The incredible technological advancements over the last century have been possible due to tiny trinkets designed using semiconducting crystalline materials, especially Silicon and III-V compounds. Silicon, a group IV element has become the first choice in developing microchips serving an ever-growing set of applications including, computation, RF communications, solar cells, power electronics, quantum computing and its periphery, optoelectronics, IOT sensors, and lately artificial intelligence. Billions of Si-based complementary transistors (CMOS) are present at the center of most computing devices used today such as HPC servers, compute farms, laptops, and smartphones. The astonishing rise in transistor count, performance, and functionality as well as the exponential reduction in cost has been possible over the past decades due to a singular idea: shrinking the device. However, this rule, also called Moore's Law has been slowing over the past two decades and has eventually come to a standstill in its traditional definition. Moore's law has since been sustained by ingenious innovations such as high-k gate dielectrics, vertical scaling, lattice strain engineering, novel material developments and, lately chiplets as well as multi-die vertical packaging. As conventional Si CMOS approaches a roadblock, this work presents research on Germanium-based multi-gate devices providing promise for faster and low-power operation. This work discusses how Ge grown on a GaAs substrate can be tuned and utilized to form a virtually defect-free channel for ultra-scaled multi-gate transistors. Calibrated solvers informed using in-house materials and devices as well as literature are used to predict device performance for advanced structures. Further, a hybrid CMOS system with the high hole mobility p-channel device formed using tensile strained Ge, and the high electron mobility n-channel device formed using the underlying InGaAs layer is proposed and simulated. As scaling approaches Gate-all-around Nanosheet FETs in 2024 and complementary-FETs (CFETs) around 2034, Ge-on-AlAs based transistors can offer unique process simplifications, defect reduction, yield improvement, and high-performance advantages showing promise for future IRDS nodes. The process design, material stack, device, and circuit performance for this novel Ge-based NSFET is presented in this work. The lack of large strain or strain relaxation in the NS multilayer starting stack is seen to be a great process advantage for the Ge-AlAs NSFET system. To a certain extent, Si seems omnipotent for all things electronics. However, one exception is on-chip light generation. A coherent electrically controllable on-chip light source is a central component critical for optoelectronics, quantum technologies, fiber communications, and sensing. Due to the indirect bandgap, Si cannot produce light hence direct bandgap materials such as GaAs and GaN have been the primary choice for off-chip light sources integrable on the platform. Interestingly, Ge has a pseudo-direct bandgap, i.e., unlike Silicon, it can be manipulated to produce light using heavy doping, tensile strain, and Sn alloying. Similar to conventional III-V light sources, reduction in the dimensionality of the gain medium, i.e., Ge can enable a drastic reduction in the current required to produce light, among other performance considerations. This reduced dimensionality can be achieved by forming quantum wells and quantum dots. In this work, two new types of Ge-based quantum well lasers are introduced and analyzed along with qualitative and quantitive benchmarking. The first QW laser uses a small epitaxial biaxial tensile strain to improve the direct-ness of the Ge gain medium. The internal quantum efficiency, net gain, and threshold current can be improved drastically by choosing the right tensile strain while staying within a certain critical thickness value. For the first time, the impact of biaxial tensile strain on the optical properties of Ge is analyzed and reported through a systematic study of the dielectric spectra and optical constant using VASE. The changes in the band structure due to tensile strain are correlated with the critical points to uncover various optical transitions. An even better QW laser architecture is possible by utilizing a GeSn QW. This QW laser uses Sn-alloying to form a GeSn active region which is further lattice matched to the waveguide (InGaAs) and the optical confinement layers (InAlAs) around it. This completely lattice-matched laser structure can offer unique advantages such as virtually defect-free active region, tunability as well as improved efficiency and threshold current density. The absence of strain and consequently strain relaxation in the laser stack enables one to steer away from the critical thickness limitation while opening doors to designing multiple quantum well lasers among other complex architectures. The impact of Sn alloying on the atomic structure, lattice coherence, and relaxation is analyzed through XRD reciprocal space maps and rocking curves as a function of Sn concentration. Further, this lattice-matched system, GeSn-InGaAs-InAlAs has the potential to mirror the benefits of the mature GaAs-AlGaAs system which led to many great technological innovations over the past decades such as lasers and LEDs. / Doctor of Philosophy / This thesis introduces two transistor technologies to extend the scaling beyond conventional Si devices into the next decade, and two QW laser technologies for integrated photonics. Through calibrated numerical solvers, a high mobility Ge and InGaAs cointegrated CMOS system for 0.5 V is introduced, analyzed and benchmarked with literature. A lattice matched Ge-on-AlAs multilayer stack is shown to have great potential to form a novel CMOS system which uses Ge Nanosheets, providing process advantage and superior performance. The next part of the thesis introduces two types of Ge based quantum well lasers, one based on tensile strained Ge and the other based on lattice matched Ge. Both show large performance improvements over previous attempts in literature. Lasing from an indirect bandgap material such as Ge, the associated challenges and performance metrics are discussed. Lastly, the optical, dielectrics and CP properties of tensile strained are presented for the first time uncovering interesting trends. Ge samples with increasing tensile strain are grown using MBE and measured using VASE to elucidate the physical phenomenon.

