Rozprawy doktorskie na temat „Polycrystalline Oxides - Grain Boundaries”

Polycrystalline materials are widely used for industrial applications. These materials are highly anisotropic with different responses under different loading conditions. This dissertation uses a crystal plasticity scheme in the finite element framework (CPFEM) to study deformation mechanisms in alumina, aluminium and stainless steel – all polycrystalline. Four research cases in this dissertation have been presented in the form of manuscripts for publication. When possible, modelling predictions have been compared against various experimental techniques such as Diffraction Contrast Tomography (DCT), Neutron Diffraction (ND) and Electron Back Scatter Diffraction (EBSD). After an introduction (Chapter 1) and a literature review (Chapter 2) on plastic deformation and modelling techniques, the methodology and results are presented and discussed (Chapters 3 and 4). Measurements of elastic strains for individual grain families (ND) and local rotations (DCT and EBSD) are compared against corresponding predictions by the model following different loading modes. Each study reveals different degrees of agreement between predictions and measurements. The individual conclusions to each study are presented in Chapter 4. Some overall conclusions and suggestions for further work are presented in Chapter 5.

Cette these presente une etude de realisation et de caracterisation de jonctions josephson fabriquees a partir de joints de grains artificiels induits dans le film d'ybco. Deux procedes differents ont ete etudies: la fabrication du joint de grains par bi-epitaxie et le depot d'une couche supraconductrice sur substrat bi-cristallin. Le but du travail a ete de developper un procede de fabrication reproductible et d'etudier les proprietes des dispositifs obtenus. Les couches minces ont ete fabriquees par ablation laser pulse. Les dispositifs ont ete obtenus en gravant des lignes de differentes largeurs traversant le joint. Pour les echantillons realises par bi-epitaxie nous avons obtenus a travers un empilement de couches tampons adapte, le joint de grains dans l'ybco sur substrat de saphir ainsi que sur srtio3. Les mesures electriques ont mis en evidence que, pour ce type de joint, le courant josephson est trop faible et que la distribution de courant dans la jonction est inhomogene. Les limitations principales de cette technique sont liees aux contraintes imposes par l'angle de desorientation et par les defauts de fabrication. Pour les jonctions fabriquees sur bi-cristaux, les mesures en champ magnetique ont montre qu'un controle soigne de l'etat de la surface est necessaire pour avoir une barriere homogene. Ce resultat permet le controle de la jonction en regime flux flow. Les resultats preliminaires obtenus sur les transistors a flux de vortex josephson ont mis en evidence que ce type de dispositifs peut etre comme element amplificateur dans un circuit electronique supraconducteur

碩士
國立臺灣科技大學
材料科學與工程系
102
Strontium titanate (SrTiO3), has been reported as the candidate of solid-oxide-fuel-cell anode materials to substitute the conventional materials of Ni-doped yttria-stabilized zirconia (YSZ) cermets because of its high chemical and thermal stability. However, the ionic conductivity of SrTiO3 is low comparing to YSZ. In general, space charge of grain boundaries (GBs) trapped oxygen ion to result low ionic conductivity. Based on previous studies, there is no evidence of space charge layers in low energy coincidence-site lattice ?? GBs which do not impede the transport of charge. So far, the reasons of low ?? GBs are abnormal grain growth (losing of low energy GBs) and difficult to orientate because ceramic is too brittle. This study attempts to increase the population of ?? GBs in polycrystalline SrTiO3 for high ionic conductivities. The strategy is to form more (111) faces (?? GB plane) on the surface starting powder by chosen suitable precursor additives. Four types of SrTiO3 powders have been synthesized using spray pyrolysis with strontium nitrate, titanium isopropoxide and additives of nitric acid (HNO3) and the mixtures of HNO3 and hydrogen peroxide (H2O2) with different concentrations. The crystalline structures of SrTiO3 particles were characterized by X-ray diffractometer and Raman spectra. The morphology and size of SrTiO3 particles were observed by using scanning electron microscope (SEM) and transmission electron microscope. And, the microstructures of sintered SrTiO3 bulks were observed by using SEM. The GB orientations were characterized by electron back-scattered diffraction (EBSD). The conductivities were measured by electrochemical impedance spectroscopy and DC method. The microstructural results suggest that the SrTiO3 particles prepared from the additive mixture of HNO3 and H2O2 have a rough surface which contains more (111) surfaces than that of the SrTiO3 particles prepared from HNO3 only. In addition, EBSD and DC measurements show that the SrTiO3 from HNO3 and H2O2 (highest population of ?? GBs) exhibit highest conductivity, which supports our microstructural observations.

