems and telecommunications. We also report previously unseen periodic oscillations in the nonlocal voltage when the magnetic field perpendicular to the device is varied. Using high-resolution simulations, we show the these oscillations can not be explained by looking at individual electron paths, and arise due to contribution from all electrons that travel through the device.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24873号 / 理博第4983号 / 新制||理||1711(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 有賀 哲也, 教授 堀毛 悟史 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24116号 / エネ博第449号 / 新制||エネ||84(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 大垣 英明, 教授 松田 一成, 教授 宮内 雄平 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Understanding the “incomprehensible” world of materials is the biggest challenge to the materials science community. To access the properties of the materials and to utilize them for positive changes in the world are of great interest. Often scientists use approximate theories to get legitimate answers to the problems. Density functional theory (DFT) has emerged as one of the successful and powerful predictive methods in this regard. The accuracy of DFT relies on the approximate form of the exchange-correlation (EXC) functional. The most complicated form of this functional can be as accurate as more complicated and computationally robust method like Quantum Monte Carlo (QMC), Random Phase Approximation (RPA). Two newest meta-GGAs, SCAN and SCAN+rVV10 are among those functionals. Instantaneous charge fluctuation between any two objects gives rise to the van der Waals (vdW) interactions (often termed as dispersion interactions). It is a purely correlation effect of the interacting electrons and thus non-local in nature. Despite its small magnitude it plays a very important role in many systems such as weakly bound rare-gas dimers, molecular crystals, and molecule-surface interaction. The traditional semi-local functionals can not describe the non-local of vdW interactions; only short- and intermediate-range of the vdW are accounted for in these functionals. In this thesis we investigate the effect of the weak vdW interactions in surface properties, rare-gas dimers and how it can be captured seamlessly within the semi-local density functional approximation. We have used summed-up vdW series within the spherical-shell approximation to develop a new vdW correction to the meta-GGA-MS2 functional. This method has been utilized to calculate binding energy and equilibrium binding distance of different homo- and hetero- dimers and we found that this method systematically improves the MGGA-MS2 results with a very good agreement with the experimental data. The binding energy curves are plotted using this MGGA-MS2, MGGA-MS2-vdW and two other popular vdW-corrected functionals PBE-D2, vdW-DF2. From these plots it is clear that our summed-up vdW series captures the long-range part of the binding energy curve via C6, C8, and, C10 coefficients. The clean metallic surface properties such as surface energy, work functions are important and often play a crucial role in many catalytic reactions. The weak dispersion interactions present between the surfaces has significant effect on these properties. We used LDA, PBE, PBSEsol, SCAN and SCAN+rVV10 to compute the clean metallic surface properties. The SCAN+rVV10 seamlessly captures different ranges of the vdW interactions at the surface and predicts very accurate values of surface energy (σ), and work function (Φ) and interlayer relaxations (δ%). Our conclusion is adding non-local vdW correction to a good semilocal density functional such as SCAN is necessary in order to predict the weak attractive vdW forces at the metallic surface. The SCAN+rVV10 has also been employed to study the hydrogen evolution reaction (HER) on 1T-MoS2. We have chosen as a descriptor differential Gibbs free energy (ΔGH to understand the underlying mechanism of this catalytic reaction. Density functional theory calculations agree with the experimental findings. In the case of layered materials like 1TMoS2, vdW interactions play an important role in hydrogen binding, that SCAN+rVV10 calculation was able to describe precisely. We have also used SCAN and SCAN+rVV10 functionals to understand bonding of CO on (111) metal surfaces, where many approximations to DFT fail to predict correct adsorption site and adsorption energy. In this case SCAN and SCAN+rVV10 do not show systematic improvements compared to LDA or PBE, rather, both SCAN and SCAN+rVV10 overbind CO more compared to PBE but less compared to the LDA. This overbinding of CO is associated with the incorrect charge transfer from metal to molecule and presumably comes from the density-driven self-interaction error of the functionals. In this thesis we assessed different semi-local functionals to inivestigate molecule surface systems of π-conjugated molecules (thiophene, pyridine) adsorbed on Cu(111), Cu(110), Cu(100) surfaces. We find the binding mechanism of these molecules on the metallic surface is mediated by short