847 research outputs found
AB-INITIO INVESTIGATION OF 2D MATERIALS FOR GAS SENSING, ENERGY STORAGE AND SPINTRONIC APPLICATIONS
The field of Two Dimensional (2D) materials has been extensively studied since their discovery in 2004, owing to their remarkable combination of properties. My thesis focuses on exploring novel 2D materials such as Graphene Nanoribbon (GNR), holey carbon nitride C2N, and MXenes for energy storage, gas sensing, and spintronic applications, utilizing state-of-the-art techniques that combine Density Functional Theory (DFT) and Non-Equilibrium Greens Functions (NEGF) formalism; namely Vienna Ab-initio Simulation Package (VASP) and Atomistic Toolkit (ATK) package.Firstly, on the side of gas sensing, the burning of fossil fuels raises the level of toxic gas and contributes to global warming, necessitating the development of highly sensitive gas sensors. To start with, the adsorption and gas-sensing properties of bilaterally edge doped (B/N) GNRs were investigated. The transport properties revealed that the bilateral B/N edge-doping of GNR yielded Negative Differential Resistance (NDR) IV-characteristics, due to the electron back-scattering which was beneficial for selective gas sensing applications. Therefore, both GNR: B/N were found to be good sensors for NO2 and SO3 respectively. After that, the catalytic activity of four magnetic transition metal “TM” elements (e.g., Mn, Fe, Co and Ni) embedded in C2N pores, as Single-Atom Catalysts (SAC), was tested towards detecting toxic oxidizing gases. The results of spin-polarized transport properties revealed that Ni- and Fe-embedded C2N are the most efficient in detecting NO/ NO2 and NO2 molecules.Secondly, on the side of energy storage, since the fossil fuels reserves are depleting at an alarming rate, there is an urgent need for alternative forms of energy to meet the ever-growing demand for energy. Hydrogen is a popular form of clean energy. However, its storage and handling are challenging because of its explosive nature. The effect of magnetic moment on the hydrogen adsorption and gas-sensing properties in Mn-embedded in C2N were investigated. Two distinct configurations of embedment were considered: (i) SAC: 1Mn@C2N; and (ii) DAC: Mn2@C2N. Based on the huge changes in electronic and magnetic properties and the low recovery time (i.e., τ ≪ 1 s, τ = 92 μs and 1.8 ms, respectively), we concluded that C2N:Mn is an excellent candidate for (reusable) hydrogen magnetic gas sensor with high sensitivity and selectivity and rapid recovery time. Then, a comparative study of hydrogen storage capabilities on Metal- catalyst embedded (Ca versus Mn) C2N is presented which demonstrated the stability of these metal structures embedded on the C2N substrate. We proposed Ca@C2N and Mn@C2N for dual applications- hydrogen storage and a novel electrode for prospective metal-ion battery applications owing to its high irreversible uptake capacity 200 mAhg-1.Thirdly, on the side of data storage, spintronics is an emerging field for the next generation nanoelectronics devices to reduce their power consumption and to increase their memory and processing capabilities. Designing 2D-materials that exhibit half-metallic properties is important in spintronic devices that are used in low-power high-density logic circuits. We tested samples comprising of SAC and DAC of Mn embedded in a C2N sample size 2×2 primitive cells as well as their combinations in neighboring large pores. Many other TM catalysts were screened, and the results show the existence of half metallicity in just five cases: (a) C2N:Mn (DAC, SAC-SAC, and SAC-DAC); (b) C2N:Fe (DAC); and (c) C2N:Ni (SAC-DAC). Our results further showed the origins of half-metallicity to be attributed to both FMC and synergetic interactions between the catalysts with the six mirror images, formed by the periodic-boundary conditions.Lastly, on the side of batteries, sodium-sulfur batteries show great potential for storing large amounts of energy due to their ability to undergo a double electron- redox process, as well as the plentiful abundance of sodium and sulfur resources. However, the shuttle effect caused by intermediate sodium polysulfides (Na2Sn) limits their performance and lifespan. To address this issue, we proposed two functionalized MXenes Hf3C2T2 and Zr3C2T2 (T= F, O), as cathode additives to suppress the shuttle effect. We found that both Hf3C2T2 and Zr3C2T2 systems inhibit the shuttle effect by binding to Na2Sn with a binding energy higher than the electrolyte solvents. The decomposition barrier for Na2Sn on the O functionalized MXenes gets reduced which enhances the electrochemical process. Overall, our findings show that the tuning of 2D materials can lead to promising applications in various fields, including energy storage, gas sensing, and spintronics
Non-Hermitian Topological Magnonics
Dissipation in mechanics, optics, acoustics, and electronic circuits is
nowadays recognized to be not always detrimental but can be exploited to
achieve non-Hermitian topological phases or properties with functionalities for
potential device applications. As elementary excitations of ordered magnetic
moments that exist in various magnetic materials, magnons are the information
carriers in magnonic devices with low-energy consumption for reprogrammable
logic, non-reciprocal communication, and non-volatile memory functionalities.
