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      • Theoretical Study on Spin and Orbital Transport in Magnetic Systems

        Hyeon-Jong Park 고려대학교 KU-KIST융합대학원 2023 국내박사

        RANK : 251663

        This thesis deals with spin and orbital transport in magnetic systems and magnetic properties originating from the spin-orbit coupling. Since the spin and orbital transport have unique features depending on the magnetic systems, there are arising interest in field of spintronics such as the anomalous and spin Hall effects in various magnetic materials, i.e., ferromagnets [1-3], antiferromagnets [4-7], nonmagnets [8-10], and the orbital Hall effect which is the orbital analogue of spin Hall effect [11-13]. Moreover, the spin transport and related spin-transfer torque in magnetic textures such as domain walls [14-15] and magnetic skyrmions [16] also have been studied. At the interface of magnetic heterostructures, there is Rashba spin-orbit coupled transport such as interfacial spin current [18, 19], spin and orbital Rashba-Edelstein effects [19,20], and intrinsic spin swapping effect [21]. In this thesis, we focus on the spin transport, orbital transport, and interfacial magnetic properties in magnetic systems. In chapter 1, we introduce the generation of spin and orbital currents such as spin Hall, orbital Hall, and spin swapping effects (section 1.2). In addition, we briefly introduce the spin-transfer torque and the spin-orbit torque (section 1.3). Finally, we show the numerical methods to calculate the spin and orbital related quantities (section 1.4). In chapter 2, we theoretically demonstrate the spin swapping effect of band structure origin in centrosymmetric ferromagnets. We show that the magnitude of intrinsic spin swapping conductivity is large at the band anticrossing which is a crossing point of different spin and orbital character bands. Also, we confirm that the intrinsic spin swapping conductivity is comparable to spin Hall conductivity in transition metal ferromagnets using density functional theory. In chapter 3, we numerically compute the spin-transfer torques for antiferromagnetic domain walls (DWs). We show that the spin-mistracking phenomenon, which results in a nonadiabatic torque, is remarkable for antiferromagnetic DWs. Furthermore, unlike for ferromagnetic DWs, we theoretically and numerically confirm that the dynamics of antiferromagnetic DWs is determined by the nondiabetic torque only. In chapter 4, we study the Rashba spin-orbit coupled spin properties. These properties include the both equilibrium and nonequilibrium properties such as surface anisotropy, Dzyaloshinskii-Moriya interaction (DMI), and Rashba-Edelstein effect. We confirm that the equilibrium spin properties can be manipulated by the electron populations, whereas nonequilibrium spin density can be induced by the lateral inversion symmetry breaking. We note that the most of results in this thesis, including the figures and schematics, have already been published in scientific journals. Results of chapter 2 and chapter 3 are reproduced from the [22, 23] with the permission of American Physical Society. Chapter 4 is reproduced from the [24, 25] with the permission of American Physical Society and [26] which are open access articles.

      • Two-dimensional Pyrene conjugated Peptide Assembly via Donor-Acceptor Interaction