and intermediate range vdW interactions. Calculated values of binding energies and adsorbed geometries imply that this kind of adsorption falls in the weak chemisorption regime. Structural phase transitions due to applied pressure are very important in materials science. However, pressure induced structural phase transition in early lanthanide elements such as Ce are considered as abnormal first order phase transition. The Ce α-to-γ isostructural phase transition is one of them. The volume collapse and change of magnetic properties associated with this transition are mediated by the localized f -electron. Semi-local density functionals like LDA, GGA delocalize this f -electron due to the inherent self-interaction error (SIE) of these functionals. We have tested the SCAN functional for this particular problem, and, it was found that the spin-orbit coupling calculations with SCAN not only predicts the correct magnetic ordering of the two phases, but also gives a correct minima for the high-pressure α-Ce phase and a shoulder for the low-pressure γ-Ce phase. / Physics

The global increase in internet usage requires an upgrade of the existing infrastruc- ture. Lasers are a key proponent to improving existing systems, and engineering better gain materials aids in this effort. (InGa)As is the leading material in this field for 1.55 μm communication wavelengths, but can be improved on by changing the substrate from InP to GaAs. Another improvement would be reducing the losses due to Auger recombination. (InGa)(BiAs) is suggested to alleviate many of these issues, as it can be grown on a GaAs substrate and is capable of decreased Auger recombination. By analyzing prospective alloys (and existing ones) using spatial electron localization, a superior candidate for industrial use can be suggested. The localization captures the disorder introduced by alloying and can be associated with material properties such as the gain characteristics and photoluminescence linewidths. These properties are important factors in determining a successor. The subject of two-dimensional materials is another topic which has shown promise in various applica- tions. Examples include flexible, transparent, and miniaturized electronics. Recent research done by Al Balushi et al. suggests that GaN may be stabilized in a two-dimensional sys- tem. By extending the material modelling approach from the telecommunication application to this system, we were able to show which III-V isoelectronic elements can be substituted into GaN. This two-dimensional system may be the only candidate capable of spanning the visible spectrum. We found Phosphorus to be the strongest candidate for decreasing the band gap. / Thesis / Master of Applied Science (MASc)

From computation to sensing, two-dimensional materials are revolutionizing the field of nanoscale electronics and devices. They enable the engineering of membranes, circuits and coatings with tailored electronic properties at ultimate, atomic thinness. Yet, the manufacturing processes to obtain these materials are not sufficiently advanced to meet industrial demands. The next step for them to push into the consumer market is the successful, large-scale integration with existing silicon technology. For many two-dimensional materials, this proves challenging due to high synthesis temperatures or low mechanical stability in transfer processes. Not so for two-dimensional noble-metal chalcogenides: PtSe2 is an exemplary candidate because it can be grown at temperatures below 500 ℃, rendering it suitable for facile integration at the back end of the line. Additionally, it features very high stability with respect to moisture, irradiation, and mechanical strain, high carrier mobilities, and electronic properties that can be fine-tuned with the number of layers. These properties collectively make it a very promising material for free-standing nanoelectromechanical sensors, such as piezoresistive pressure sensors and motion detectors for the Internet of Things. Unfortunately, one cannot have their cake and eat it too: The broadly tunable properties of PtSe2 lead to challenges in fabricating devices with reproducible performance. This issue can be overcome with sufficient understanding and control of the nanostructure of PtSe2 thin films. The aim of this thesis is to study these nanostructures in depth, employing state-of-the-art density-functional theory and a machine learning approach to get closer to modelling PtSe2 under realistic conditions. Firstly, the family of noble-metal dichalcogenides is introduced and discussed. Secondly, the role of stacking disorder in PtSe2 is taken into account and its impact on electromechanical properties is analyzed. Lastly, a machine learning approach is employed to study edges and surfaces of nanoplatelets of PtSe2, which are the building blocks of polycrystalline thin films. Through these studies, crucial parameters have been identified that need to be controlled during the manufacturing process of PtSe2, and the groundwork to built up large-scale models has been laid out.