Non-Hermitian topological magnonics deals with the engineering of dissipation
and/or gain for non-Hermitian topological phases or properties in magnets that
are not achievable in the conventional Hermitian scenario, with associated
functionalities cross-fertilized with their electronic, acoustic, optic, and
mechanic counterparts, such as giant enhancement of magnonic frequency combs,
magnon amplification, (quantum) sensing of the magnetic field with
unprecedented sensitivity, magnon accumulation, and perfect absorption of
microwaves. In this review article, we address the unified approach in
constructing magnonic non-Hermitian Hamiltonian, introduce the basic
non-Hermitian topological physics, and provide a comprehensive overview of the
recent theoretical and experimental progress towards achieving distinct
non-Hermitian topological phases or properties in magnonic devices, including
exceptional points, exceptional nodal phases, non-Hermitian magnonic SSH model,
and non-Hermitian skin effect. We emphasize the non-Hermitian Hamiltonian
approach based on the Lindbladian or self-energy of the magnonic subsystem but
address the physics beyond it as well, such as the crucial quantum jump effect
in the quantum regime and non-Markovian dynamics. We provide a perspective for
future opportunities and challenges before concluding this article.Comment: 101 pages, 35 figure
Magnetic Domains and Domain Wall Oscillations in Planar and 3D Curved Membranes
This dissertation presents a substantial contribution to a new field of material science, the investigation of the magnetic properties of 3D curved surfaces, achieved by using a self-assembled geometrical transformation of an initially planar membrane. Essential magnetic properties of thin films can be modified by the process of transforming them from a 2D planar film to a 3D curved surface. By investigating and controlling the reasons that influence the properties, it is possible to improve the functionality of existing devices in addition to laying the foundation for the future development of microelectronic devices based on curved magnetic structures. To accomplish this, it is necessary both to fabricate high-quality 3D curved objects and to establish reliable characterization methods based on commonly available technology.
The primary objective of this dissertation is to develop techniques for characterizing the static and dynamic magnetic properties of self-assembled rolled 3D geometries. The second objective is to examine the origin of shape-, size- and strain/curvature-induced effects.
The developed approach based on anisotropic magnetoresistance (AMR) measurement can quantitatively define the rolling-induced static magnetic changes, namely the induced magnetoelastic anisotropy, thus eliminating the need for microscopic imaging to characterize the structures. The interpretation of the AMR signal obtained on curved stripes is enabled by simultaneous visualization of the domain patterns and micromagnetic simulations. The developed approach is used to examine the effect of sign and magnitude of curvature on the induced anisotropies by altering the rolling direction and diameter of the 'Swiss-roll'.
Furthermore, a time-averaged imaging technique based on conventional microscopies (magnetic force microscopy and Kerr microscopy) offers a novel strategy for investigating nanoscale periodic domain wall oscillations and hence dynamic magnetic characteristics of flat and curved structures. This method exploits the benefit of a position-dependent dwell time of periodically oscillating DWs and can determine the trajectory and amplitude of DW oscillation with sub-100 nm resolution. The uniqueness of this technique resides in the ease of the imaging procedure, unlike other DW dynamics imaging methods.
The combined understanding of rolling-induced anisotropy and imaging DW oscillation is utilized to examine the dependence of DW dynamics on external stimuli and the structure's physical properties, such as lateral size, film thickness, and curvature-induced anisotropy. The presented methods and fundamental studies help to comprehend the rapidly expanding field of 3-dimensional nanomagnetism and advance high-performance magneto-electronic devices based on self-assembly rolling
Selected problems of materials science. Vol. 2. Nano-dielectrics metals in electronics. Mеtamaterials. Multiferroics. Nano-magnetics
The textbook examines physical foundations and practical application of current electronics materials. Modern theories are presented, more important experimental data and specifications of basic materials necessary for practical application are given. Contemporary research in the field of microelectronics and nanophysics is taken into account, while special attention is paid to the influence of the internal structure on the physical properties of materials and the prospects for their use. English-language lectures and other classes on the subject of the book are held at Igor Sikorsky Kyiv Polytechnic Institute at the departments of “Applied Physics” and “Microelectronics” on the subject of materials science, which is necessary for students of higher educational institutions when performing scientific works.
