One third of world’s total energy is used in production of electricity and one fifth of the total electricity produced in the world is used in lighting. Hence, the materials that have high potential in the field of photovoltaic’s and photoluminescence have recently drawn special attention to meet the ever increasing energy demands. In this thesis, we have studied a few materials that hold tremendous promises in fabricating photovoltaics and photoluminescent devices. Any ferroelectric material is an efficient solar energy converter as it contains an the intrinsic dipolar field which can effectively separate the photo excited electron and hole. We have developed a few materials which possess inherent polarization efficiently absorb over a wide portion of the solar spectrum and hence can find application in the field of photovoltaics. Secondly, we also dealt with semiconductor nonmaterial’s which are technologically very important owing to their improved photoluminescence properties. We tried to improve their light emitting efficiency by engineering crystal structure in nanometer length scales. The thesis deals with such advanced energy materials and is divided in seven chapters. Chapter 1 provides a brief introduction to the fundamental concepts that are relevant in the subsequent chapters. The chapter is started with a brief scenario of current status of energy production and its usage. Next, we have discussed the prospects of ferroelectric materials in photovoltaic devices. This is followed by a brief background on ferroelectricity and related properties which we have studied subsequently. At the end of this chapter a brief overview of photoluminescence properties in semiconductor nonmaterial’s is presented. In this section we have addressed the particular issues that need to be taken care of in order to improve their light emission properties. Chapter 2 describes different experimental and theoretical methods that have been employed to carry out different studies presented in the thesis. Chapter 3 addresses the possibility of employing BaTiO3 (BTO) based composite perovskite oxides as a potent photovoltaic material. It is known that BTO can produce photocurrent upon excitation with suitable light source. However, inability of BTO to absorb sufficient sunlight owing to its near UV band gap prevents to make use of this material in photovoltaic devices. In order to reduce the band gap we have tried to tune the electronic structure at the band edge by doping non-d0 transition metal ions at Ti site. As it is known in the literature an isovalent substitution of Ti4+ stabilizes non-polar phase of BTO we employed a co-doping strategy to substitute tetravalent Ti with equal percentage of a trivalent and a pentavalent metal ion. Keeping in mind off-centering of Ti4+ is primary reason behind the large ferroelectric polarization of BTO, a judicious choice of co-dopant was necessary to minimize reduction of polarization due to replacement of Ti. We have found at least two pairs of co-dopants, namely Mn3+-Nb5+ and Fe3+-Nb5+ which at low doping concentration ( < 10%) effectively reduces the band gap of BTO without affecting its polarization to a large extent. We systematically increase the doping concentration of both the pair of dopants and found Mn3+-Nb5+ pair is more efficient over Fe3+-Nb5+ both in terms of reducing band gap and retaining the polarization of BTO. We have characterized the ferroelectric nature of all the doped compositions with the help of dielectric, polarization and pyroelectric measurements. We have also performed first principle density functional theory (DFT) calculations for an equivalent doped composition and addressed the nature of modulations of electronic structure at the band edges which is responsible for such large reduction of band gap. Chapter 4 deals with composite perovskite materials which posses large tetragonal distortions with reduced optical band gaps. Here we have exploited Cu-Nb and Cu-Ta pair which upon complete substitution of Ti of BTO leads to composite perovskites with enhanced tetragonal distortion of the perovskite lattice. For two resultant compositions, namely BaCu1/3Nb2/3O3 and BaCu 1/3Ta2/3O3 we have characterized the optical and ferroelectric properties. We found though these material possess small band gap (∼ 2 eV), these are not ferroelectric in nature. Results of second harmonic generation measurements and refinement of powder X-ray diffraction both establish Centro symmetric nature of these materials. We infer from these results that presence of large tetragonal distortion is a result of symmetric Jahn-Teller type distortion of Cu2+ and not due to off-centering of any of the metal ions in their MO6 octahedral geometries. In Chapter 5, we have considered the material