Polycrystalline materials are widely used in large area electronic devices such as flat panel x-ray image detectors, and solar cells due to their suitability to deposit over large area at low cost. The performance of polycrystalline-based flat panel detectors are showing encouraging results (good sensitivity, good resolution and acceptable dark current) and give possibility to replace existing x-ray film/screen cassette. Therefore large area polycrystalline based flat panel detectors have opened new clinical possibilities and the polycrystalline solar cells give the opportunity of manufacturing low cost photovoltaic cells. Consequently, active research has been carried out to find out suitable polycrystalline materials (e.g. HgI2, CdTe, CdZnTe, PbI2, PbO etc) for various large area applications. However a polycrystalline material is composed of micro crystallites joined together by grain boundaries (complex structure, consisting of a few atomic layers of disordered atoms) which posses trap centers for charge carriers. Therefore, grain boundaries can trap a large amount of charges during detector operation. A potential barrier for drifting carriers may exist at the grain boundary, which controls the carrier mobility. Moreover, the performance of these polycrystalline detectors are affected due to the polarization phenomena (any change in the performance of the detector after the detector biasing) under applied bias. Therefore, in this research work, an analytical model is developed to study the electrical properties (electric field and potential distributions, potential barrier height, and polarization phenomenon) of polycrystalline materials at different doping levels for detector and solar cell applications by considering an arbitrary amount of grain boundary charge and a finite width of grain boundary region. The general grain boundary model is also applicable to highly doped polycrystalline materials. The electric field and potential distributions are obtained by solving the Poisson’s equation in both depleted grains and grain boundary regions. The electric field and potential distributions across the detector are analyzed under various doping, trapping and applied biases. The electric field collapses, i.e., a nearly zero average electric field region exists in some part of the biased detector at high trapped charge densities at the grain boundaries. The model explains the conditions of existence of a zero average field region, i.e., it explains the polarization mechanisms in polycrystalline materials. The potential barrier at the grain boundary exists if the electric field changes its sign at the opposite side of the grain boundary. The potential barrier does not exist in all grain boundaries in the low doped polycrystalline detector and it never exists in intrinsic polycrystalline detectors under applied bias condition provided there is no charge trapping in the grain.

The successful exfoliation of graphene in 2004 ushered in the era of 2D van der Waals materials, paving the way for a wide variety of applications in the field of electronics, optoelectronics, sensors, catalysis, flexible and wearable electronics. Chemical vapour deposition (CVD) is a low-cost, scalable technique which allows the direct and controllable synthesis of large-area uniform films of 2D materials for wafer-scale technologies. A major drawback of this technique lies in the polycrystalline nature of the films due to the inevitable presence of lattice point defects and extended line defects such as grain boundaries (GBs) which is a serious detriment to electronic transport. Recent improvements in CVD growth have shown that it is possible to tailor the growth conditions specifically in order to obtain high quality grains by grain boundary engineering. This thesis work is focused mainly on the intrinsic electrical properties of GBs in polycrystalline 2D material films and their role in hindering the device performance of 2D field effect transistors (FETs). In the first part of the thesis, we describe the use of a symbiotic two-pronged approach of time-averaged conductance and low frequency noise measurements to establish the extent to which GBs enhance carrier localization in transition metal dichalcogenide (TMDC) systems which manifests itself not only in the reduction of the localization length by 30% − 70% in the GBs as compared to the single crystalline region but also leads to an overall noise enhancement factor of nearly five orders of magnitude. In doing so, our work also serves to extend the range of application of the well-established McWhorter's noise model to localized systems by explaining the origin of the uncharacteristic exponential dependence of low frequency noise with temperature. In the second half of the thesis, we describe how our study of time-dependent universal conductance fluctuations (UCF) via low frequency noise measurements at ultra-low temperatures point towards the spontaneous breaking of time reversal symmetry across graphene grain boundaries. The magnetic ordering is found to be gate-tunable and is attributed to the formation of localized magnetic moments at the octagon-pentagon defects of the disordered GB region, which is further enhanced by the inbuilt lattice strain leading to the dephasing of spins.