For master’s degree applicants in specialty 105 “Applied physics and nanomaterials”.Розглянуто фізичні основи та практичне застосування актуальних матеріалів електроніки. Подано сучасні теорії, наведено найважливіші експериментальні дані та специфікації основних матеріалів, які потрібні для практичного застосування. Враховано сучасні дослідження у галузі мікроелектроніки та нанофізики, при цьому особливу увагу приділено впливу внутрішньої структури на фізичні властивості матеріалів і на перспективи їх використання. Англомовні лекції та інші види занять за тематикою книги проводяться в КПІ ім. Ігоря Сікорського на кафедрах «Прикладна фізика» та «Мікро-електроніка» за напрямом матеріалознавство, що необхідно студентам вищих навчальних закладів при виконанні наукових робіт.
Для здобувачів магістратури за спеціальністю 105 «Прикладна фізика та наноматеріали»
Functional surfactants as energy valves in gradient structures of organic inorganic perovskite structures
Hybrid perovskites are considered one of the most promising semiconductor materials of our time. Their ionic composition enables low-cost and simple production at low temperatures, making them a highly demanded semiconductor for photovoltaics, but also optoelectronic applications such as LEDs, lasers or photodiodes. Their hybrid nature enables the integration of organic cations, which brings a wide range of possible materials.
The classical perovskite structure permits the incorporation of small organic cations. If the given space in the structure is exceeded by the organic molecule, a layered crystalline phase with alternating arrangement of organic cations and inorganic 2D lead bromide layers is formed. This allows the use of a great variety of organic cations which become an integral part of the semiconducting material. Thus, molecules can be chosen that contribute to the functionality of the crystalline phase, for example, by using conductive conjugated π systems. Energy transfer between the components of the layered phases becomes possible and extraordinary electronic and optical properties can result.
The aim of this thesis was the development of functional surfactants for the synthesis of hybrid lead halide perovskite particles with a special switchable feature. The switching was intended to introduce an energy valve into the phases, which could be switched by external stimuli (i.e. light or chemically). The obtained phases should be investigated for structural, optical and electronic properties, both before and after a switching of the ligands.
For this purpose, ligands based on photoswitchable azobenzene, redox active ferrocene and conductive five-ring heterocycles were developed and their functionality was studied before and after incorporation into 2D layered hybrid perovskite phases. It was found that electronic exchange between the organic molecule and the perovskite framework is present in all the crystal phases obtained. Thus, the molecules are more than just a structural component of the phases, but contribute to the electronic properties.
The oxidation of ferrocene in particular made it possible to integrate a switchable energy valve. The decisive factor is the change in the energy of the molecular orbitals, which was achieved by the oxidation. Thus, the optical and electronic properties of the semiconductor could be greatly changed.
This work provides a comprehensive basis for the study of semiconducting particles with switchable ligands. Especially promising are redox-active hybrid perovskites, which emerge as a completely new class from these investigations
Disease progression and genetic risk factors in the primary tauopathies
The primary tauopathies are a group of progressive neurodegenerative diseases within the frontotemporal lobar degeneration spectrum (FTLD) characterised by the accumulation of misfolded, hyperphosphorylated microtubule-associated tau protein (MAPT) within neurons and glial cells. They can be classified according to the underlying ratio of three-repeat (3R) to four-repeat (4R) tau and include Pick’s disease (PiD), which is the only 3R tauopathy, and the 4R tauopathies the most common of which are progressive supranuclear palsy (PSP) and corticobasal degeneration (CBD). There are no disease modifying therapies currently available, with research complicated by the wide variability in clinical presentations for each underlying pathology, with presentations often overlapping, as well as the frequent occurrence of atypical presentations that may mimic other non-FTLD pathologies. Although progress has been made in understanding the genetic contribution to disease risk in the more common 4R tauopathies (PSP and CBD), very little is known about the genetics of the 3R tauopathy PiD.
There are two broad aims to this thesis; firstly, to use data-driven generative models of disease progression to try and more accurately stage and subtype patients presenting with PSP and corticobasal syndrome (CBS, the most common presentation of CBD), and secondly to identify genetic drivers of disease risk and progression in PiD. Given the rarity of these disorders, as part of this PhD I had to assemble two large cohorts through international collaboration, the 4R tau imaging cohort and the Pick’s disease International Consortium (PIC), to build large enough sample sizes to enable the required analyses.
In Chapter 3 I use a probabilistic event-based modelling (EBM) approach applied to structural MRI data to determine the sequence of brain atrophy changes in clinically diagnosed PSP - Richardson syndrome (PSP-RS). The sequence of atrophy predicted by the model broadly mirrors the sequential spread of tau pathology in PSP post-mortem staging studies, and has potential utility to stratify PSP patients on entry into clinical trials based on disease stage, as well as track disease progression.