SrTiO3 (STO) which is stable in cubic paraelectric phase at room temperature. But at the same time this material is considered as an incipient ferroelectric due to presence of an active polar vibrational mode which does not become completely soft even at temperature close to 0 K. While this polar vibrational mode can easily be frozen by making substitution at Sr site, a similar attempt by making substitution at Ti site failed earlier. Keeping in mind Ti is easier to substitute than Sr we employed same co-doping strategy that we have considered in Chapter 3. We found Mn- Nb and Mn-Ta co-dopants at low doping concentration are extremely useful in transforming incipient ferroelectric STO into a dipolar glass. We have characterized the glassy dipolar property of doped STO with the help of tem-perature dependent dielectric response of these material. At the same time we found these co-doped STO possess enhanced static dielectric constant at room temperature with favourable dielectric loss values in comparison to pure STO. We have also ad-dressed the origin of a glassy dipolar state with the help of DFT calculation performed on equivalent doped composition that we have considered for our experiments. In Chapter 6, we have considered another incipient ferroelectric material TiO2 in rutile phase which also possess polar vibrational mode at temperature close to 0 K. A lattice strain along the polar vibrational mode make symmetric non-polar structure unstable with respect to the distorted polar structure. In this context, we found two particular compositions FeTiTaO6 and CrTiTaO6 that are also stable in rutile phases at room temperature but possess similar strain due to presence of larger Fe or Cr and Ta in rutile lattice. Considering the fact these two composite rutile oxides are relaxer ferroelectric in nature, we critically evaluated the effect of the particular kind of strain that these materials introduce in rutile lattice. We also characterized relaxor ferroelectric property and optical band gap of these materials and commented on the potential of these materials in exploiting them in photovoltaic devices. Chapter 7 presents a unique strategy of making use of crystal defects in improving photoluminescent properties of semiconductor nanocrystals. We have shown defects when introduced in nanocrystals in a controlled protected manner efficiently overcome the problem of self absorption which is known to reduce quantum efficiency of emit-ted light. Controlling synthesis conditions we separately prepared CdS nanocrystals with and without intergrowth defects. We characterized the presence of the intergrowth defect with the help of high resolution transmission electron microscope (HRTEM) image. We have also characterized Stokes’ shifted PL emission and ultrafast charge carrier dynamics of these NCs with intergrowth defects. To support these experimental findings we have computed the electronic structures of model nanoclusters possessing similar intergrowth defects that has been observed in HRTEM images. We find that the presence of defects in a nanocluster particularly affect the position of the band edge. However our joint density of state calculation shows that contribution of these defect states to an absorption spectra is negligible. Thus presence of defect states at band edge ensures a Stokes’ shifted emission without affecting the position of absorption. In a separate section of this chapter we have shown apart from intergrowth defects presence of twin boundary also provide similar mid-gap states that can alter its’ optical proper-ties to large extent. In summary, we have studied a few bulk and nano-materials which can show improved photovoltaic and photoluminescence property. We investigated effect of external dopant ions on a classical ferroelectric material BaTiO3 and two incipient ferroelectric materials SrTiO3 and rutile TiO2. We have also shown that efficient defect engineering could be extremely useful in improving photoluminescent property of CdS nanocrystals which is a prototype of II-VI semiconductor nanomaterials. In a separate Appendix Chapter, we have shown an easy and efficient way to suppress coffee ring effect which takes place universally when a drop of colloidal suspension is dried on a solid substrate. We have shown temporary modification of hydropho-bicity of a glass substrate not only can suppress the coffee ring effect but also leaves the particle in a highly ordered self-assembled phase after completion of drying process