碩士
長庚大學
光電工程研究所
98
Polycrystalline silicon thin film transistors (poly-Si TFTs) are widely used in active matrix liquid crystal displays (AMLCDs). Grain boundaries will cause the variation of threshold voltage in poly-Si TFTs. This thesis focuses on the effect of the locations of grain boundaries on the threshold voltage. New analytical models were developed. Base on the solution by two dimensional Poisson’s equation, lateral surface potential with a single grain boundary was obtain by assuming the grain boundary as a region with trapped charges. La-place transform was calculated to obtain the surface potential with multiple grain boundaries in poly-Si TFTs.

The work presented in this doctoral thesis employs colloidal suspensions to explore key open problems in condensed matter physics. Colloidal suspensions, along with gels, polymers, emulsions and liquid crystals belong to a family of materials that are collectively labelled as soft matter. Compositionally, colloidal suspensions consist of particles whose size ranges from a few nanometers to a few microns, dispersed in a solvent. A hallmark feature of these systems is that they exhibit Brownian motion, which makes them suitable for investigating statistical mechanical phenomena. Over the last fifteen years or so, colloids have been used extensively as model systems to shed light on a wide array of such phenomena typically observed in atomic systems. The chief reason why colloids are good mimics of atomic systems is their large size and slow dynamics. Unlike atomic systems, the dynamics of colloids can be probed in real time with single-particle resolution, which allows one to establish the link between macroscopic behavior and the microscopic processes that give rise to it. Yet another important feature is that colloidal systems exhibit various phases of matter such as crystals, liquids and glasses, which makes them versatile model systems that can probe a broad class of condensed matter physics problems. The work described in this thesis takes advantage of these lucrative features of colloidal suspensions to gain deeper insights into the physics of glass formation as well as shear-induced anisotropic grain growth in polycrystalline materials. The thesis is organized into two preliminary chapters, four work chapters and a concluding chapter, as follows. Chapter 1 provides an introduction to colloidal suspensions and reviews the chief theo-retical concepts regarding glass formation and grain boundary dynamics that form an integral part of subsequent chapters. Chapter 2 describes the experimental methods used for performing the work presented in the thesis and consists of two parts. The first part describes the protocols followed for synthesizing the size-tunable poly (N-isoprolypacrylamide) (PNIPAm) particles used in our study of shear-induced grain growth. The second part describes the instrumentation and techniques, such as holographic optical tweezers, confocal microscopy, rheology and Bragg diffraction microscopy, used to perform the measurements described in the thesis. Chapter 3 deals with our work on the dynamical facilitation (DF) theory of glass forma-tion. Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. While obser-vations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the DF theory has thus far lacked experimental support. Further, for glass transitions induced by randomly freezing a subset of particles in the liquid phase, theory and simulations support the existence of an underlying thermodynamic phase transi-tion, whereas the DF theory remains unexplored. In Chapter 3, using video microscopy and holographic optical tweezers, we show that dynamical facilitation in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion, which is consid-ered to be consistent with thermodynamic theories, can also emerge naturally within the framework of facilitation. These findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches. In Chapter 4, we further explore the question of whether glass formation is an intrinsi-cally thermodynamic or dynamic phenomenon. A major obstacle in answering this question lies in determining whether relaxation close to the glass transition is dominated by activated hopping, as espoused by various thermodynamic theories, or by the correlated motion of localized excitations, as proposed in the Dynamical Facilitation (DF) approach. In Chapter 4, we surmount this central challenge by developing a scheme based on real space micro-scopic analysis of particle dynamics and applying it to ascertain the relative importance of hopping and facilitation in a colloidal glass-former. By analysing the spatial organization of excitations within cooperatively rearranging regions (CRRs) and examining their parti-tioning into shell-like and core-like regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a hopping-dominated one close to the glass transition. Remarkably, this crossover coincides with the change in morphology of CRRs predicted by the Random First-Order Transition theory (RFOT), a prominent ther-modynamic framework. Further, we analyse