        Taeyeon Kim 고려대학교 KU-KIST융합대학원 2023 국내박사

        RANK : 251663

        Supramolecular assemblies based on weak non-covalent intermolecular interactions are attractive tools for the sophisticated fabrication of various nanostructures and stimuli-responsive materials. Furthermore, supramolecular materials can be reassembled into dynamic architectures in response to external stimuli, including ions, temperature, pH, and light. Among the various self-assembling building blocks, aromatic amphiphiles, consisting of hydrophobic aromatic segments and hydrophilic flexible segments, are good candidates for well-defined supramolecular structures. Such structures include micelles, nanofibers, vesicles, and two-dimensional (2D) sheets with a hydrophobic aromatic core surrounded by hydrophilic flexible segments in an aqueous solution. The physical and chemical properties of 2D assemblies can be attributed to their large surface area, flexibility, low cytotoxicity, enhanced molecular loading, and high bioconjugation efficiency in biological applications. This study reports supramolecular 2D materials based on a pyrene-grafted amphiphilic peptide, which contains a peptide sequence (Asp-Gly-Glu-Ala; DGEA) reported to bind to the integrin α2β1 receptor in cell membranes. The addition of acceptor molecules to the pyrene-grafted peptide can induce a well-ordered 2D assembly by face-centered donor-acceptor interactions. In Chapter 1, the pyrene-grafted peptide as the addition of octafluoronaphthalene (OFN) with a flat structure, structural stability against enzymatic degradation, and a larger size can enhance the proliferation and differentiation of muscle cells via continuous interactions with cell membrane receptors integrin α2β1. The DGEA–peptide 2D assembly exhibits low intracellular uptake (15 %) compared with vesicular peptide assembly (62 %). Peptide assembly via a supramolecular approach can overcome the inherent limitations of bioactive peptides, such as proteolytic degradation and rapid internalization into the cytosol. In Chapter 2, we observed that pyrene-grafted peptide with acceptor molecules demonstrated two-dimensional materials via D-A interaction. Furthermore, amphiphilic pyrene showed novel light-responsive systems via co-assemblies of acceptor molecules with octafluoronaphthalene (OFN), Nile red, and N,N,N',N'-tetrakis(4- dibutylaminophenyl)-1,4-benzoquinone diiminium bis (NIR dye) that could be excited on the multi-wavelength. As the replacement of each acceptor molecule that absorbs longer wavelengths, 2D materials based on amphiphilic pyrene caused light-responsive performances from the visible region to the NIR region, leading to rapid structural aggregation according to the direction of light irradiation. In addition, the aromatic rings of the D-A complex weakened by light irradiation demonstrated exposure of inner aromatic molecules to the outside surface, which eventually induced irregular aggregation due to exposed hydrophobicity. The weakened D-A complex with a lower band gap and distant intermolecular interaction by the photo-excitation was transformed into micelles (OFN complex), nanosheets (Nile red complex), and nanofibers (NIR complex) under continuous light irradiation. This research is expected to bring considerable interests to a range of interest to both supramolecular chemistry and biology, as follows. These supramolecular approaches via the D-A interaction provide a strategy to fabricate well-defined 2D peptide materials with an understanding of assembly at the molecular level. Bioactive peptide-based supramolecular 2D assemblies could overcome the limitations of having the instability of conventional peptide materials and will provide detailed insights into the peptide-based drug field. Furthermore, through continuous light irradiation, the photoexcited D-A complex with two-dimensional structures eventually demonstrated the transformation of micelles (OFN complexes), nanosheets (NIR complexes), and nanofibers (NIR complexes) as the inner aromatic molecules reverse outward. In this study, the novel light-responsive system can be deployed as a next-generation material in various light-mediated fields because the one assembly constructed between two molecules can respond to most of the wavelengths from the short visible regions to the NIR region.

      • All-solution Synthesized High-performance 2D Bi2O2Se Thin-film Transistor

        Kim, Jin Seok 고려대학교 KU-KIST융합대학원 2023 국내석사

        RANK : 251663

        Two-dimensional (2D) semiconductors have emerged as a next-generation electronic material because of their excellent electrical and mechanical properties in the atomically thin regime. These materials with a van der Waals layered structure are particularly promising for emerging electronics capable of heterogeneous integration and flexibility. For this purpose, low-temperature, and high-quality synthesis of 2D semiconductors are essential, wet chemical synthesis has remarkable advantages in low process temperature, scalability, and cost-effectiveness compared to conventional chemical vapor deposition processes. However, it remains a considerable challenge to achieve high quality and device performance. Here, we report the wet chemical synthesis via a bottom-up process of 2D Bi2O2Se semiconductors showing a high mobility characteristic. The all-solution-based processes are carried out at a low temperature below 200 ℃ producing free-standing 2D flakes with a lateral size of over 10 μm and thickness down to 8 nm. In addition, the single-crystalline Bi2O2Se channel in a back-gated field-effect transistor geometry exhibited high mobility up to 132 cm2V-1s-1 at room temperature. Notably, this solution can be assembled into a thin film for large-area device fabrication through a simple method such as liquid/air interface self-assembly. Our demonstration provides an innovative bottom-up synthesis approach to preparing high-quality semiconductors cost- and energy-effectively.