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Hat sections, single and double, made of steel are frequently encountered in automotive body structural components such as front rails, B-Pillar, and rockers of unitized-body cars. These thin-walled components can play a significant role in terms of crashworthiness and impact energy absorption, through a nonlinear phenomenon called as progressive dynamic buckling. As modern vehicle safety design relies heavily on computer-aided engineering, there is a great need for analysis-based predictions to yield close correlation with test results. Although hat sections subjected to axial loading have been studied widely in the past, there is scanty information in published literature on modeling procedures that can lead to robust prediction of test responses. In the current study, both single-hat and double-hat components made of mild steel are studied extensively experimentally and numerically to quantify statistical variations in test responses such as peak load, mean load and energy absorption, and formulate modeling conditions for capturing elasto-plastic material behavior, strain rate sensitivity, spot-welds, etc. that can lead to robust predictions of force-time and force-displacement histories as well as failure modes. In addition, keeping initial stages of vehicle design in mind, the effectiveness of soft computing techniques based on polynomial regression analysis, radial basis functions and artificial neural networks for quick assessment of the behaviors of steel hat sections has been demonstrated. The study is extended to double-hat sections subjected to eccentric impact loading which has not been previously reported. A lightweight enhancement of load carrying capacity of steel hat section components has been investigated with PU (polyurethane) foam-filled single and double hat sections, and subjecting the same to quasi-static and axial impact loading. Good predictions of load-displacement responses are again obtained and shortening of fold lengths vis-à-vis hollow sections is observed. Finally, the performance of hat sections made of glass fiber-reinforced composites is studied as a potential lightweight substitute to steel hat section components. The challenging task of numerical prediction of the behaviors of the composite hat sections has been undertaken using a consistent modeling and analysis procedure described earlier and by choosing an appropriate constitutive behavior available in the popular explicit contact-impact analysis solver, LS-DYNA.

Click chemistry is a molecular synthesis strategy based on reliable, highly selective reactions with thermodynamic driving forces typically in excess of 20 kcal mol-1. The 1,3-dipolar cycloaddition of azides and alkynes developed by Rolf Huisgen saw dramatic rate acceleration using Cu(I) as a catalyst in 2002 reports by Barry Sharpless and Morten Meldal enabling its click chemistry eligibility. Since these seminal reports, the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) has become the quintessential click reaction finding diverse utility. The popularity of the CuAAC has naturally led to interest in new catalyst systems with improved efficiency, robustness, and reusability with particular focus on nanomaterial catalysts, a common trend across the field of catalysis. The high surface area of nanomaterials lends to their efficacy as colloidal and heterogeneous nanocatalysts, but the latter boasts the added benefit of easy separation and recyclability. With any heterogeneous catalyst, a common question arises as to whether the active catalyst species is truly heterogeneous or rather homogeneous through metal ion leaching. Differentiating these processes is critical, as the latter would result in reduced efficiency, higher cost, and inevitable environmental and heath side effects. This thesis explores the CuAAC from an interdisciplary approach. First as a synthetic tool, applying CuAAC-formed triazoles as functional, modular building blocks in the synthesis of optical cation sensors by combining azide and alkyne modified components to create a series of sensors selective for different metal cations. Next, single-molecule spectroscopy techniques are employed to observe the CuNP-catalyzed CuAAC in real time. Combining bench-top techniques with single-molecule microscopy to monitor single-catalytically generated products proves to be an effective method to establish catalysis occurs directly at the surface of copper nanoparticles, ruling out catalysis by ions leached into solution. This methodology is extended to mapping the catalytic activity of a commercial heterogeneous catalyst by applying super-localization analysis of single-catalytic events. The approach detailed herein is a general one that can be applied to any catalytic system through the development of appropriate probes. This thesis demonstrates single-molecule microscopy as an accessible, effective, and unparalleled tool for exploring the catalytic activity of nanomaterials by monitoring single-catalytic events as they occur.