the variation of the concentration of excitations with distance from an amorphous wall and find that the evolution of these concentration profiles with area fraction is consistent with the presence of a crossover in the relaxation mechanism. By identifying regimes dominated by distinct dynamical processes, our study offers microscopic insights into the nature of structural relaxation close to the glass transi-tion. In Chapter 5, we extend our investigation of the glass transition to systems composed of anisotropic particles. The primary motivation for this is to bridge a long-standing di-vide between theories and simulations on one hand, and experiments on molecular liquids on the other. In particular, theories and simulations predominantly focus on simple glass-formers composed of spherical particles interacting via isotropic interactions. Indeed, even the prominent theory of Dynamical Facilitation has not even been formulated to account for anisotropic shapes or interactions. On the other hand, an overwhelming majority of liquids possess considerable anisotropy, both in particle shape as well as interactions. In Chapter 5, we mitigate this situation by developing the DF theory further and applying it to systems with orientational degrees of freedom as well as anisotropic attractive interactions. By analyzing data from experiments on colloidal ellipsoids, we show that facilitation plays a pivotal role in translational as well as orientational relaxation. Further, we demonstrate that the introduction of attractive interactions leads to spatial decoupling of translational and rotational facilitation, which subsequently results in the decoupling of dynamical het-erogeneities. Most strikingly, the DF theory can predict the existence of reentrant glass transitions based on the statistics of localized dynamical events, called excitations, whose duration is substantially smaller than the structural relaxation time. Our findings pave the way for systematically testing the DF approach in complex glass-formers and also establish the significance of facilitation in governing structural relaxation in supercooled liquids. In Chapter 6, we turn our attention away from the glass transition and address the problem of grain growth in sheared polycrystalline materials. The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. While computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the disparate length and time scales involved. In Chapter 6, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the anisotropy in mobility emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. Finally, in Chapter 7, we present our conclusions and discuss possible future directions.

The work presented in this doctoral thesis employs colloidal suspensions to explore key open problems in condensed matter physics. Colloidal suspensions, along with gels, polymers, emulsions and liquid crystals belong to a family of materials that are collectively labelled as soft matter. Compositionally, colloidal suspensions consist of particles whose size ranges from a few nanometers to a few microns, dispersed in a solvent. A hallmark feature of these systems is that they exhibit Brownian motion, which makes them suitable for investigating statistical mechanical phenomena. Over the last fifteen years or so, colloids have been used extensively as model systems to shed light on a wide array of such phenomena typically observed in atomic systems. The chief reason why colloids are good mimics of atomic systems is their large size and slow dynamics. Unlike atomic systems, the dynamics of colloids can be probed in real time with single-particle resolution, which allows one to establish the link between macroscopic behavior and the microscopic processes that give rise to it. Yet another important feature is that colloidal systems exhibit various phases of matter such as crystals, liquids and glasses, which makes them versatile model systems that can probe a broad class of condensed matter physics problems. The work described in this thesis takes advantage of these lucrative features of colloidal suspensions to gain deeper insights into the physics of glass formation as well as shear-induced anisotropic grain growth in polycrystalline materials. The thesis is organized into two preliminary chapters, four work chapters and a concluding chapter, as follows. Chapter 1 provides an introduction to colloidal suspensions and reviews the chief theo-retical concepts regarding glass formation and grain boundary dynamics that form an integral part of subsequent chapters. Chapter 2 describes the experimental methods used for performing the work presented in the thesis and consists of two parts. The first part describes the protocols followed for synthesizing the size-tunable poly (N-isoprolypacrylamide) (PNIPAm) particles used in our study of shear-induced grain growth. The second part describes the instrumentation and techniques, such as holographic optical tweezers, confocal microscopy, rheology and Bragg diffraction microscopy, used to perform the measurements described in the