Редкоземельные цирконаты со структурой пирохлора R2Zr2O7 (R=La-Lu), обладают разнообразными свойствами, в том числе имеют потенциальное применение как люминофоры, при активации другими редкоземельными ионами. Экспериментальные данные по ИК и КР спектрам редкоземельных цирконатов, по упругим свойствам, по ширине запрещенной щели отрывочны, и имеются в научной для 2-3 представителей ряда. Представляется актуальным в рамках единого ab initio подхода исследовать комплекс свойств ряда редкоземельных цирконатов R2Zr2O7(R=La-Lu). В работе проведен ab initio расчет фононного спектра всего ряда редкоземельных цирконатов, определены частоты и типы ИК и КР-мод, что позволило дополнить экспериментальные данные по ИК и КР спектрам. Выявлены моды, в которых участвуют преимущественно ионы кислорода. Изменение этих мод может говорить об искажении кислородной подрешетки под влиянием внешних воздействий на кристалл. Рассчитаны упругие постоянные, модули упругости и твердость по Виккерсу для ряда R2Zr2O7 (R=La-Lu), что дополнило отсутствующие экспериментальные данные. Показано, что при лантаноидном сжатии усиливается анизотропия упругих свойств. Показано, что в примесных центрах La2Zr2O7:R3+ расстояние «примесный ион-лиганд» изменяется в пределах ~ 0.1 Å, что существенно меньше, чем различие ионных радиусов по Шеннону La и примесного иона R 3+. Показано, что замещение ионов La в кристалле La2Zr2O7 другими редкоземельными ионами R3+ до 25% изменяет упругие модули кристалла в пределах 10%. В работе показана возможность заменять на псевдопотенциал внутренние оболочки редкоземельных ионов по 4f включительно при расчете кристаллической структуры, фононного спектра, упругих свойств 3 редкоземельных цирконатов R2Zr2O7 (R=La-Lu). Такой подход может быть использован и в других кристаллах с РЗ подрешеткой для минимизации затрат компьютерных ресурсов. Результаты работы представлены на международной и всероссийской конференциях: LXVII Международная конференция «Актуальные проблемы прочности» («АПП-2024», Екатеринбург), «XXIII Всероссийская школа-семинар по проблемам физики конденсированного состояния вещества» («СПФКС-23», Екатеринбург). / Rare earth zirconates with a pyrochlore structure R2Zr2O7 (R=La- Lu), have a variety of properties, including potential using as luminophores when activated by others rare earths ions. Experimental data on the IR and Raman spectra of rare earths zirconates, elastic properties, band gap width are poor, and are available in scientific journals for 2-3 crystals of the row. It seems actual to study complex of properties of the all row of rare earth zirconates R2Zr2O7(R=La-Lu) within the framework of ab initio approach. The work carried out an ab initio calculation of the phonon spectrum of the all row of rare earth zirconates. The frequencies and types of IR and Raman modes have been determined, which made it possible to supplement the absent experimental data on the IR and Raman spectra. Phonon modes have been identified in which predominantly oxygen ions participate. A change of these modes may indicate to a distortion of the oxygen sublattice under the influence of external effects on the crystal. Calculated elastic constants, elastic moduli and Vickers hardness for the series R2Zr2O7 (R=La-Lu), which supplemented the missing experimental data. It has been shown that the anisotropy of elastic properties increases by lanthanide pressure. It has been shown that in La2Zr2O7:R3+ impurity centers the distance “impurity ion-ligand” varies within ~ 0.1 Å, which is significant less than the difference between the Shannon ionic radii between La and the impurity ion R3+. It has been shown that the replacement of La ions in the La2Zr2O7 crystal by other rare earth ions R3+ up to 25% changes the elastic moduli of the crystal in within 10%. The work shows the possibility of replacing internal shells of rare earth ions up to 4f inclusive by calculating crystal structure, phonon spectrum, elastic properties of rare earth zirconates R2Zr2O7 (R=La-Lu). This approach could be used in other crystals with rare-earth sublattice to minimize the computer cost. The results of the work were presented at the international and all-Russian conferences: LXVII International Conference “Current Problems strength" ("APP-2024", Ekaterinburg), "XXIII All-Russian School- seminar on problems of condensed matter physics" (“SPFKS-23”, Ekaterinburg).