Dans le cadre d'un projet de recherche proposé par l'Institut National de Recherche et de Sécurité (INRS), cette thèse aborde les nanomatériaux manufacturés (NMM) sous l'angle philosophique à la recherche des conditions de possibilité d'une protection juridique efficace et évolutive, des travailleurs en industrie de production et d'utilisation de ces objets. Les NMM sont des objets fondamentalement nouveaux, polémiques et polymorphes avec des propriétés souvent inédites.La première partie de la thèse rend compte des problèmes spécifiques à la production de normes dans l'expérience humaine, plus précisément des normes juridiques sur le travail, puisque ces problèmes impactent les possibilités d'une qualification juridique des NMM et par voie de conséquence la protection des travailleurs. La deuxième partie fait un état des connaissances sur les NMM afin d'identifier les difficultés propres à l'objet, dans la mesure où une connaissance stabilisée est nécessaire à une qualification juridique. La troisième partie propose d'analyser l'activité de travail comme enchâssement de débats de normes qui construisent en amont un monde qualifié par rapport à des choix de vie qui se manifestent sous forme de normes antécédentes, et a fortiori sous la forme de normes juridiques dans l'activité. La thèse considère les NMM à la fois comme des objets d'études pour les sciences de la matière, dont ils sont issus, et comme des objets des sciences humaines et sociales, entendues comme sciences de l'Homme en activité. Ainsi notre apport se retrouve dans l'analyse de l'activité comme outil de maïeutique, source d'une communication entre les différents acteurs de ce domaine. / In the frame of a research project proposed by the French National Institute of Research and Security (INRS), this thesis approaches manufactured nanomaterials (MNM) from the point of view of a philosophical inquiry into the conditions of possiblity of an efficacious and progressive juridical protection of workers in the industry of manufacturing and of the usage of these materials. The MNM are fundamentally new, controversial and often polymorphic objects, with unique properties.The first part of the thesis reports on specific problems in the production of standards in human experience, specifically legal labor standards, since these issues impact the possibilities of a legal characterization of MNM and consequently the protection of workers. The second part proposes an assessment of the state of knowledge concerning the MNM in order to identify the difficulties proper to the material, considering consolidated knowledge is necessary for any qualification in terms of Law.The third part attempts to analyze the activity of work as a grounding of the debate on standards which, from the outset, constructs a world qualified in relation to life choices that become manifest in the shape of already existing standards and a fortiori in the shape of legal standards within the activity of work.This thesis considers MNM as both the object of study for the science of Matter, from which they have sprung, and the object of the social and human sciences, understood as the science of Man in activity. Thus our contribution is to be found within the analysis of the activity as a maieutic implement, and therefore a source of communication between the different actors in this domain.

Nous avons étudié les comportements dynamiques d'auto-assemblage des tensioactifs cationiques non-chiral en présence du contre-anion chiral.Lorsque le nucléotide anionique chiral est ajouté à des vésicules cationiques, la transition morphologique se produit et transforme in situ des vésicules sphériques en hélices micrométriques.D'autres types de Gemini tensioactifs cationiques forment des rubans nanométriques hélicoïdaux, en présence de tartrate contre-anions. La forme et l'hélicité de ces rubans peuvent être contrôlés in situ par la variation de l'excès énantiomérique.En outre, les nanohélices organiques peuvent être transcrite en nanohélices 3D de silice via une polycondensation sol-gel.Ces nanohélices de silice fonctionnalisées avec des groupes aminés peuvent interagir fortement avec des nanoparticules d'or (GNPs; 1 ~ 20 nm). Le réseau 3D de -nanohélices GNPs/silice sont potentiellement utilisables pour des applications de capteurs basée sur les SERS comme ceux chimiques et biologiques ultra-sensibles en phase liquide. / We have studied the dynamic self-assembly behaviors of non-chiral cationic surfactants in thepresence of chiral counter-anion.When the chiral anionic nucleotides are added to cationic vesicles, morphology transitionoccurs and spherical vesicles transform in situ to micrometric helices.Other types of cationic surfactant, gemini surfactants form nanometric helical ribbons in thepresence of tartrate counter-anion. The shape and helicity of these self-assembled structurescan be controlled in situ by the variation of enantiomeric excess.In both cases, they form gels in water by creating extended networks of nanometric tomicrometric chiral fibers.Additionally, the organic nanohelices can be transcribed to 3D silica nanostructures via solgelpolycondensation. These silica nanohelices functionalized with amino group can interactstrongly with gold nanoparticles (1 ~ 20 nm). The 3D network of GNPs/silica-nanohelices canpotentially be used for SERS-based sensing applications such as ultra-sensitive chemical andbiological sensors in liquid phase.