thesis. Chapter 3 deals with our work on the dynamical facilitation (DF) theory of glass forma-tion. Despite decades of research, it remains to be established whether the transformation of a liquid into a glass is fundamentally thermodynamic or dynamic in origin. While obser-vations of growing length scales are consistent with thermodynamic perspectives, the purely dynamic approach of the DF theory has thus far lacked experimental support. Further, for glass transitions induced by randomly freezing a subset of particles in the liquid phase, theory and simulations support the existence of an underlying thermodynamic phase transi-tion, whereas the DF theory remains unexplored. In Chapter 3, using video microscopy and holographic optical tweezers, we show that dynamical facilitation in a colloidal glass-forming liquid grows with density as well as the fraction of pinned particles. In addition, we observe that heterogeneous dynamics in the form of string-like cooperative motion, which is consid-ered to be consistent with thermodynamic theories, can also emerge naturally within the framework of facilitation. These findings suggest that a deeper understanding of the glass transition necessitates an amalgamation of existing theoretical approaches. In Chapter 4, we further explore the question of whether glass formation is an intrinsi-cally thermodynamic or dynamic phenomenon. A major obstacle in answering this question lies in determining whether relaxation close to the glass transition is dominated by activated hopping, as espoused by various thermodynamic theories, or by the correlated motion of localized excitations, as proposed in the Dynamical Facilitation (DF) approach. In Chapter 4, we surmount this central challenge by developing a scheme based on real space micro-scopic analysis of particle dynamics and applying it to ascertain the relative importance of hopping and facilitation in a colloidal glass-former. By analysing the spatial organization of excitations within cooperatively rearranging regions (CRRs) and examining their parti-tioning into shell-like and core-like regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a hopping-dominated one close to the glass transition. Remarkably, this crossover coincides with the change in morphology of CRRs predicted by the Random First-Order Transition theory (RFOT), a prominent ther-modynamic framework. Further, we analyse the variation of the concentration of excitations with distance from an amorphous wall and find that the evolution of these concentration profiles with area fraction is consistent with the presence of a crossover in the relaxation mechanism. By identifying regimes dominated by distinct dynamical processes, our study offers microscopic insights into the nature of structural relaxation close to the glass transi-tion. In Chapter 5, we extend our investigation of the glass transition to systems composed of anisotropic particles. The primary motivation for this is to bridge a long-standing di-vide between theories and simulations on one hand, and experiments on molecular liquids on the other. In particular, theories and simulations predominantly focus on simple glass-formers composed of spherical particles interacting via isotropic interactions. Indeed, even the prominent theory of Dynamical Facilitation has not even been formulated to account for anisotropic shapes or interactions. On the other hand, an overwhelming majority of liquids possess considerable anisotropy, both in particle shape as well as interactions. In Chapter 5, we mitigate this situation by developing the DF theory further and applying it to systems with orientational degrees of freedom as well as anisotropic attractive interactions. By analyzing data from experiments on colloidal ellipsoids, we show that facilitation plays a pivotal role in translational as well as orientational relaxation. Further, we demonstrate that the introduction of attractive interactions leads to spatial decoupling of translational and rotational facilitation, which subsequently results in the decoupling of dynamical het-erogeneities. Most strikingly, the DF theory can predict the existence of reentrant glass transitions based on the statistics of localized dynamical events, called excitations, whose duration is substantially smaller than the structural relaxation time. Our findings pave the way for systematically testing the DF approach in complex glass-formers and also establish the significance of facilitation in governing structural relaxation in supercooled liquids. In Chapter 6, we turn our attention away from the glass transition and address the problem of grain growth in sheared polycrystalline materials. The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. While computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the disparate length and time scales involved. In Chapter 6, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the anisotropy in mobility emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. Finally, in Chapter 7, we present our conclusions and discuss possible future directions.