The Lyons group denoted by Ly is a Sporadic Simple Group of order 51765179004000000 = 28 37 56 7 11 31 37 67. It(Ly) has a trivial Schur Multiplier and a trivial Outer Automorphism Group. Its maximal subgroups are G2(5) of order 5859000000 and index 8835156, 3 McL:2 of order 5388768000 and index 9606125, 53 L3(5) of order 46500000 and index 1113229656, 2 A11 of order 29916800 and index 1296826875, 51+4 + :4S6 of order 9000000 and index 5751686556, 35:(2 M11) of order 3849120 and index 13448575000, 32+4:2 A5 D8 of order 699840 and index 73967162500, 67:22 of order 1474 and index 35118846000000 and 37:18 of order 666 and index 77725494000000. Its existence was suggested by Richard Lyons. Lyons characterized its order as the unique possible order of any nite simple group where the centralizer of some involution is isomorphic to the nontrivial central extension of the alternating group of degree 11 by the cyclic group of order 2. Sims proved the existence of this group and its uniqueness using permutations and machine calculations. In this dissertation, we compute the (p; q; t)-generations of the Lyons group for dis- tinct primes p, q and t which divide the order of Ly such that p < q < t. For computations, we made use of the Computer Algebra System GAP / Mathematical Sciences / M.Sc. (Mathematics)

No description available.

No description available.

Nuclear magnetic resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids because nuclear spin-lattice relaxation times are dependent upon the details of molecular motion. The combined application of Raman and Infrared (IR) lineshape analysis can furnish more complete information to characterize the anisotropic rotation of molecules. Presented here are the studies of NMR relaxation times, together with Raman/IR Mneshape analysis of the solvent and temperature dependence of rotational diffusion in 1,3,5-tribromobenzene and 1,3,5-trifluorobenzene. In these experiments, it was found that the rotational diffusion constants calculated from Perrin's stick model were two to three times smaller than the measured values of D, and D,,. Similarly, rotational diffusion constants predicted by the Hu-Zwanzig slip model were too large by a factor of 2. Application of the newer Hynes-Kapral-Weinberg model furnished rotational diffusion constants that were in reasonable agreement with the experimental results. The vibrational peak frequencies and relaxation times of the isotropic Raman spectra of the υ1 modes of CD2Br2 and CHBr3 were studied in solution. The frequency shifts in non-interactive solvents were explained well on the basis of solution variations in the dispersion energy. In Lewis bases, the displacements were in some, but not all, cases greater than predicted. On the other hand, it was found that the vibrational relaxation times of the C-H/C-D modes decreased dramatically in all Lewis base solvents. Therefore, it was concluded that relaxation times of the υ1 modes, rather than frequency shifts, furnish a more reliable measure of hydrogen bonding interactions of halomethanes in solution.