Les nanomatériaux manufacturés (comme les nanoparticules d’oxydes métalliques, les nanotubes de carbone, les nanofibres etc.) possèdent des propriétés remarquables qui leur confèrent des applications industrielles innovantes. Néanmoins, ces nouveaux matériaux soulèvent des inquiétudes vis à vis de leurs potentiels risques. Ces nanomatériaux manufacturés connaissent une production et une commercialisation croissantes. Par conséquent, de plus en plus de personnes sont potentiellement exposées à ces nanomatériaux (aussi bien les consommateurs que les opérateurs) à travers les aérosols qui pourraient être émis au cours du cycle de vie du matériau. L’une des approches possibles de réduction de risque serait la prévention de l’émission qui consisterait en une conception réfléchie du matériau avec un compromis performance/sûreté. La thèse présentée ici suit cette approche. Il s’agit de comprendre le phénomène et les mécanismes d’émission des nanomatériaux manufacturés à l’aide d’outils théoriques et expérimentaux. Le dispositif expérimental développé au cours de cette étude vise (i) à reproduire à l’échelle laboratoire des activités en conditions réelles, (ii) à identifier les mécanismes d’émission, et (iii) à mener simultanément des analyses qualitatives et quantitatives* des nanomatériaux manufacturés émis. Pour la sollicitation mécanique, le procédé d’abrasion a été choisi ; quant au vieillissement environnemental, le choix s’est porté sur un procédé d’exposition accélérée aux rayons d’UV en présence d’humidité et de chaleur. Les résultats suggèrent que les entités microscopiques présentes à la surface d’un matériau (appelées aspérités ou rugosités) subissent globalement 4 types de mécanismes d’enlèvement pendant l’abrasion, suivant la variation de 18 paramètres (liés au matériau et au procédé). Ces mécanismes déterminent la forme, la taille et le nombre de particules de l’aérosol émis. De plus, dans le cas des échantillons testés dans les conditions expérimentales données, il a été observé, lors des essais mécaniques seuls, la génération d’aérosols dans lesquels sont retrouvées des nanomatériaux manufacturés liées à leur matrice. Il s’agit de particules nanométriques et micrométriques. Cependant, dans le cas du couplage abrasion/vieillissement environnemental, après un temps donné de détérioration, il est constaté l’émission de nanomatériaux manufacturés libres, en plus des nanomatériaux manufacturés liés à leur matrice. Les résultats expérimentaux relatifs aux sollicitations mécaniques ont été mis en corrélation avec des lois de mécanique classique utilisant des modèles analytiques. Le modèle utilise en partie des relations semi-empiriques ; après ajustement, on observe une très bonne convergence modèle-expérience. Ce modèle a été utilisé pour réaliser une étude de sensibilité sur les 18 paramètres évoqués précédemment, et ce pour une variation de 25% pour chaque paramètre. Ceci permet d'illustrer la capacité du modèle à hiérarchiser l'influence des différents paramètres sur l'émission de particules, pour des conditions données. Ainsi, ce travail a permis de développer un ensemble constitué d’une part d’outils expérimentaux et d’autre part d’un modèle. Si cet ensemble est largement perfectible, il permet toutefois d’ores et déjà d’entamer une conception “nanosafe by design”. / Engineering nanomaterials (ENM) like metal oxide nanoparticles, carbon nanotubes, nanofibers, etc. possess various innovative properties and their industrial use creates new opportunities. However, they also present new risks and uncertainties. There is an ever growing production and use of the products containing these ENM, like nanocomposites or nanocoatings, which result in an increasing number of workers and consumers exposed to ENM upon their emission (in the form of aerosols) from the products containing them. One of the most favored approaches, to minimize this emission, would be a preventive one which would focus on altering the product’s material properties during its design phase itself without compromising with any of its added benefits.This thesis advocates this approach. It attempts to understand the ENM emission phenomenon and its yielding mechanisms on the basis of combined experimental and theoretical