The experimental discovery of graphene in 2004 has opened up a new research field in the direction of atomically thin two-dimensional layered materials for exploration of many fundamental research problems and technological applications. The charge carriers in graphene are massless Dirac fermions due to which they exhibit absence of localization, thereby giving rise to huge intrinsic mobilities and ballistic transport even at room temperatures. But it was observed that the extrinsic disorder and intrinsic structural disorder can significantly influence the transport in graphene films. This thesis focuses on three different aspects of graphene -disorder, magnetism and proximity-induced superconductivity. We have reported conductance fluctuations-based transport studies to investigate these aspects as they provide more detailed information than what can be obtained from the standard transport measurements. Even though these conductivity fluctuations pose a serious bottleneck for various applications, they can also yield useful insights into the various scattering mechanisms and the symmetry properties of graphene. In the first half of the thesis, we describe the measurement of low frequency 1/f noise in large area polycrystalline graphene films to understand the role of grain boundaries in charge carrier transmission in graphene. TEM studies on the low and high angled GBs formed in these graphene samples showed that they form distinct disordered regions of varying widths depending on the tilt angle of the GBs. At low temperatures, the 1/f noise measurements indicated spontaneous breaking of time reversal symmetry across graphene grain boundaries which suggests the magnetic nature of these grain boundaries. In the second half of the thesis, we will concentrate on the universal conductance fluctuations (UCF) in graphene which is the manifestation of quantum interference phenomena at low temperatures. We find that the absolute magnitude of the UCF is directly related to various symmetry-breaking disorder present in graphene. We also discuss how the UCF can be used to study the nature of proximity-induced superconducting correlations in graphene. In the end, we have proposed new device schemes for the integration of ferromagnetic and superconducting materials with graphene.

The experimental discovery of graphene in 2004 has opened up a new research field in the direction of atomically thin two-dimensional layered materials for exploration of many fundamental research problems and technological applications. The charge carriers in graphene are massless Dirac fermions due to which they exhibit absence of localization, thereby giving rise to huge intrinsic mobilities and ballistic transport even at room temperatures. But it was observed that the extrinsic disorder and intrinsic structural disorder can significantly influence the transport in graphene films. This thesis focuses on three different aspects of graphene -disorder, magnetism and proximity-induced superconductivity. We have reported conductance fluctuations-based transport studies to investigate these aspects as they provide more detailed information than what can be obtained from the standard transport measurements. Even though these conductivity fluctuations pose a serious bottleneck for various applications, they can also yield useful insights into the various scattering mechanisms and the symmetry properties of graphene. In the first half of the thesis, we describe the measurement of low frequency 1/f noise in large area polycrystalline graphene films to understand the role of grain boundaries in charge carrier transmission in graphene. TEM studies on the low and high angled GBs formed in these graphene samples showed that they form distinct disordered regions of varying widths depending on the tilt angle of the GBs. At low temperatures, the 1/f noise measurements indicated spontaneous breaking of time reversal symmetry across graphene grain boundaries which suggests the magnetic nature of these grain boundaries. In the second half of the thesis, we will concentrate on the universal conductance fluctuations (UCF) in graphene which is the manifestation of quantum interference phenomena at low temperatures. We find that the absolute magnitude of the UCF is directly related to various symmetry-breaking disorder present in graphene. We also discuss how the UCF can be used to study the nature of proximity-induced superconducting correlations in graphene. In the end, we have proposed new device schemes for the integration of ferromagnetic and superconducting materials with graphene.