Notre travail de recherche concerne l’étude théorique de la structure électronique des molécules diatomiques telles que les mono-halogénures d’Aluminium AlX(X=Br,I) et les mono-halogénures de Lutécium LuX(X=F,Cl). Les méthodes ab-initio sont utilisées pour réaliser notre étude. Il s’agit des méthodes Hartree-Fock SCF, CASSCF (Complete Active-Space Self-Consistent Field) et les méthodes d’interaction de configuration multi-référence MRCI avec et sans la correction de Davidson. Ces calculs sont effectués à l’aide du progiciel en chimie quantique MOLPRO, en bénéficiant de l’usage de l’interface graphique GABEDIT. Nos résultats ont regroupé les courbes d’énergie potentielle CEPs, les constantes spectroscopiques, y compris la fréquence harmonique ωe (cm-1), la distance internucléaire à l’équilibre Re (Å) et la valeur énergétique Te(cm-1) pour un ensemble des états électroniques singulets et triplets de représentation 2s+1Λ(+/-) (L’effet de spin-orbite est négligeable) pour ces quatre molécules. Par comparaison entre nos résultats obtenus et ceux apportés de la littérature, on a trouvé un bon accord avec un faible pourcentage d’erreur ne dépassent pas le 3% par rapport à la valeur expérimentale considérée comme valeur exacte / Our research concerns the theoretical study of the electronic structure of diatomic molecules such as Aluminum mono-halides AlX (X = Br,I) and Lutetium mono-halides LuX (X = F, Cl). The ab-initio methods are used for our study. These methods SCF, CASSCF (Complete Active-Space Self-Consistent Field) and interaction of configuration multi-reference MRCI with and without Davidson correction. These calculations are performed using the quantum chemistry software package MOLPRO, benefiting from the use of graphic interface GABEDIT. Our findings have consolidated the potential energy curves PECs, spectroscopic constants, including harmonic frequency ωe(cm-1), the internuclear distance at equilibrium Re(Å) and energy Te(cm-1) for a set of singlet and triplet electronic states in the representation 2s +1 Λ (+/-) (neglecting spin-orbit effects) for these four molecules. By comparison between our results and those contributed to the literature, we found a good agreement with a low percentage of error does not exceed 3% from the experimental value was considered as exact

This diploma thesis is concentrated on the novel production of the original author of the 20th century Aldo Palazzeschi (1885 - 1974). The aim of the thesis is to reveal the common thematic motives and attributes in his three novels: Il codice di Perelà (Man of smoke, 1911), Sorelle Materassi (Materassi sisters, 1934) and Il doge (The doge, 1967). Firstly the thesis acquaints with its aim, subsequently submits the chronology of the author's biography. Then briefly outlines the important events of the 20th century. Afterwards the thesis offers a summary of the evolution of Aldo Palazzeschi's production in the cultural-aesthetic context of the 20th century. The thesis is mainly devoted to the textual analysis of the three above mentioned novels. The analysis are focused on the function of the protagonists and on the main thematic motives. In the final chapter are summarized the common thematic motives and attributes of the three novels - abstract character and isolation of the main protagonists, conformity of the masses, dramatic attributes of the novels, opposition between anarchy and rules, provocation of the provincial moral, criticism of the prejudice or the absurd. The appendix brings the photos of Aldo Palazzeschi.