      • Hierarchically Interpenetrated and Reentrant Micro-Cellular Frameworks for Stretchable Lithium Metal Batteries

        An, Yoo Joo 고려대학교 KU-KIST융합대학원 2023 국내석사

        RANK : 251663

        Human-friendly wearable devices have been rapidly developed these days and there are strong demands for skin-like stretchability to fit the human body more closely and comfortably. In addition, it is crucial to integrate a stretchable energy storage component with high energy density and a high voltage window into wearable devices with small dimensions for long-term usage. In this study, we introduce a hierarchically interpenetrated reentrant microcellular structure combined with two-dimensional microcellular structure of graphene-MXene-carbon nanotubes (CNTs) and three-dimensional cellular melamine foam serving as a stretchable structure for lithium metal composite electrodes to provide stretchability for lithium metal electrodes, which hold great promise as advanced energy storage systems of the future. The non-conductive and deformable melamine foam, provide stable structural deformability, while the graphene/CNT/MXene network ensures high electrical conductivity, lithiophilicity, and mechanical stability, facilitating the deposition of lithium during electrodeposition. The reentrant structure was fabricated by radially compressing the hierarchical cellular structures, leveraging the structural stretchability of the accordion-like reentrant frameworks. The resulting composite electrodes with lithium deposition exhibit significantly lower overpotential during Li stripping and plating compared to conventional lithium metal foil anodes, and they demonstrate stable electrochemical performance even under a mechanical strain of 30%. The reentrant micro-cellular electrodes exhibit significant potential in the advancement of lithium metal electrodes with a high energy density for stretchable batteries. 최근 스마트 워치, 스마트 글래스 등 인간 친화적인 웨어러블 기기가 급속도로 발전하면서 인체에 보다 편안하게 밀착이 가능한 높은 신축성을 가진 디바이스에 대한 수요가 증가하고 있다. 또한 웨어러블 디바이스의 편의성을 높이기 위해 배터리가 차지하는 공간은 줄이되 충전 후 방전까지의 시간은 늘릴 수 있는 높은 에너지 밀도를 가지는 배터리가 요구된다. 따라서 본 연구는 높은 전도성 및 비표면적을 가지는 그래핀-맥신-탄소나노튜브의 안쪽으로 구부러진 재진입 구조를 리튬 증착을 위한 뼈대로 사용하여 신축 가능한 고성능의 복합 리튬 메탈 배터리 음극을 구현하고자 한다. 그러나 그래핀/탄소나노튜브로만 이루어진 뼈대에 리튬을 증착하여 복합 음극을 형성할 경우 그래핀과 탄소나노튜브에 금속 리튬이 둘러싸여 리튬 금속이 전극의 기계적 물성을 지배하게 되어 신축 시 쉽게 파손된다. 이를 보완하기 위해 전도성이 없어 리튬이 증착되지 않으면서도 유연성을 가져 형태 변형이 가능하며, 적은 부피에도 높은 기계적 안정성을 유지하는 삼차원 구조의 멜라민 폼을 이용한다. 이러한 구조를 통해 안정적인 구조적 변형성을 성공적으로 얻었으며 동시에 전기도금법으로 그래핀-맥신-탄소나노튜브 네트워크에 리튬을 안정적으로 전착하였다. 재진입 구조는 그래핀-맥신-탄소나노튜브/멜라민 폼을 방사형으로 압축하여 아코디언과 같은 프레임워크의 구조적 신축성을 가질 수 있도록 하였다. 제작된 복합 리튬 메탈 배터리 음극은 충방전 테스트에서 낮은 과전위를 가지며 30% 신축시에도 안정적인 전기화학적 성능을 보였다. 이를 통해 높은 에너지 밀도의 신축성 배터리용 복합 리튬 메탈 배터리 음극으로의 활용 가능성 및 잠재력을 확인하였다.

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