Les travaux de recherche menés dans cette thèse de doctorat se sont focalisés sur la compréhension des interactions graphène-plasma dans le cas de l’exposition de graphène polycristallin à un plasma d’argon pouvant contenant du diborane (B2H6). Une attention particulière est portée sur la cinétique de génération de dommage dans un plasma d’argon pur. Ainsi dans le cas d’un plasma continu, l’absence de seuil en énergie pour la génération de dommage due à un bombardement ionique est mis en évidence. Ceci ne peut s’expliquer que par une gravure à deux étapes, facilitée par la densité ionique élevée caractéristique des plasmas inductifs opérés en mode H. La caractérisation Raman des échantillons exposés au plasma montre une large distribution sur la petite zone sondée. Afin de relier ces fluctuations à l’état initial du graphène, l’imagerie Raman (RIMA) est adaptée dans le but d’extraire des données quantitatives sur l’état du graphène et utilisée pour le reste des travaux. Par la suite, l’étude temporelle des plasmas pulsés en puissance permet de trouver des conditions opératoires avec une fluence ionique drastiquement diminuée. Les traitements subséquents combinés aux analyses RIMA ont permis de suivre l’évolution de l’état du graphène et de distinguer l’état des joints du graphène des domaines de croissance. Ainsi, pour la première fois, l’autoréparation des joints de grains dans un matériau 2D est mis en évidence expérimentalement. Cet effet, théorisé dans les matériaux 3D mais difficilement observé expérimentalement, était effectivement prédis dans le cas du graphène. De plus, un contrôle fin des conditions opératoires du plasma pulsé d’argon a permis d’extraire des paramètres plasmas dans lesquels les métastables d’argons puis les photons VUV émis par les états résonants de l’argon sont les principaux vecteurs d’énergie. Suivant la même méthodologie que précédemment, ces traitements ont mis en lumière les rôles respectifs des ions, des métastables et des photons VUV dans la transmission d’énergie du graphène. Enfin, l’introduction de 5% de diborane a pour conséquence une modification radicale des paramètres physique du plasma. L’exposition de graphène à ce graphène à ce plasma démontre l’intérêt de cette technique pour l’incorporation élevé de bore tout en minimisant la génération de dommages
The research realized in this PhD thesis focuses on the understanding of plasma-graphene interactions during exposure of polycrystalline graphene films to a low-pressure argon RF plasma containing diborane (B2H6). A particular attention is devoted to the kinetics driving the damage formation dynamics. In the case of a continuous, argon plasma, the absence of energy threshold for the production of ion-induced damage is demonstrated. This is explained by two-step etching, facilitated by the high number density of charged species in the H-mode of RF plasmas. Raman characterization of plasma-treated graphene films shows a wide distribution over the small area surveyed. In order to link these fluctuations to the initial state of graphene, Raman imaging (RIMA) is adapted to extract quantitative data on the state of graphene before and after plasma treatment. Subsequently, the temporal study of argon RF plasmas in the pulsed regime makes it possible to find operating conditions with a drastically reduced fluence of charged species compared to the continuous regime; in combination with RIMA studies, this allows temporally- and spatially-resolved investigations of plasma-graphene interactions. For the first time, a preferential self-healing of ion-irradiation damage at grain boundaries of graphene films is experimentally demonstrated. Moreover, by using several electrical and optical diagnostics of the argon plasma in the pulsed regime, it is possible to determine operating conditions in which either the ions, the metastables or the VUV photons emitted by the resonant states become the main energy vectors. From these experiments, the respective roles of each of these species in the physics of plasma-graphene interactions could be highlighted. Finally, the introduction of 5% of diborane into the argon plasma induces a radical modification of the physicochemical properties of the plasma. Exposure of graphene films to this highly reactive plasma reveals high boron incorporation with minimal ion and hydrogen damage.