Wooden objects have been widely used in the history of humanity and play an important role in our cultural heritage. The preservation of such objects is of great importance and can be a challenging task. This thesis investigates the static and time-dependent mechanical behaviour of archaeological oak wood from the Vasa warship. Characterisation of mechanical properties is necessary for the formulation of a numerical model to design an improved support structure. The ship was impregnated with polyethylene glycol (PEG) for dimensional stabilisation. All elastic engineering constants of the Vasa oak have been identified and compared with those of recent oak by means of the static and dynamic testing. The experiments were done on samples with cubic geometry, which allowed obtaining all elastic constants from a single sample. The usage of cubic samples with orthotropic mechanical properties during compressive experiments was validated with finite-element simulations. The Young's moduli of the Vasa oak in all orthotropic directions were smaller than those for the recent oak. The shear moduli of Vasa oak was determined and verified with the resonant ultrasound spectroscopy. The time-dependent mechanical behaviour of the Vasa oak has been studied. Creep studies were performed in uniaxial compression on the cubic samples in all orthotropic directions. The samples loaded in the longitudinal direction were subjected to different stress levels. A stress level below 15% of the yield stress in the longitudinal direction did not result in non-linear creep with increasing creep rates within the time frame of the tests. The results of the studies in radial and tangential directions showed that creep was dominated by the effect of annual fluctuations in relative humidity and temperature. The weight changes based on annual fluctuations of relative humidity were measured for Vasa oak and recent oak. The Vasa oak showed higher variations due to an increased hygroscopicity which is the result of the impregnation with PEG. In conceiving a full-scale finite-element model of Vasa ship, not only the stress-strain relations of the material but also those of the structural joints are needed. Since the in-situ measurement of joints is not an option, a replica of a section of the ship hull was built and tested mechanically. The load-induced displacements were measured using 3D laser scanning which proved to have advantages to conventional point displacement measurements. The mechanical characteristics of the Vasa oak and joint information presented in this work can be used as input for a finite-element model of the Vasa ship for simulation of static and time-dependent behaviour on a larger scale. / Stötta Vasa

Afin de réduire la consommation en énergie fossile et ainsi limiter les émissions de gaz à effet de serre, l’un des objectif du Grenelle de l’Environnement est de porter à 23% la part des énergies renouvelables dans la consommation d’énergie finale en France en 2020. Le bois-énergie représente une alternative à l’utilisation des énergies fossiles, mais c’est également une source de polluants dans l’atmosphère et il est essentiel de déterminer sa contribution potentielle à la dégradation de la qualité de l’air intérieur et extérieur. Au cours de cette thèse, mes travaux de recherche se sont focalisés sur l’étude en chambres de simulation de la dégradation atmosphérique de composés émis par la combustion du bois : les méthoxyphénols. Au Laboratoire de Physico-Chimie de l’Atmosphère (LPCA) de l’Université du Littoral Côte d’Opale (ULCO), des tests ont tout d’abord été réalisés afin de s’assurer que les parois de la chambre, en PMMA (PolyMéthacrylate de Méthyle), n’induisaient pas d’artéfacts lors de son irradiation et des réactions chimiques réalisées avec l’ozone, les radicaux hydroxyles et les radicaux nitrates. La constante de réaction du syringol avec les radicaux OH a été déterminée à (294 ± 3) K. La valeur obtenue (9,65x10⁻¹¹ cm³.molécule⁻¹.s⁻¹) conduit à une durée de vie atmosphérique du syringol d’environ 2 heures pendant la journée. L’oxydation du guaiacol et du syringol par les radicaux hydroxyles a permis d’observer la formation d’aérosols organiques secondaires (AOS) avec des rendements de 0,003 - 0,87 et 0,10 - 0,36, respectivement. L’étude des produits d’oxydation gazeux et particulaires de la réaction du guaiacol avec les radicaux OH a mis en évidence principalement la présence de nitroguaiacols dans la phase gazeuse et nous avons suggéré d’utiliser ces composés comme traceurs de la combustion du bois du fait de leur faible réactivité atmosphérique.Les études cinétiques des réactions des radicaux nitrates avec le guaiacol, le 3-méthoxyphénol et le syringol réalisées à (294 ± 3) K ont permis de