approaches. The experimental set-up, developed during this thesis, is equipped with the necessary elements which can (i) seek to reproduce the real life activities on a laboratory scale (ii) identify the emission mechanism (iii) carry out both qualitative as well as quantitative*analysis of the emitted ENM simultaneously. Whilst the mean chosen for applying the mechanical solicitation or stress is an abrasion process, for the environmental weathering, it is an accelerated UV exposure process in the presence of humidity and heat. The results suggest that depending upon 18 material and process properties/parameters, the microscopic entities present on the surface of a product, called asperities, undergo mainly 4 types of removal mechanisms during abrasion. It is these mechanisms that decide the shape, size and the number of the aerosol particles emitted. Moreover, for the given test samples and experimental conditions studied during the thesis, application of the mechanical stresses alone was found to generate the emitted ENM aerosols in which ENM is always embedded inside the product matrix, thus, a representative product element. In such a case, the emitted aerosols comprise of both nanoparticles as well as microparticles. But if the mechanical stresses are coupled with the environmental weathering, then the eventual deterioration of the product, after a certain weathering duration, may lead to the emission of the free ENM aerosols too. All these experimental findings, pertaining to the effect of the mechanical stresses alone, have also been put into the perspective with classical material and mechanics state laws using a predictive analytical model. A close agreement** of the estimated results of this model with the experimentally measured ones has validated its functioning. This model was used to perform a sensitivity analysis on the aforementioned 18 parameters to rank the influence of a25% variation in each of their values on the particle emission for the given conditions.Thus, during the present thesis, both experimental and theoretical approaches have been developed to study the emission. Despite the fact that these approaches are perfectible, they can still be used during product design phase for the product to be “nanosafe by design”.

Parmi les méthodologies d’appréciation du danger ayant connu une forte croissance ces dernières décennies figurent le Control Banding (CB). Selon une estimée du NIOSH (National Institute for Occupational Safety and Health), cette approche qualitative a été développé dans l’industrie pharmaceutique dans un but concret de protéger près de 90% de travailleurs n’ayant pas accès à des services de santé, de sécurité et d’hygiène au travail. Actuellement, cette approche peut être adaptée aux spécificités des nanomatériaux (NMs) pour lesquelles peu de connaissances scientifiques sont disponibles sur les risques potentiels pour la santé et pour la sécurité des travailleurs. Au cours des dernières années, différentes études ont porté sur l’application de l’approche CB et plusieurs pays ont développé leur propre méthode adaptée aux NMs. Par contre, tous les modèles développés sont basés sur des critères qualitatifs du danger et de l’exposition. Une approche semi-quantitative permettrait de mieux gérer les dangers liés à la manipulation des NMs. L’objectif de ce mémoire était de développer une approche semi-quantitative d’évaluation des dangers sur la base d’une approche de CB. Pour ce faire, une analyse systématique de la littérature scientifique des 20 dernières années sur l’approche de CB a été effectué. Les bases de données Toxline, Pubmed et Google Scholar ont été consultées, couvrant la période de janvier 1996 à novembre 2016, en utilisant 4 mots-clés: control banding, nanomaterials, physicochemical, biological characteristics. Cette recherche a permis d’identifier 982 articles, dont 11% (91) furent retenus en première intention pour au final en garder 6 % (51/982). Il ressort de cette revue que le CB est une approche complémentaire aux méthodes d’évaluation quantitative et que les outils CB développés pour les NMs sont tous de nature qualitative, en réponse à une exposition. Une approche semi-quantitative où il y a maillage entre la caractérisation