Molecules adsorbed on two-dimensional (2D) materials can show interesting physical and chemical properties. This thesis presents scanning probe microscopy (SPM) investigation of emerging 2D materials, molecular nanostructures on 2D substrates at the nanometer scale, and biophysical processes on the biological membrane. Two main techniques of nano-probing are used: scanning tunneling microscopy (STM) and atomic force microscopy (AFM). The study particularly emphasizes on self-assembled molecules on flat 2D materials and quasi-1D wrinkles. First, we report the preparation of novel 1D C60 nanostructures on rippled graphene. Through careful control of the subtle balance between the linear periodic potential of rippled graphene and the C60 surface mobility, we demonstrate that C60 molecules can be arranged into a 1D C60 chain structure of two to three molecules in width. At a higher annealing temperature, the 1D chain structure transitions to a more closely packed, quasi-1D hexagonal stripe structure. The experimental realization of 1D C60 structures on graphene is, to our knowledge, the first in the field. It could pave the way for fabricating new C60/graphene hybrid structures for future applications in electronics, spintronic and quantum information. Second, we report a study on nano-morphology of potential operative donors (e.g., C60) and acceptors (e.g., perylenetetracarboxylic dianhydride, aka. PTCDA) on wrinkled graphene supported by copper foils. We realize sub-monolayer C60 and PTCDA on quasi-1D and quasi-2D real periodic wrinkled graphene, by carefully controlling the deposition parameters of both molecules. Our successful realization of acceptor-donor binary nanostructures on wrinkled graphene could have important implications in future development of organic solar cells. Third, we report an STM and spectroscopy study on atomically thin transition-metal dichalcogenides (TMDCs) material. TMDCs are emerging 2D materials recently due to their intriguing physical properties and potential applications. In particular, our study focuses on molybdenum disulfide (MoS2) mono- to few-layers and pyramid nanostructures synthesized through chemical vapor deposition. On the few-layered MoS2 nanoplatelets grown on gallium nitride (GaN) and pyramid nanostructures on highly oriented pyrolytic graphite (HOPG), we observe an intriguing curved region near the edge terminals. The measured band gap in these curved regions is consistent with the direct band gap in MoS2 monolayers. The curved features near the edge terminals and the associated electronic properties may contribute to understanding catalytic behaviors of MoS2 nanostructures and have potential applications in future electronic devices and catalysts based on MoS2 nanostructures. Finally, we report a liquid-cell AFM study on the endosomal protein sorting process on the biological lipid membrane. The sorting mechanism relies on complex forming between Tom1 and the cargo sorting protein, Toll interacting protein (Tollip). The induced conformational change in Tollip triggers its dissociation from the lipid membrane and commitment to cargo trafficking. This collaborative study aims at characterizing the dynamic interaction between Tollip and the lipid membrane. To study this process we develop the liquid mode of AFM. We successfully demonstrate that Tollip is localized to the lipid membrane via association with PtdIns3P (PI(3)P), a major phospholipid in the cell membrane involved in protein trafficking. / Ph. D. / Two-dimensional (2D) materials are layered materials with thickness of single atom or few atoms. The ultimate thickness leads to novel properties that are useful for a wide range of applications in photovoltaics, electronics and quantum information. In order to explore these properties at the nanometer scale, we used scanning probe techniques, i.e., scanning tunneling microscopy (STM) and atomic force microscopy (AFM), to perform comprehensive investigations on these emerging materials. 2D materials, such as graphene and atomically thin transition-metal dichalcogenides (TMDCs), are promising candidates for building economic, safe and mechanically flexible solar cells with desirable optical and electronic properties, e.g. tunable sunlight absorption. The first part of the thesis focuses on graphene, a single-atom-thick carbon sheet. We deposited key components in organic solar cells, such as perylenetetracarboxylic dianhydride (PTCDA) and C₆₀ molecules, on graphene. On these materials we observed various novel nanostructures, like quasi-1D C₆₀ nanochains. The second part of the thesis focuses on mono- to few-layered MoS₂, which can be used as an active layer in high-efficiency solar cells. Our study has important implications in improving efficiency of organic solar cells in the future. In the final part of the thesis, we extended our subject to the biological lipid membrane, a 2D material critical in biology, and biophysical processes occurring on the membrane. Using a liquid-cell AFM, we investigated the endosomal protein sorting process on the biological membranes. Our study contributes to understanding of the interactions between the adaptor proteins and cell membranes in the protein sorting process that guides proteins to their proper destinations.