déterminer les constantes de réactions correspondantes. Celles-ci se trouvent dans la gamme (1,15 – 21,7) × 10⁻¹¹ cm³.molécule⁻¹.s⁻¹ et les durées de vie associées sont d’environ 2 minutes pendant la nuit. À la Bergische Universität Wuppertal (en Allemagne), la réaction d’une série de composés aromatiques méthoxylés (anisole, 2-méthylanisole, guaiacol, 3-méthoxyphénol, 4-méthoxyphénol, 2-méthoxy-4-méthylphénol, syringol et 2,3-diméthoxyphénol) avec les radicaux hydroxyles a été étudiée. Les constantes des méthoxybenzènes et méthoxyphénols obtenues sont comprises entre (2,12 – 4,64) x 10⁻¹¹ cm³.molécule⁻¹.s⁻¹ et (5,75 - 8,10) x 10⁻¹¹ cm³.molécule⁻¹.s⁻¹, respectivement, ce qui conduit à des durées de vie de 4-8 et 3-2 heures. Pour ces mêmes composés, nous avons également déterminé, les constantes pour leur réaction avec les atomes de chlore qui sont dans la gamme (1,07 – 1,20) x 10⁻¹⁰ cm³.molécule⁻¹.s⁻¹, pour les méthoxybenzènes et (2,71 – 4,73) x 10⁻¹⁰ cm³.molécule⁻¹.s⁻¹ pour les méthoxyphénols. Leurs durées de vie vis-à-vis de cette réaction sont respectivement de 46-52 heures et 12-21 heures. Cette étude sur l’oxydation troposphérique des méthoxyphénols est à notre connaissance la première qui ait été réalisée. Elle a permis de mettre en évidence une réactivité élevée diurne et nocturne de ces composés ainsi que leur contribution à la formation d’AOS. Le bois-énergie est donc à la fois une source d’aérosols primaires mais également secondaires et son utilisation a donc des effets sur l’homme (santé) et l’environnement. / One of the objectives of the Grenelle Environment Forum is to increase the quantity of the renewable energy up to 23% in the final energy consumption in France in 2020, to reduce fossil fuel consumption and thus restrict the level of greenhouse gas emissions. The wood-energy represents an alternative to fossil fuel, but it also a source of atmospheric pollutants. It is necessary to determine its potential contribution to the degradation of air quality (indoor and outdoor). During this PhD, my works focused on the study, in simulation chambers, of the atmospheric degradation of compounds emitted by wood combustion : the methoxyphenols. In the Laboratory of Physical Chemistry of the Atmosphere (LPCA) of the Universite of Littoral-Côte d’Opale (ULCO), tests were carried out to be sure that the walls of the chamber (in PMMA PolyMethacrylate of Methyl) are not a source of artifacts during its irradiation and chemical reactions with ozone, hydroxyl radicals and nitrate radicals. The rate coefficient of the reaction of syringol with OH radicals was determinate at (294 ± 2) K and is 9,65 x 10−¹¹ cm³ molecule−¹ s−¹. Then the atmospheric lifetime was calculated : it is about 2 hours during the day. During the oxidation of guaiacol and syringol, we observed the formation of Secondary Organic Aerosol (SOA) with yields ranging from of 0.003 to 0.87 and from 0.10 to 0.36, respectively. Oxidation products study in the gas- and particle- phases for the reaction of guaiacol with OH radicals showed principally the presence of nitroguaiacols in the gas phase, which may be potential wood combustion tracers due to their low atmospheric reactivity. The kinetic studied of NO₃ radicals with guaiacol, 3-methoxyphenol and syringol were realized at (294 ± 3) K. They were leaded to rate coefficients in the range of (1,15 – 21,7) x 10−¹¹ cm³ molecule−¹ s−¹ and so associated atmospheric lifetimes about 2 minutes, overnight. At the Bergische Universität Wuppertal (Germany), the reaction of a series of methoxylated aromatic compounds (anisole, 2-methylanisole, guaiacol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-methylphenol, syringol and 2,3-dimethoxyphenol) with hydroxyl radicals were studied leading to the following rate coefficients for methoxybenzenes and metoxyphenols, (2,12 -4,64) x 10−¹¹ cm³ molecule−¹ s−¹ and (5,75 -8,10) x 10−¹¹ cm³ molecule−¹ s−¹, respectively. The estimated atmospheric lifetimes are in the range from 4 to 8 hours and from 2 to 3 hours, for methoxybenzenes and methoxyphenols, respectively. For these compounds, we also determined, the rate coefficients for their reaction with chlorineatoms, which are between (1,07 – 1,20) x 10−¹¹ cm³ molecule−¹ s−¹, for methoxybenzenes, and (2,71 – 4,73) x 10−¹¹ cm³ molecule−¹ s−¹, for methoxyphenols. Thus, their respective atmospheric lifetimes are 46-52 hours and 12-21 hours. This study of tropospheric oxidation of methoxyphenols is to our knowledge the first one. It allows underlining a high reactivity of these compounds during the day and overnight and also their contribution to SOA formation. The wood-energy is thus both a source of primary and secondary aerosols. Its use therefore impacts human health and the environment.