biologique avec les tests in vitro et la caractérisation physicochimique par des analyses chimiques pour mieux caractériser le niveau de dangérosité des NMs tel que présenté dans le présent mémoire permettrait une utilisation plus judicieuse du CB. Cette approche novatrice du CB dépasse largement l’utilisation que l’on en fait actuellement en hygiène du travail, devrait accroître la confiance dans le jugement des experts en santé au travail, afin d’orienter les travailleurs et la population générale vers une utilisation sécuritaire des NMs. / Among the hazards assessment methodology that has grown exponentially during the last decade, mention Control Banding (CB). According to the National Institute for Occupational Safety and Health (NIOSH), this qualitative approach originally developed in the pharmaceutical industry, aims to protect approximately 90% or 2.7 billion workers that do not have access to occupational safety, health, and hygiene. Currently, this approach can be adapted to the specificities of nanomaterials (NMs), considering the significant lack of scientific knowledge about their potential health and safety risks to workers. In recent years, several CB models have been developed, and many countries have created their own nano-specific CB instruments. However, a semi-quantitative approach would better managing the hazards of handling nanomaterials in the workplace. This thesis aimed to perform a systematic literature review over the past 20 years about the CB approach and then to suggest a semi-quantitative hazard assessment. The official Web pages of the databases Toxline, Pubmed and Google Scholar were used, covering the literature from January 1996 to November 2016, with use of the 4 keywords to locate relevant articles: Control Banding, nanomaterials, physico-chemical, biological characteristics. These searches yielded a total of 982 articles, 11% (91) were retained to eventually retain 6% (51/982). This review shows that the CB approach is an interesting and complementary methodology to quantitative evaluation methods and the CB tools developed for NMs are all qualitative in nature, in response to an exposure and adapted to different work environments. It is possible to make better use by proposing a semi-quantitative approach based on physicochemical and toxicity parameters of NMs to better characterize their degree of dangerousness. We propose here an original methodology proposing the interaction of in vitro tests and chemical analyzes. This innovative Control Banding approach should increase confidence in the judgment of experts and industry, as well as to guide both exposed workers and the uses of NMs in this industry.

<div>In this work, we investigate the trade-off between scalability and reliability for next generation logic-transistors i.e. Gate-All-Around (GAA)-FET, Multi-Bridge-Channel (MBC)-FET. First, we analyze the electronic properties (i.e. bandgap and</div><div>quantum conductance) of ultra-thin silicon (Si) channel i.e. nano-wire and nano-sheet based on first principle simulation. In addition, we study the influence of interface</div><div>states (or dangling bonds) at Si-SiO₂ interface. Second, we investigate the impact of bandgap change and interface states on GAA-FETs and MBC-FETs characteristics by</div><div>employing Non-equilibrium Green's Function based device simulation. In addition to that, we calculate the activation energy of Si-H bond dissociation at Si-SiO₂ interface for different Si nano-wire/sheet thickness and different oxide electric-field. Utilizing these thickness dependent activation energies for corresponding oxide electric-field, in conjunction with reaction-diffusion model, we compute the characteristics shift and analyze the negative bias temperature instability in GAA-FET and MBC-FET. Based on our analysis, we estimate the operational voltage of these transistors for a life-time of 10 years and the ON current of the device at iso-OFF-current condition. For example, for channel length of 5 nm and thickness < 5 nm the safe operating voltage needs to be < 0.55V. Furthermore, our analysis suggests that the benefit of Si thickness scaling can potentially be suppressed for obtaining a desired life-time of GAA-FET and MBC-FET.</div>