To better characterise the spatiotemporal heterogeneity of the 4R tauopathies, I go on to use Subtype and Stage Inference (SuStaIn), an unsupervised machine algorithm, to identify population subgroups with distinct patterns of atrophy in PSP (Chapter 4) and CBS (Chapter 5). The SuStaIn model provides data-driven evidence for the existence of two spatiotemporal subtypes of atrophy in clinically diagnosed PSP, giving insights into the relationship between pathology and clinical syndrome. In CBS I identify two distinct imaging subtypes that are differentially associated with underlying pathology, and potentially a third subtype that if confirmed in a larger dataset may allow the differentiation of CBD from both PSP and AD pathology using a baseline MRI scan.
In Chapter 6 I investigate the association between the MAPT H1/H2 haplotype and PiD, showing for the first time that the H2 haplotype, known to be strongly protective against developing PSP or CBD, is associated with an increased risk of PiD. This is an important finding and has implications for the future development of MAPT isoform-specific therapeutic strategies for the primary tauopathies.
In Chapter 7 I perform the first genome wide association study (GWAS) in PiD, identifying five genomic loci that are nominally associated with risk of disease. The top two loci implicate perturbed GABAergic signalling (KCTD8) and dysregulation of the ubiquitin proteosome system (TRIM22) in the pathogenesis of PiD.
In the final chapter (Chapter 8) I investigate the genetic determinants of survival in PiD, by carrying out a Cox proportional hazards genome wide survival study (GWSS). I identify a genome-wide significant association with survival on chromosome 3, within the NLGN1 gene. which encodes a synaptic scaffolding protein located at the neuronal pre-synaptic membrane. Loss of synaptic integrity with resulting dysregulation of synaptic transmission leading to increased pathological tau accumulation is a plausible mechanism though which NLGN1 dysfunction could impact on survival in PiD
A multidisciplinary approach to the development of innovative tools for pharmaceutical and technological applications
The research activity carried out during the Ph.D. in Chemical and Pharmaceutical Sciences has regarded the design, synthesis, and characterization of innovative tools relevant to both pharmaceutical and technological fields. Great interest has been dedicated to the investigation of the “affinity polymerization” mechanism of novel polymeric materials founded on repetitive monomeric units based on the 3-phenylbenzofulvene scaffold that spontaneously polymerize by simple removal of the solvent. In this context, the attention has been focused on the synthesis of novel benzofulvene-based derivatives bearing complexed and non-complexed pyridine rings in different positions of the benzofulvene scaffold, to evaluate the effects generated by the insertion of a bulky substituent in the aggregation/polymerization behavior. The experience acquired with this study has been then capitalized on the design, synthesis, and characterization of a novel visible-light-sensitive biomimetic molecular switch inspired by the benzofulvene scaffold and the Green Fluorescent Protein (GFP) chromophore. The chemical-structural manipulation of the benzofulvene structure has made possible the development of a novel set of biomimetic photoswitches inspired by the supramolecular properties of the 3-phenylbenzofulvene scaffold and the molecular features of the GFP chromophore.
In the framework of material chemistry, the well-known click-chemistry reaction of hyaluronic acid (HA) derivatives bearing propargylated ferulic groups has been exploited to obtain biomimetic and biocompatible materials useful in different biopharmaceutical fields. In particular, low molecular weight HA has been anchored on the hydrophobic surface of low-generation poly(propylene imine) (PPI) dendrimers by the click-chemistry reaction between their azido-functionalized surfaces and low molecular weight HA derivatives bearing propargylated ferulic groups. The resulting materials have been proposed as biocompatible drug delivery systems (DDSs) of Doxorubicin. Another application of HA has concerned the hyaluronan-based graft copolymers showing low and medium molecular weight values that have been exploited in cross-linking by the click-chemistry reaction. Interestingly, the interaction of resulting HA materials with water led to the formation of hydrogels, and the tunable rheological behavior of these materials led to their applicability in different biomedical fields.
Lastly, the knowledge in medicinal chemistry has guided the design and synthesis of innovative bioactive compounds such as novel Cyclooxygenase‑2 (COX-2) inhibitors containing Nitric Oxide (NO) donor moiety (CINODs) endowed with vasorelaxant properties.
The outcomes of these studies would provide fertile ground for future projects that will hopefully contribute to accelerate the research in several fields. Indeed, the increased knowledge on the behavior of these innovative tools, by means of a multidisciplinary approach, is the key for boosting the development of novel materials for pharmaceutical and technological applications
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